Table of Contents · Takasago Fine Chemicals Division was established about 20 years ago when...

Table of Contents Biographical Sketch ......................................................................................................1 Chiral Ligands & their Complexes, Newly Available on a Commercial Scale................3

SEGPHOS & BINAP Family of Ligands and their Complexes ...............................4 Application to Catalytic Asymmetric Syntheses .....................................................7 Conclusion ...........................................................................................................26 Future Aspects.....................................................................................................26

Products Referenced in the Article ..............................................................................30 New SEGPHOS Catalyst and Ligand Kits...................................................................52 New BINAP Catalyst and Ligand Kits..........................................................................53 New Kits Introduced Since Catalog 21........................................................................55 New Products Introduced Since Catalog 21................................................................57 Congratulations to the following 2007 recipients of awards sponsored by Strem:

Robert A. Angelici American Chemical Society Award

for Distinguished Service in the Advancement of Inorganic Chemistry Deryn Fogg

Canadian Society for Chemistry Award for Pure or Applied Inorganic Chemistry

©Copyright 2007 by STREM CHEMICALS, INC. 7 Mulliken Way Newburyport, MA 01950-4098 Tel.: (978) 499-1600 Fax: (978) 465-3104 (Toll-free numbers below US & Canada only) Tel.: (800) 647-8736 Fax: (800) 517-8736 Email: [email protected]

STREM CHEMICALS, INC. 15, rue de l’Atome Zone Industrielle 67800 BISCHHEIM (France) Tel.: (33) 03 88 62 52 60 Fax: (33) 03 88 62 26 81 Email: [email protected]

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STREM CHEMICALS UK 48 High Street Orwell, Royston England SG8 5QN Tel.: 01223 207430 Fax: 01223 208138 Email: [email protected]

The Strem Chemiker Vol. XXIII, No. 1 May, 2007

www.strem.com

1

Chiral Ligands & their Complexes, Newly Available on a Commercial Scale

Takasago Fine Chemicals Division Dr. Takao Saito

Born in Ibaraki, Japan, in 1960. He joined Takasago

International Corporation in 1985 and received his Ph.D. from

Osaka University under the supervision of Professor Shunichi

Murahashi in 1996. He is the inventor of SEGPHOS ligands and

has also developed unique processes for pharmaceutical

intermediates. He was promoted to be Vice President, General

Manager and Sales Manager at the Fine Chemicals Division,

Takasago International Corporation in 2006.

R&D Members Takasago Fine Chemical Laboratory consists of 24 chemists. They are developing new chiral

technologies and their applications to pharmaceutical intermediates and functional materials.

The head of the laboratory is Dr. Noboru Sayo (the center of the front row in the picture

below), who joined Takasago in 1984 after obtaining his Ph. D. from Tokyo Institute of Technology

under the supervision of Professor Takeshi Nakai and is now the executive director at the

laboratory.

Catalysts Marketing Team JAPAN: Shigeru Mitsuhashi (Director at Planning Department of Fine Chemicals Division)

Yuri Yoshimi (Planning Department of Fine Chemicals Division)

Motonobu Takenaka (Senior Account Executive at Sales Department of Fine Chemicals Division)

USA: Yutaka Okamura (Director at Fine Chemicals Division in Takasago International Co. USA)

2

About Takasago Fine Chemicals Takasago was established in 1920 as a perfumery company. Our synthetic technology traces

back to manufacture of Vanillin and Heliotropine in 1927. Ever since, many aroma chemicals have

been produced. Our chiral technologies commenced with ℓ-Menthol synthesis by catalytic

asymmetric isomerization using BINAP ligand, which was developed in collaboration with Professor

Ryoji Noyori, who was awarded the Nobel Prize for Chemistry in 2001, and who is a Takasago

board member. The technology expanded to asymmetric hydrogenation to produce various kinds of

chiral compounds, such as flavors, fragrances, and agrochemical and pharmaceutical ingredients.

Our current chiral output from the technology is approximately 3,000 tons annually.

Takasago Fine Chemicals Division was established about 20 years ago when Takasago

developed the catalytic asymmetric synthesis technology using BINAP ligands. In Takasago, we

refer to BINAP as the first generation ligand. Over time Takasago Fine Chemicals has discovered

several generations of novel chiral ligands, as well as many catalysts. Although we still think BINAP

is the most famous chiral ligand in the world, Takasago is now focusing on the next generation

ligand, SEGPHOS.

Though we had used the technology within Takasago only, now chiral ligands and their

complexes have become commercially available through Strem Chemicals, Inc.

About the Cover of this Strem Chemiker When you enter the main entrance of Strem Chemicals in Newburyport, you immediately see a

large wood block print entitled “Sunset Snow” that presents a peaceful, tranquil influence. The

artist is Eimei Machida, an artist/scientist who has a Ph.D. in Chemistry but is self-taught as an

artist. His interest in art began in 1980 and in the past several years he has won several prizes at

exhibits in Japan. He has also begun to exhibit in the USA and Europe.

Since this edition of The Strem Chemiker introduces Strem’s cooperation with Takasago, we

have added to the cover, the structure of Segphos, which Takasago relates to a seagull. We think

the seagull fits well in the skies over Sunset Hill.

3

TAKASAGO’s Ligands and Complexes, their Potential

By Dr. Wataru Kuriyama, Dr. Noboru Sayo, Dr. Takao Saito

1. SEGPHOS & BINAP Family of Ligands and their Complexes

1-1. Introduction

1-2. Ligands

1-3. Complexes

1-4. Design Concept of SEGPHOS

2. Application to Catalytic Asymmetric Syntheses

2-1. Background

2-2. Asymmetric Hydrogenation

2-2-1. Historical Overview

2-2-2. Functionalized Ketones

2-2-3. Simple Ketones

2-2-4. Olefins

2-2-5. Enamino Esters and Reductive Amination to β-Amino Acid

Derivatives

2-3. Other Reactions Using SEGPHOS Type Ligands

2-3-1. Aldol-Type Reaction

2-3-2. Alkenylation and Arylation

2-3-3. Mannich Reaction

2-3-4. Fluorination

2-3-5. Michael Addition

2-3-6. Hydrosilylation

2-3-7. Reductive Aldol Reaction

2-3-8. Aryl Amination

2-3-9. [2 + 2+ 2] Cycloaddition

2-3-10. [3 + 2] Cycloaddition

2-3-11. 1,3-Dipolar Cycloaddition

2-3-12. Diels-Alder Reaction

2-3-13. Ene-Type Reaction

2-3-14. Nucleophilic Addition to π-Allylpalladium Complexes

2-3-15. Aryl Addition Reaction

2-3-16. Cyclopropanation

2-3-17. C-C Bond Cleavage

3. Conclusion

4. Future Aspects

4

1. SEGPHOS & BINAP Family of Ligands and their Complexes 1-1. Introduction

Both enantiomers of SEGPHOS (1), DM-SEGPHOS (2), DTBM-SEGPHOS (3)1, BINAP (4)2, TolBINAP (5)3, XylBINAP (6)4, H8-BINAP (7)5 and their ruthenium complexes - [RuCl(p-cymene)(P^P)]Cl (I)6, [NH2Me2][{RuCl(P^P)}2(μ-Cl)3] (II)7, [Ru(OAc)2(P^P)] (III)8, [RuCl2(P^P)(N^N)] (IV)9 - are Now Commercially Available.

Figure 1 SEGPHOS & BINAP Family of Ligands

Figure 2 Various Types of Ruthenium Precatalysts for Asymmetric Hydrogenation

Takasago Int. Corp. produces these ligands and complexes based on our chiral technology. i) Over 500 ligands and their complexes, and investigations about their applications. ii) Over 20 years experience of industrial production, and laboratory research works. iii) Over 2,000 Mt of annual production with cGMP & ISO certified facilities equipped with

1m3 to 10m3 Hastelloy & Stainless Autoclaves with 400 to 1,280 psi. (http://www.takasago.com)

Now, everyone can access to Takasago’s technologies by using these ligands and complexes.

O

O

O

O

P

P

SEGPHOSes

OMe

SEGPHOS(1)

DM-SEGPHOS(2)

DTBM-SEGPHOS(3)

Ar;

P

P

ArAr

ArAr

BINAPs

P

P

ArAr

ArAr

Ar

Ar

Ar

BINAP(4)

TolBINAP(5)

XylBINAP(6)

H8-BINAP(7)

Ar

Ru

O

PP

OOO NaOAc

RuPP

Cl

RuClRu

Cl

Cl

Cl

Cl-Me2NH.HCl

Ru

Cl

PP

ClN

N

NH2Me2+

+

P^P

N^N

[RuCl(p-cymene)(P^P)]Cl (I)

[RuCl2(P^P)(N^N)] ( IV)

[NH2Me2][{RuCl(P^P)}2(μ-Cl)3] (II)[Ru(OAc)2(P^P)] (III)

Functionalyzed KetonesEnaminesα,β-Unsaturated Carboxylic AcidsAllyl AlcoholsImines etc.

Simple Ketones

For

ForN^N; DiamineP^P; Diphosphine

Ru

P

P

Cl

ClCl Cl

Ru

P

P

Cl -

5

Scheme 1 Examples of Takasago’s Chiral Technologies: Efficient and Unique Catalysts

OMe

O O

NHC(O)Ph

R1 OR2

O O

R1 OR2

NH2 O

NH3 HOAc, H2

R5 OMe

O O

NHAc

Ar R3

O

R5 OMe

OH O

NHAc

OMe

OH O

NHC(O)PhNH

OAc

O

TBSO H

R5 OH

OH

NHC(O)R6

R1 OR2

NH2 O

β-Amino Acids

Direct Reductive Amination Hydrogenation

of Enamino esters

*

Chiral Alcohols

[RuCl2(P^P)(N^N)]

KOtBu, IPA, H2

α-Substituted-β-Hydroxy Esters

(R)-DTBM-SEGPHOS / Ru

(S)-DM-SEGPHOS / Ru

Ceramide 16

8 9

13a 14a

13b 14b

OHO

NEt2

OHOH

NEt2

NO

CO2HO

N

F

N

OH

1,2-Propanediol

(R)-SEGPHOS / Ru

Levofloxacin 19

Menthol Since 1983

AsymmetricIsomerization

l-Menthol 23

17a (R)-18a

Myrcene 2021 22

Ar R3

OH

*

Carbapenem key Intermediate 15

10

11 12

R5 = -(CH2)14CH3

SEGPHOSes / Ru

H2

H2

H2

Dynamic Kinetic Resolution(DKR)

R6 = -(CH2)16CH3

Features of Ligands and Complexes are Outlined Below;

1-2. Ligands

SEGPHOS (1) shows its greatest competence in hydrogenation of α-, β- and γ-functionalized ketones. In most cases, higher catalytic activities and enantioselectivities are achieved by use of SEGPHOS / Ru complexes than by use of BINAP complexes. 1

DM-SEGPHOS (2) has a slightly bulkier pendant group than SEGPHOS, which gives higher enantioselectivity in reductive amination of β-keto esters to β-amino acids.10 Replacing XylBINAP with 2 as ligand in Noyori’s [RuX2(P^P)(N^N)] complex also could increase the enantioselectivity in difficult hydrogenations.11

6

DTBM-SEGPHOS (3) produces an extremely sterically demanding environment around the metal center. In the asymmetric hydrogenation of 13a, the DTBM-SEGPHOS Ru complex provides the highest enantioselectivity as well as dynamic kinetic resolution (DKR) to form a second chiral center. The former is enhanced by the SEGPHOS backbone and the latter is enhanced by the DTBM pendant group (Scheme 1).1 Because of its unique structural features, many complexes of 3 with metals such as gold,12 palladium, 13 and especially copper14 show excellent activity and enantioselectivity in a variety of hydrogenation and C-C bond forming reactions.

BINAP (4)

is the parent compound of axially chiral biaryl ligands. BINAP is still a standard, much used

ligand.

TolBINAP (5) enjoys high solubility in organic solvents. This property solves the problems caused by low

solubility intrinsic to BINAP and its complexes.15 XylBINAP (6) is usually used in the Noyori’s Ru-Diphosphine-Diamine complexes for hydrogenation of simple

ketones. In many cases this ligand gives higher ee values than those with BINAP or TolBINAP.16 H8-BINAP (7)

hydrogenates unsaturated carboxylic acids in higher enantioselectivities than BINAP does.17

1-3. Complexes

[RuCl(p-cymene)(P^P)]Cl (I) is easily prepared and can be applied to the asymmetric hydrogenation of various substrates.

Slightly higher temperature is necessary to dissociate the arene ligand to activate this type of complex. This feature is advantageous when higher reaction temperature gives better results.

[NH2Me2] [{RuCl(P^P)}2(μ-Cl)3] (II) shows catalytic activity even at relatively lower temperature, due to ease of generation of active

species [Ru(OAc)2(P^P)] (III) is frequently used for asymmetric hydrogenation of allyl alcohols,18 and unsaturated carboxylic

acids,17 and for asymmetric reductive amination,10 etc. [RuCl2(P^P)(N^N)] (VI)

is precatalyst, which gives excellent activity and enantioselectivity in the asymmetric

hydrogenation of simple ketones.16

1-4. Design Concept of SEGPHOS

SEGPHOS resulted from an effort at Takasago to optimize the enantioselective hydrogenation of

acetol (17a). First, a detailed survey was made of mechanistic studies of known ruthenium-

catalyzed hydrogenation reactions of functionalized ketones, such as β-keto esters.1 It was

observed that in the asymmetric hydrogenation of acetol there was a tendency of ligands with

narrower dihedral angles to give better ees (Scheme 2).1 This became a driving force for us to

design a ligand with a smaller dihedral angle.

7

Scheme 2 Asymmetric Hydrogenation of Acetol

OHO

BINAP

OHOHRu-Biaryl bisphosphine, H2

*

BIPHEMP MeO-BIPHEP New Ligand

89.0% ee 92.5% ee 96.0% ee more than 98% eeProduct ee

Dihedral Angle19 73.49o 72.07o 68.56o around 65o>

< <<

> >

17a 18a

It was predicted that a ligand with dihedral angle of around 65o would achieve more than 98% ee

values of product. Finally, computational chemistry was used to predict that a ligand with the

structure of SEGPHOS would have the desired smaller dihedral angle.

Figure 3 SEGPHOS Ligand: Named after the Figure of Top View

The SEGPHOS Ruthenium complex A has a narrow dihedral angle (64.99o). 19 Hydrogenation of

acetol resulted in 98.5% ee with S/C = 10,000 (Compare: 89% ee with S/C = 3,000 in the case of

BINAP). The ligand remarkably increases not only enantioselectivity but also catalytic activity.1

2. Applications to Catalytic Asymmetric Syntheses

2-1. Background

Molecular chirality is an important characteristic in the pharmaceutical, agrochemical, flavor and

fragrance sphere, because it affects biological activities and functions of compounds. 20 In 1992 the

FDA (Food and Drug Administration in the U.S.) introduced a guideline for drugs to be composed of

single stereoisomers in consideration of effects on human health. As a result, the importance of

chiral manufacturing technologies that produced single enantiomers (stereoisomers) for the

pharmaceutical industry increased dramatically. 21 Among such technologies, catalytic asymmetric

synthesis has played a significant role because of its atom efficiency and wide application.22 Highly

efficient asymmetric catalysis promotes green sustainable chemistry through waste reduction, rapid

production and energy efficiency.

SEGPHOS-Ru A PPRu

OO OO

8

2-2. Asymmetric Hydrogenation

Asymmetric hydrogenation is one of the leading technologies for catalytic asymmetric

synthesis.23 Chiral ligands developed for such reactions have been critical to success.

2-2-1. Historical Overview

In 1966, Nozaki, Noyori, and Takaya reported the first transition metal complex catalyzed

homogeneous asymmetric reaction.24 At almost the same time, Knowles25 and Horner26

independently discovered that prochiral olefins were asymmetrically hydrogenated by using

Wilkinson’s catalyst modified by chiral mono-phosphine. In 1971 Kagan invented DIOP,27 a ligand

based on a new concept of diphosphine and non-P-chiral compound. The diphosphine concept has

been used for most ligands after DIOP. Optically active L-DOPA had been manufactured by using

P-chiral DIPAMP28, developed by Knowles.

In 1980, Noyori and Takaya introduced atropisomeric chiral triarylphosphines to the ligand design

concept by synthesizing enantiomerically pure BINAP.2 As the BINAP complex, ruthenium has the

ability to hydrogenate various kinds of multiple bonds, though rhodium complexes with various

kinds of ligands have been applied mainly to asymmetric hydrogenation of C-C double bond.

Finally in 1995, Noyori discovered the Ru-Diphosphine and diamine system that can hydrogenate

even simple ketones.29

In industrial applications, it is very fortunate that the metal which best achieves hydrogenation of

various multiple bonds is not rhodium but ruthenium, because rhodium is one of the most expensive

rare metals. Today, the less expensive ruthenium based technology is widely applied to industrial

production.22 In 2001, Professor Ryoji Noyori won the Nobel Prize with Professor William S.

Knowles for their excellent works on chirally catalyzed hydrogenation reactions.30

Since the discovery, BINAP has been used for many types of asymmetric reactions. Success of

the ligand has inspired many chemists to great efforts to attain higher activity and/or selectivity than

those of BINAP by creating new ligands on the basis of various kinds of hypotheses and

concepts.31 Today we can usually achieve optimum performance in every way by choosing from

the large library of ligands and complexes available on a commercial scale.

2-2-2. Functionalized Ketones

The term ‘Functionalized ketone’ means ketones having additional functional groups that help

coordinate to the center metal, i.e. –C(O)OR, -OR, -NR2 etc. Such functional groups play a role like

an anchor to facilitate hydrogenation. Complexes of type of I or II, shown in figure 2, are usually

used for this purpose.

β- & γ- Keto Esters

These materials are hydrogenated to hydroxy esters with promising high ee values and high

catalytic activity.

9

Scheme 3 Hydrogenation of β- & γ- Keto Esters

R OR'

O O

n

n = 1 or 2

OMe

OH O

OEt

OH OCl

(R)-SEGPHOS; 98.5% ee, S/C = 20,000(R)-BINAP; 95.9% ee, S/C = 1,000

OEtOH

O

O O

(S)-SEGPHOS; 99.0% ee(S)-TolBINAP; 97.2% ee

OMe

OH O


OEt

OH OO

(R)-SEGPHOS; 99.4% ee(R)-TolBINAP; 97.4% ee

>99% ee

O O

HO

(R)-SEGPHOS, (R)-BINAP

8x

24a32

24b1

24c1, 23f

24d1, 23f24e1, 23f

2533

2736

NH

O

HO

2634

2835

HO CO2tBu

O O

Key Intermediate to simvastatin or pravastatin,

HMG-CoA reductase inhibitors

α-Substituted-β- Keto Esters

α-Substituted-β-hydroxy esters are obtained by asymmetric hydrogenation via dynamic kinetic

resolution.37 Asymmetric Hydrogenation via Dynamic Kinetic Resolution is a reaction where one

enantiomer of racemic starting material is asymmetrically hydrogenated much faster than the other

(kinetic resolution) with concurrent rapid racemization (dynamic). One of the four possible

stereoisomers is obtained predominantly with 100% consumption of starting material. Thus two

chiral centers can be constructed simultaneously. In the case of β-keto esters, strong acidity of the

proton at 2-position leads to the required easy racemization. In general, high ee but low de values

are obtained in Methanolic solvent. In dichloromethane de values improve, yet rate of reaction

becomes too slow to apply the reaction industrially. Mixed dichloromethane and methanol solvent

is usually used to obtain a reasonable balance of reaction rate and de selectivity. Furthermore

DTBM-SEGPHOS or DM-SEGPHOS, ligands with narrow dihedral angles and bulky pendant

groups, show superior ee and de values as observed in the hydrogenation of 13a or 13b. Tol-

BINAP, used in industrial production of 15 in former times has now been replaced with DTBM-

SEGPHOS.

10

Scheme 4 Hydrogenation of α-substituted-β- Keto Esters

OMe

OH O

OMe

OH O

(R)-SEGPHOS; 99.5% ee, 97.3% de(R)-BINAP; 99% ee, 98% de

(S)-DM-SEGPHOS; >98% ee, 97.5% deTolBINAP; 93% de

SEGPHOS; 99.4% ee, 98.6% deBINAP; 95.3% ee, 94.4% de

R1 OR3

O O

R2

Cl

NHAc

(R)-DTBM-SEGPHOS; 99% ee, 98% de

R1 OMe

OH O

NHAcR1 OH

OH

NHC(O)R2

Ceramide

OH

(R)-DTBM-SEGPHOS; 98% ee, 98% de

OMe

OH O

NHC(O)PhNH

O

OAcHTBSO

(R)-DTBM-SEGPHOS; 99.4% ee, 98.6% de(R)-TolBINAP; 99.0% ee, 86.0% de

CarbapenemIntermediate

DM-SEGPHOS; 93.5% de

N

OH O

Bn

OMe

O

13

1539 14a1, 4, 23f

14b23f

14c38

14d23f

14e1, 23e

14f23f

1640

SEGPHOS; 79.6% de

R1 = -(CH2)14CH3R2 = -(CH2)16CH3

1,2- or 1,3-Diol; From Ketol

The Ru-SEGPHOS class of complexes are best for hydrogenation of α-hydroxy ketones. Thus, in

the manufacture of 1,2-Propanediol, a chiral intermediate of Levofloxacin 19, the ligand has been

switched to SEGPHOS.

Scheme 5 Hydrogenation of α-, or β-Hydroxy Ketones

OHOH R OH

OOH

OH

NO

CO2HO

N

F

Nn

n = 1 or 2 (R)-SEGPHOS; 98.5% ee, S/C = 10,000(R)-TolBINAP; 89.0% ee, S/C = 3,000 Levofloxacin

(R)-BINAP; 98% ee17 18a1

18b41

1942

Other Functionalized Ketones

Asymmetric hydrogenations of all types of functionalized ketones are known.

11

Scheme 6 Hydrogenation of Various Kinds of Functionalized Ketones

R3 R4

O O

OEtOH

O

OH OH

R1 OR2

O

O

R SO3NaO

P(OCH3)2

OH O

BrR5 P

O OR7

R8

R6

(S)-BINAP

P(OCH3)2

OH O

Br

OMe

O

OH

SO3NaOH

P(OMe)2

OH O


(R)-SEGPHOS; 98.6% ee(R)-TolBINAP; 84.0% ee

α-Hydroxyketone1, 23f

(R)-BINAP; 100% ee, 98% de

1,3-Diketone41

Syn; 98% ee, 84% Anti; 94% ee, 9%

+

(R)-BINAP; 98% ee, 99%

Phosphorous Compounds44

(R)-BINAP; 96% ee

Sulfonic Acids43

2829a 29b

30 31 3233

3435a 35b35c

2-2-3. Simple Ketones

Asymmetric hydrogenation of simple ketones is practiced using either of two methods. One is

Noyori’s hydrogenation using [RuCl2(P^P)(N^N)] complex and molecular hydrogen45 and another is

transfer hydrogenation with [RuCl(arene)(N^N)] complex and a hydride source such as Isopropyl

alcohol or HCO2H-Et3N.46 Both reactions are proposed to proceed in the outer coordination sphere

of the complex via a 6-membered transition state TS-A.47 Catalytic activity of the hydrogenation

reaction using [RuCl2(P^P)(N^N)] complex is extremely high up to over 2,400,000 TON.

12

Scheme 7 Catalytic Asymmetric Reduction of Simple Ketones

P

P Cl

Ru

Cl

N

N

ArAr

ArAr H H

H H

RuCl2(P^P)(N^N)

Hydrogenation with Molecular Hydrogen

RuN

NCl

Ph

Ph

RuCl(arene)(N^N)

HP

P N

NO

HP

P N

NO

VS

OH RuN

NH

OH

H

6-Membered Transition State

Favored

OH

Transfer HydrogenationUsing IPA, HCO2H-Et3N etc

Ts

HH

Ru

N

NH

Ph

Ph

Ts

H

HO

H

Ru

N

NH

Ph

Ph

Ts

H

HO

H

CH / πattraction FavoredUnfavoured

vs

(S, SS)-Complex (SS)-Complex

(R)-12Aa(S)-12Aa

36 37

TS-1 TS-2

TS-3TS-4

TS-A

In many cases the [RuCl2(XylBINAP)(N^N)] complex gives excellent enantioselectivity. When results are not satisfactory, DM-SEGPHOS, used in place of XylBINAP, may solve the problem (Scheme-8).

Scheme 8 Hydrogenation of Quinuclidinone48; DM-SEGPHOS Afforded Better Result.

N

O [RuCl2(P^P){(R)-DAIPEN}]

H2, KOtBu, IPA N

OH (R)-DM-SEGPHOS; 90.5% ee(R)-XylBINAP; 74.5% ee

38 39

Figure 4 Phosphine and Diamine Ligands for Noyori’s Complex

NH2

NH2

NH2

NH2

OMe

MeO

P

P

P

P

O

O

O

O

(S,S)-DPEN 40 (S)-DAIPEN 41(S)-2(S)-6 (S)-DM-SEGPHOS(S)-XylBINAP

Various other combinations of diphosphines and diamines may improve enantioselectivities.

13

Simple Acetophenone, Benzophenone, and Heteroaryl Type Ketones

Application of the [RuCl2(P^P)(N^N)] system to a large variety of ketones has been investigated.23a

In most cases, ee values of products exceed 95% ee with excellent catalytic activity. Over 99% ee

values are often observed.

Scheme 9 Hydrogenation of Simple Ketones

R8

OHH2

IV

R7

R4

OH

R3

X

R1 R2

O

OH

OHMeO

NOH

SOH

OOH

IPA

OH

F3C12A

12B50

12Ba12Ca51

OH

MeO

R5

12Ac23a

12C

OH

R6

Acetophenone Type Ketones

Benzophenone Type KetonesHetero aryl Type Ketones

*

(S)-XylBINAP, (S)-DAIPEN; 99.0% ee, S / C = 100,000

RuCl2(P^P)(N^N)Base

(S)-TolBINAP, (S,S)-DPEN; 80.0% ee, S / C = 2,400,000

(S)-XylBINAP, (S)-DAIPEN; 99.0% ee, S / C = 2,000(S)-BINAP, (S,S)-DPEN; 24.4% ee, S / C = 500

*

*

99.6% ee 100% ee

99% ee99% ee96% ee

(S)-XylBINAP, (S)-DAIPEN

11

12Aa49 12Ab23a

12Bb 12Bc

(R)-XylBINAP, (R)-DAIPENS/C = 2,000 S/C = 5,000 S/C = 40,000

Ketone Selective Reduction

Carbonyl groups are selectively reduced even when olefins exist in the same molecule, during the

hydrogenation reaction when using Noyori’s [RuCl2(P^P)(N^N)] complex.

Scheme 10 Ketone Selective Hydrogenation

R1

O R2

R4

R3

OH

OH

OHS

OH

OH

94 - 96% ee

97% ee 100% ee

91% ee

97% ee

(S)-XylBINAP, (S)-DAIPEN

(S)-XylBINAP, (S)-DAIPEN(S)-XylBINAP, (S)-DAIPEN(S)-XylBINAP, (S)-DAIPEN

42

43a49a 43b49a43c49a

43d50 43e52

or(S)-TolBINAP

(R,R)-DPEN(S)-BINAP

14

Hydrogenation of Simple Ketones via Dynamic Kinetic Resolution

Simple ketones, having substituents at α-position, are also hydrogenated to alcohols, producing

two chiral carbon centers in high yield via dynamic kinetic resolution (DKR).

Scheme 11 Simple Ketones; Dynamic Kinetic Resolution

OHO R1OHOCH3

(CH2)n

(S)-XylBINAP, (S,S)-DPEN99% ee, 99% de 93% ee, 99.6% de

(S)-BINAP, (R,R)-DPEN

4445a53 49b54

The DKR is caused by the basic KOtBu used in Noyori’s reduction. With alternative use of BH4-

Complex under neutral condition, no DKR is observed, and one enantiomer of the starting material

remains unhydrogenated.55

2-2-4. Olefins

Carboxylic acid

Among biaryl phosphine ligands, H8-BINAP is promising for olefin hydrogenation, affording higher

enantioselectivities than BINAP.

Scheme 12 Hydrogenation of Unsaturated Carboxylic Acids56

CO2HR3

R1

R2

CO2H CO2H

CO2H

MeO

CO2H

(S)-H8-BINAP

n

n = 0 or 1

(S)-H8-BINAP; 96% eeBINAP; 84% ee

(S)-H8-BINAP; 89% eeBINAP; 30% ee

From E olefin From E olefin

46

47a 47b

47c

47d

97% ee

92% ee, S / C = 5,000

15

Allyl Alcohol or Homo Allyl Alcohol

Olefins at the β,γ - or the γ,δ-position of the hydroxyl group are selectively hydrogenated.

Scheme 13 Hydrogenation of Allylic Alcohols57

n

R3R1

R2

n = 1 or 2

OHOH OH

OH

OH

(S)-BINAP-Ru

(S)-BINAP-Ru(R)-BINAP-Ru

(R)-BINAP-Ru

98% ee98% ee

98% ee

OH

(S)-BINAP-Ru

OH

Vitamin E side chain

48

E-49

Z-49

(S)-50 (R)-50

51 52

NEt222 l-Menthol Intermadiate 99%(R,R)

Other Olefins

Diketene is hydrogenated to chiral β-lactone 54, which can be transformed to various chiral 3-

sustituted carboxylic acids. Enol ethers and enol esters are also hydrogenated in high ees.

Scheme 14 Hydrogenation of Other Type of Olefins

OO

OO Nu

Nu OH

O

(S)-SEGPHOS; 93.8% ee, TON = 10,830(S)-Tol-BINAP; 93.4% ee, TON = 1,500

Diketene

R2 R3

OR4

R1

OEt

O

OAc

(R)-BINAP; 98% eeFrom E/Z = 70/30

Enol ether and Enol ester

53 (R)-5458 5559

56 5760

2-2-5. Enamino Esters and Reductive Amination to β-Amino Acid Derivatives

β-Amino Acids

Chiral non-protected β-amino acids are obtained through Direct Reductive Amination (DRA) of β-

ketoesters or through hydrogenation of enamino esters. Ruthenium catalysts give β-Amino acid

derivatives in good yield via DRA as do Rhodium catalysts in low to modest yield. These methods

are superior from both the economical and environmental point of view, because omission of two

steps, protection and deprotection, decreases not only cost but also industrial waste.

16

Scheme 15 Synthesis of β-Amino Acids by Hydrogenation61

R1 OR2

O O

+RNH2

or its saltR = H, Alkyl, Alyl etc

DirectReductiveAmination

R1 OR2

NHRO

* R1 OR2

NHRO

Hydrogenationof

Enamino esteror salt

8

910

Various kinds of β-amino acid derivatives have already been synthesized using this method. In

almost all cases, crude β-amino acid derivatives have high ee values of 94 to 99%.

Figure 5 β-Amino Acid Library

OMe

NH2 O

*

OMe

NH2 O

OMe

NH2 O

* OMe

NH2 O

* OMe

NH2 O

*

OEt

NH2 O

OMeSNH2 O

OMe

NH O

Cl

*

*

*OMe

NH2 O

*OBn*

87.8% ee

10a 10b 10c 10d

10e 10g 10h10f

10i OMe

NH O

10j88.4% ee

Cl

Cl

94.4%ee 98.4%ee 98.7%ee 99.3%ee

95.7%ee 98.5%ee 96.7%ee Anti (99%ee)/Syn (95%ee) = 86/14

Other N-Containing Compounds

Enamines and imines can be hydrogenated by using Ru-complexes or the related Ir-complexes.

Scheme 16 Synthesis of Amine

R7 R8

NR6

NH

R3

R5

NR1R2

R4

NC(O)CH3

H3CO

H3COOCH3

OCH3

HN

HN

(R)-BINAP; 99.5% ee

(S)-BINAP / Ir; 85% ee (S)-BINAP / Ir; 91% ee(R)-TolBINAP / Ru; 88.9% ee

Enamines

Imines

58 598

6061a62 61b63 65c64

(From Z-Enamine)

17

2-3. Other Reactions

There are numerous investigations of metal-biaryl phosphine complex catalyzed asymmetric

reactions. Examples of SEGPHOS-related catalytic asymmetric reactions will be described below.

2-3-1. Aldol-Type Reaction65

Cross Aldol type reactions of acetonitrile with aldehydes, including linear aldehydes, have been

achieved. σ−Donating solvents improved chemical yield, preventing aldehydes from self-

condensation but not inhibiting coordination of nitrile.

Scheme 17 Nitrile Aldol Reaction

R H

O

CH3CN

OHCN

R CNOH

OHCN

H3C(CH2)5CN

OH

OHCN

OHCN

OHCN

TolBINAP; 16% ee, 21%, at 50oC

Ph-BPE; 0% ee, 32%, at 50oCJosiphos; 6% ee, 18%, at 50oC

DTBM-SEGPHOS; 58% ee, 84%, at 50oCDTBM-SEGPHOS; 74% ee, 72%

rt+

Ligand / CuOtBu

* *

** *

* *

68% ee, 67% 76% ee, 88% 75% ee, 86% 75% ee, 91% 51% ee, 85%

Ligand = DTBM-SEGPHOS

62

6364 64a

64b 64c 64d 64e 64f

2-3-2. Alkenylation and Arylation66

Alkenylation and phenylation of aldehydes by alkenyl or phenyl silanes were improved using the

SEGPHOS class of ligands. Bulkiness is more important than electronic features for the ligand-

acceleration effect.

Scheme 18 Alkenylation and phenylation

R1 R2

O

R3 Si(OMe)2Y

OH

Cl

OH

MeO

R1 R2

OH

R3

SOH

OH

OH OH

Ph CO2Me

OH

+ TolBINAP; 61% ee, 47%, 24hEt-DuPHOS; 38% ee, 51%, 24h

iPr-DuPHOS; 64% ee, 87%, 6h

DTBM-SEGPHOS; 94% ee, 99%, 0.5h

98% ee, 84%Y = Me

*

**

Ligand = DTBM-SEGPHOS

1) Ligand / CuF2 H2O

2) TBAF *

R1 = Ph, R2 = H, R3 = -CH=CH2, Y = -OMe

* * * *

97% ee, 99%Y = -OMe

92% ee, 99%Y = -OMe

91% ee, 99%Y = -OMe

90% ee, 83%Y = Ph

84% ee, 76%Y = -OMe

65

6667 67a

67b 67c 67d 67e 67f 67g

18

2-3-3. Mannich reaction

Palladium aqua complex [Pd(P^P)(H2O)2][X]2 catalyzes the asymmetric Mannich reaction of β-keto

esters. Palladium enolate derived from β-keto ester reacts with aldimines.

Scheme 19 Mannich Reaction of β-Keto esters67

R1

O

R2OtBu

ON

R3

R4

O

CO2EtHN

CO2tBu

OMe

R1 R3O

R2

NHR4

OOtBu

DM-SEGPHOS; 93% ee (major), 50% ee (minor), 98/2 (dr)

+ * *

**

SEGPHOS; 99% ee (major), 98% ee (minor), 81/19 (dr)TolBINAP; 97% ee (major), 91% ee (minor), 83/17 (dr)

BINAP; 98% ee (major), 97% ee (minor), 83/17 (dr)

Ligand / Pd

13a 68 69

69a

A DTBM-SEGPHOS / Cu complex also catalyzes a Mannich type reaction between Aryl-Alkyl

ketimines and silyl enolate 71.

Scheme 20 Mannich Reaction of Ketimines68

Ar R

N P(xylyl)2O

OBu

OTBS

Cu(OAc)

(EtO)2Si(OAc)2

OBu

NH(xylyl)2PO

O

XOBu

NH(xylyl)2PO

O

Ar OBu

NH

R

(xylyl)2PO

O

OBu

NH(xylyl)2PO

OO OBu

NH(xylyl)2PO

O

S

Ar OH

NH2

R

O

OBu

NH(xylyl)2PO

O

+

DTBM-SEGPHOS

*

*

X = H; 95% ee, 81%X = Cl; 97% ee, 82%

X = -OMe; 97% ee, 87%

*

96% ee, 74%

*

96% ee, 74%

*

97% ee, 92%

*

91% ee, 61%

1) 3N HCl. aq

2) 0.5N NaOH aq. *70 71 72 73

72a72b72c

72d 72e 72f 72g

DuPHOS / Cu complex catalyzes a Mannich type reaction between aliphatic ketimines and silyl

enolate 71 with moderate ee values.

2-3-4. Fluorination

In contrast to the Mannich reaction (scheme 9) and the Michael addition (scheme 23), palladium μ-

hydroxo complex [Pd(P^P)(μ-OH)]2[X]2 also catalyzes the asymmetric fluorination of β-keto ester

using N-Fluorobenzenesulfonimide (NFSI) 75. In many cases, reaction using DTBM-SEGPHOS as

ligand gives the best result with high enantioselectivity.

19

Scheme 21 Fluorination of β-keto esters69

R1 OR3

O O

R2

O

OtBu

O

F

O O

OtBuF

R1 OR3

O O

R2 F

O O

OtBuF

NF

PhO2S SO2Ph

NFSI

HN OtBu

OO

F*

DTBM-SEGPHOS; 90% ee at 0oCXylBINAP; 88% ee at -20oC

BINAP; 79% ee at -20oC

XylBINAP; 91%ee 91%ee

*

94%ee

*

Ligand / Pd, NFSI *

*

13 74 75

74a 74c74b 74d

DTBM-SEGPHOSPd-Aqua Complex

Pd-μ-Hydroxo ComplexDTBM-SEGPHOS; 92% ee at 20oC

Fluorinated β-Amino acids are obtained from the α-Fluorinated keto ester products. All four

stereoisomers can be prepared individually by using proper reagents.

Scheme 22 Synthesis of α-fluorinated β-Amino Acids69a

R1 OR3

O O

R2 F

R1 OR3

OH O

R2 F

R1 OR3

OH O

R2 F

R1 OR3

NH2 O

R2 F

R1 OR3

NH2 O

R2 F

PhMe2SiH

Ph3SiH74

76a

76b

77a

77b

2-3-5. Michael Addition

Sodeoka’s Pd-aqua complex also catalyzes hetero Michael reactions to afford β-amino acid

derivatives.

Scheme 23 Pd-Catalyzed Hetero Michael Addition70

R1 N

O

OR3

O

R2 Ligand / Pd

R4R5NH+ R1 N

O

OR3

O

R2

NR4 R5

*N

NH O

O

O

*

BINAP; 94% ee

N

NH O

O

O

*

MeO

SEGPHOS; 83%, 97% ee, S/C = 1,000BINAP; 92%, 98% ee, S/C = 200

78

79 8080a 80b

20

2-3-6. Hydrosilylation

B. Lipshutz’s Group has reported hydrosilylation of aryl and heteroaryl ketones, α,β-unsaturated

carbonyl compounds, and imines in many papers, where DTBM-SEGPHOS / Cu complexes give

good results in terms of enantioselectivity and catalytic activity. Polymethylhydrosiloxane (PMHS),

an inexpensive and air and moisture stable reagent, is commonly used as hydride source.

Scheme 24 Hydrosilylation of Aryl & Heteroaryl Ketones71

Scheme 25 1,4-Reduction of Cyclic α,β-Unsaturated ketones72

O

Rn

O

Rnn = 0 or 1

*

O

98.5% ee88%( isolated yield)S/L = 275,000/1

O

97.3% ee

O

97.0% ee

OMe

O

Ligand / CuCl, NaOtBu, PMHSor

Ligand / [CuH(PPh3)]6, PMHS

Ligand = (R)-DTBM-SEGPHOS82 8383a 83b 83c

In the case of acyclic α,β-unsaturated ketones, PPF-P(tBu)2 often works well.

Scheme 26 Hydrosilylation of Imines73

N

R1

R3

HN P(3,5-xylyl)2O

HN P(3,5-xylyl)2O

R2 R2

HN

R1

R3

HN P(3,5-xylyl)2O

F3C

TMDS

Si O SiH

H

HN P(3,5-xylyl)2O

MeO*

99.3% ee

*

98.4% ee

*

97.3% ee

*

94.2% ee

DTBM-SEGPHOS / Cu

NaOtBu, TMDS *

84 85

85a 85b 85c 85d

86

In this case, 1,1,3,3-tetramethyldisiloxane (TMDS) gives good result, though PMHS gives only

modest results.

NOH

(R)-DTBM-SEGPHOS; 90% ee(R)-Xyl-MeO-BIPHEP; 70% ee

(R)-DTBM-MeO-BIPHEP; 51% ee

OOH

(R)-DTBM-SEGPHOS; 92% ee(R)-Xyl-MeO-BIPHEP; 90% ee

OH

(R)-DTBM-SEGPHOS; 96% ee

(R)-Xyl-MeO-BIPHEP; 94% ee(R)-DTBM-MeO-BIPHEP; 90% ee

(R)-DM-SEGPHOS; 95% ee

Ar R1

O Ligand / Cu

NaOtBu, PMHS Ar R1

OH

*Si O Si

H

O Sin

PMHS11 12 81

12Aa 12Bc 12Ba

21

2-3-7. Reductive Aldol Reaction.

Copper enolates generated as a result of hydrosilylation of α,β-unsaturated esters react with

ketones to form Aldol adducts. SEGPHOS and MeO-BIPHEP are efficient.

Scheme 27 Intramolecular Reaction74

R2O

O

R1

O

n R2O

O

R1

O

n

Cu

Aldol ReactionO

O

HOR2

R1

n

O

O

HO

(S)-SEGPHOS; 74% ee, 62%

TMDSLigand / Cu

(S)-Xyl-MeO-BIPHEP; 70% ee, 69%

O

O

HOCl

(S)-SEGPHOS; 82% ee, 73%(S)-Xyl-MeO-BIPHEP; 83% ee, 71%

O

O

HO

(S)-SEGPHOS; 80% ee, 68%(S)-Xyl-MeO-BIPHEP; 80% ee, 61%

87 88 89

89a 89b 89c

An intermolecular reductive aldol reaction is also reported. DTBM-SEGPHOS affords γ-adducts

whereas Taniaphos gives α-adducts.

Scheme 28 Intermolecular Reaction75

R1

O

.

O

OEtR1 CO2R2OH

(R3)2Zn

CO2Et

OH

CO2Et

OH

Cl CO2Et

OH

O

O

Ph R3

R1CO2R2

OH

+*

*

Taniaphos / Cupinacolborane

1)

2) H2O

R1 = Ph, R2 = Me84% ee, 10/1 (dr), 90%

*

(R)-DTBM-SEGPHOS / Cu

1) pinacolborane2) H2O

R3 = Et; 77% ee, 47%R3 = Me; 88% ee, 60%

99% ee, 25/1 (γ/α), 96%

*

98% ee, 13/1 (γ/α), 93%

*

98% ee, >8/1 (γ/α), 80%

α−adduct

γ−adduct

9065a 91

92

93

93a 93b 93c

*

2-3-8. Aryl Amination

Palladium-catalyzed asymmetric N-Arylations of 2-substituted-N-acyl anilines afford optically active

atropisomeric anilides.

22

Scheme 29 Optically Active Atropisomeric Anilines 76

2-3-9. [2 + 2+ 2] Cycloaddition Asymmetric [2+2+2] cycloaddition reactions between intermolecular or Intramolecular 3-triple bonds, 2-triple bonds and 1-double bond, and 1-triple bond and 2-double bonds proceed by rhodium catalysts.

Scheme 30 Various Types of [2+2+2] Cycloaddition Reaction77

R7

R8

O

O

CO2Me

CO2MeCO2Me

CO2Me

IH

J

G

L

M

K

N

R1

R2

100A

A

BR4

R3

NTs

100Ca

AR1

R2R3

R4

B

R2

R1

I JHG

GHFE

MeO2C CO2Me

MeO2CMeO2C

EtO2C

CO2Et

EtO2C

CO2Et

OAc

OAc

100C100B

R8

R7R6

R5

E FDC

R5

R6

Cl

NMeO2CMeO2C O

Bn

ED

F

CR8

R7

OMeOMeNTs

100Ba

3-(Triplebonds)

2-(Triplebonds) + 1-(Doublebond)

SEGPHOS; >99% ee, 59%

* *

SEGPHOS; 98% ee, 24%

BINAP; 93% ee, 77%TolBINAP; 97% ee, 81%XylBINAP; 91% ee, 36%H8-BINAP; 95% ee, 83%


*

*

DTBM-SEGPHOS; 92% ee, 89%

**

1-(Triplebonds) + 2-(Doublebonds)

BINAP; 97% ee, 69%TolBINAP; >99% ee, 81%XylBINAP; 99% ee, 82%H8-BINAP; 95% ee, 71%


100

100Aa100Ab

100Bb

99a

99b

99c

99d

99e

99f

99g

99h

99i

I

O2N

Ar X

NH

O

tBu

R

NHBut

R2

O

R1

Base

Ar NtBu

R2

R1

O

Ar NtBu

R

O

R =H

I

NH

O

tBu

R

Cs2CO3

Cs2CO3 N OtBu

R

Intramolecular

R = H; 70% eeR = tBu; 96% ee

Intermolecular

+

PHANEPHOS; 0%Me-DuPHOS; 15% ee, 16%

Et-FerroTANE; 33% ee, 12%TolBINAP; 53% ee, 48%XylBINAP; 78% ee, 56%

BINAP; 77% ee, 78%DTBM-SEGPHOS; 89% ee, 28%

Base

KOtBu DTBM-SEGPHOS; 93%ee, 84%R = tBu DTBM-SEGPHOS; 95%ee, 81%

(S)-BINAP / Pd

Ligand / Pd

(S)-Productfrom

(R)-DTBM-SEGPHOS

+

Ligand / Pd

Base94

95 96 97 98

95a

94a

96a

Ar = p-Nitrophenyl

23

2-3-10. [3 + 2] Cycloaddition

Copper-catalyzed asymmetric [3+2] cycloaddition reactions between allenylsilanes 101 and highly

reactive aldimine 102 were achieved. When R1 is H, the reaction did not proceed. Dehydroproline

derivative 103 can be converted to keto amino acid 104. DM-SEGPHOS gave the best result.

Scheme 31 [3+ 2] Cycloaddition Between Allenylsilane and Aldimine78

. SiR23

R1

N

EtO2C H

Ts

NTs

EtO2C R1

SiR23

EtO2C

NHTs

O

NTs

EtO2C

Si(tBu)(Ph)2

+

Ligand / Cu(R)-BINAP; 58% ee, 48%

(R)-TolBINAP; 57% ee, 67%(R)-SEGPHOS; 67% ee, 65%

(R)-DM-SEGPHOS; 85% ee, 53%

101

102

103 104

103a

R = iPr, (R)-DM-SEGPHOS; 84% ee, 92%

aq. HI

2-3-11. 1,3-Dipolar Cycloaddition

Cu-phosphine complex catalyzed asymmetric 1,3-dipolar cycloaddition reactions showed exo

selectivities, whereas most chiral metal complexes produced endo selectivities.

Scheme 32 Cu-Phosphine-Catalyzed exo Selective 1,3-Dipolar Cycloaddition Reactions79

E

E

R N EEt3N

HN

E E

R E

NO OPh

R N CO2Me

HN

N

Ph CO2Me

O OPh

HN

N

Ph CO2Me

O O

Ph+

+

exo endo

BINAP; 64% ee, >95/5 (exo/endo), 71%TolBINAP; 47% ee, >95/5 (exo/endo), 40%

H8-BINAP; 60% ee, 93/7 (exo/endo), 25%

SEGPHOS; 72% ee, 85/15 (exo/endo), 78%

+Ligand / Cu105

106 107

105a

106a

107α 107β

2-3-12. Diels-Alder Reaction

Nitroso Diels-Alder reactions between 6-Methyl-2-nitrosopyridine 108 and cyclic diene 109 were

achieved with high enantioselectivities and complete regioselectivity catalyzed by Cu-SEGPHOS

complex. Diels-Alder adducts can be transformed to protected amino alcohol 111.

24

Scheme 33 Nitroso Diels-Alder Reaction80

N

NO

+ Ligand / Cu NO

N

SEGPHOS; 92% eeMeO-BIPHEP; 90% ee

BINAP; 87% ee

H8-BINAP; 67% ee

NHTs

OTBS

108

109110

111

R1

R2

n

n

R2

R1

NO

N110a

TolBINAP; 81% ee

2-3-13. Ene-Type Reaction

Chiral quaternary carbon centers can be efficiently constructed.

Scheme 34 Ene-Type Reactions

O

CO2Me

O

CO2Me(R)-SEGPHOS; >99% ee (S), >99%

(R)-TolBINAP; 94% ee (S), >99%(S)-H8-BINAP; 95% ee (R), >99%

(S)-Xyl-H8-BINAP; 2% ee (R), >99%

nn = 1 or 2

Ligand / Pd, AgSbF6

nCO2Et

OHF3C

*

*F3C CO2Et

O+

Ligand / Pd

SEGPHOS; 97% ee, 84%, n = 1SEGPHOS; 96% ee, quant., n = 2

BINAP; 95% ee, n = 2

Ene Reaction81

Carbonyl-Ene Reaction82

R R'

O OLigand / Pd

Yb(OTf)3R R'

O OOEt

O O

89% ee, 86%

O O

70% ee, 90%Ligand = DTBM-SEGPHOS

* **

Conia-Ene Reaction83

112 113

114 115 116

117 118 118b118a

I

OCO2Et

OEtO O

*Reductive

Heckcyclization

118c85% ee, 95%

119

2-3-14. Nucleophilic Addition to π-Allylpalladium Complexes

Chiral Allenyl compounds were synthesized from bromodiene 120 or allenyl phosphate 123. In the

case of allenyl phosphate 123, kinetic resolution was observed.

25

Scheme 35 Allene Compounds84

= Cs[C(NHAc)(CO2Et)2]

.

H

H

Me3Si

C(NHAc)(CO2Et)2

(R)-BINAP; 62% ee, 8% in CH2Cl2 at 20oC(R)-SEGPHOS; 88% ee, 12% in CH2Cl2 at 20oC(R)-SEGPHOS; 87% ee, 63% in THF at 50oC

Me3Si

Br+

Nu-M+

Ligand / Pd .

H

H

Me3Si

Nu Nu-M+

.

H

H

R1

OP(OEt)2O

+

R2

HN R3

.

H

H

R1

N R3

R2

.

H

HtBu

N Bn

Me

.

H

HtBu

N

.

H

HtBu

N Boc

Boc84% ee, 72% 91% ee, 56%

97% ee, 77%

(R)-SEGPHOS / Pd

120

121 122

122a121a

123

124 125

125a 125b

125c

2-3-15. Aryl Addition Reaction

Asymmetric additions of aryl boronic acids and aryl titanium reagents were developed by means of

rhodium catalysts.

Scheme 36 1,2-, 1,4-, 1,6-Aryl Addition Reactions

R2

R1

R3R4

O

R5

O

R8

R6

R7

ArB(OH)2R3

R1Ar

R4

O

R2

. R5

Ar

R6

R7

OSiMe3

R8

O O

O

nBu

ArTi(OiPr)4LiMe3SiCl

N R9R10

H R10 Ar

NHR9

Me3SiCl

NHSO2Ar'

F3C

ArTi(OiPr)4Li

ArTi(OiPr)3

O O

Ph

OC(O)tBu

. PhnBu

1, 6-Addition86

Ligand / RhSEGPHOS; 90% ee, 86%

BINAP; 80% eePPF-P(tBu)2; 14% ee

MeO-MOP; 0% ee

Ligand / Rh

*

*

*

(S)-SEGPHOS; 93% ee, 98%(S)-H8-BINAP; 82% ee, 86%

(S)-BINAP; 71% ee, 58%

Ligand / Rh*

(R)-SEGPHOS; 99.6% ee, 88%(R)-P-Phos; 97.1% ee, 93%(R)-BINAP; 96.4% ee, 75%

Ar' =

1,4-Addition85

1,2-Addition; Aldimine87

Ligand / Rh1)

2) MeLi, ClC(O)tBu

126 127126a 127b

128 129

128a 129a

130 131 130a

26

2-3-16. Cyclopropanation

High cis selective asymmetric cyclopropanation reaction proceeded by means of gold-phosphine

catalysts.

Scheme 37 Gold-catalyzed cyclopropanation reaction of olefins using propargyl esters88

OR1

+ R2R5

R4

R3

Ligand / Au

R1O

R3R2

R4

R5AcO

PhDIOP; 0% ee, 67%

BINAP; 22% ee, 85%XylBINAP; 44% ee, 86%

DTBM-SEGPHOS; 60% ee, 72%131 132133 133a

DTBM-SEGPHOS; 94% ee, 71%; R1 = Piv., R2 = 2,6-Me-4-tBuPh, R3 = R4 = R5 = H

2-3-17. Enantioselective C-C Bond Cleavage

A chiral quaternary carbon center was produced by enantioselective C-C bond cleavage of rhodium

cyclobutanolate, an intermediate in the following reaction.

Scheme 38 C-C Bond Cleavage89

BO

O

OR

K3PO4O

R

O

Et(S)-SEGPHOS; 95% ee, 96%

(R)-MeO-BIPHEP; 75% ee (R), 98% (S)-BINAP; 69% ee, 93%

Ligand / Rh

134 135 135a

*

3. Conclusion

As seen above, reactions show diverse results depending on catalysts and/or ligands used, so

chemists always desire to keep on hand a large variety of both catalysts and ligands to try.

There has been an enthusiastic acceptance of Takasago's new ligands and complexes which in

addition to producing high activities and selectivities in catalysis, are now available in commercial

quantities and in high quality via fully developed manufacturing processes.

4. Future Aspects

New catalysts, ligands and reactions are being developed at TAKASAGO. Some examples are

shown in Figure 5.

27

Figure 5 Future Aspects.

O

O

O

O

PR12

PR12

Cy-SEGPHOS Ipr-SEGPHOS

SEGPHOSes

O

O

O

O

P

P

R2

R2

R2R2

= R2 =

-CH3

MP2-SEGPHOS P3-SEGPHOS

R32P P

UCAPs

OMe

DTBM-UCAP

R3 =

P P

BeePHOS

OPPh2

PPh2

DPBP

for Noyori's Complex

[RuCl(arene)(N^N)] complexes

for Asymmetric Transfer Hydrogenation

R1

136 137 138 139

140

141 142 143

RuN

NCl

Ph

PhTs

HH

References: (1) (a) Saito, T.; Yokozawa, T.; Ishizaki, T.; Moroi, T.; Sayo, N.; Miura, T.; Kumobayashi, H. Adv. Synth. Catal.

2001, 343, 264. (b) Absolute Configuration of DTBM-SEGPHOS was determined at TAKASAGO. Levorotatory DTBM-SEGPHOS has (R)-configuration.

(2) Miyashita, A.; Yasuda, A.; Takaya, H.; Toriumi, K.; Ito, T.; Souchi, T.; Noyori, R. J. Am. Chem. Soc. 1980, 102, 7932.

(3) (a) Inoue, S.; Osada, M.; Koyano, K.; Takaya, H.; Noyori, R. Chem. Lett. 1985, 1007. (b) Takaya, H.; Mashima, K.; Koyano, K.; Yagi, M.; Kumobayashi, H.; Taketomi, T.; Akutagawa, S.; Noyori, R. J. Org. Chem. 1986, 51, 629.

(4) (a) Mashima, K.; Matsumura, Y.; Kusano, K.; Kumobayashi, H.; Sayo, N.; Hori, Y.; Ishizaki, T.; Akutagawa, S.; Takaya, H. J. Chem. Soc., Chem. Commun. 1991, 609. (b) Mashima, K.; Kusano, K.; Sato, N.; Matsumura, Y.; Nozaki, K.; Kumobayashi, H.; Sayo, N.; Hori, Y.; Ishizaki, T.; Akutagawa, S.; Takaya, H. J. Org. Chem. 1994, 59, 3064.

(5) Zhang, X.; Mashima, K.; Koyano, K.; Sayo, N.; Kumobayashi, H.; Akutagawa, S.; Takaya, H. Tetrahedron Lett. 1991, 32, 7283.

(6) (a) Mashima, K.; Kusano, K.; Ohta, T.; Noyori, R.; Takaya, H.; J. Chem. Soc., Chem. Commun. 1989, 1208. (b) See also ref. 4b.

(7) Sayo, N.; Mashima, K. (Takasago Int. Corp.), patent, JP H10-95792A, 1998. (8) Noyori, R.; Ohta, M.; Hsiao, Y.; Kitamura, M.; Ohta, T.; Takaya, H. J. Am. Chem. Soc. 1986, 108, 7117. (9) Doucet, H.; Ohkuma, T.; Murata, K.; Yokozawa, T.; Kozawa, M.; Katayama, E.; England, A. F.; Ikariya, T.;

Noyori, R. Angew. Chem. Int. Ed. 1998, 37, 1703. (10) See section 2-2-5. (11) See scheme-8. (12) See scheme-37. (13) (a) See scheme-19. (b) See scheme-21. (c) See scheme-23. (d) See scheme-29. (14) (a) See scheme-17. (b) See scheme-18. (c) See scheme-20. (d) See section 2-3-6. (15) Org. Synth. 2002, 79, 43. (16) See section 2-2-3. (17) See scheme-12. (18) See scheme-13. (19) Dihedral angles in Ru-complexes of these ligands were estimated by CAChe MM2 calculation. (20) for example;

(a) Anti-fungal Drug ofloxacin vs levofloxacin; Imamura ,M.; Shibamura, S.; Hayakawa, I.: Osada, Y. Antimicro. Agents Chemother. 1987, 31, 325.

28

(b) Insect Pheromone; Haniotakis, G.; Francke, W.; Mori, K.; Redlich, H.; Schurig, V. J. Chem. Ecol. 1986, 12, 1559. (c) Aroma chemical l-Menthol & d-Menthol; Wartney, E.; Heymann, H. J. Sens. Stud. 1996,10, 393. (d)Sweetener Aspartame; Pavlova, L. A.; Komarova, T. V.; Davidovich, Y. A.; Rogozhin, S. V. Russ. Chem. Rev. 1981, 50, 316.

(21) (a) Stinson,S. C.Chem. Eng. News 2000, 78, 55. (b) Stinson,S. C.Chem. Eng. News 2001, 79, 45. (22) (a) Kumobayashi, H. Recl. Trav. Chim. Pays-Bas, 1996, 115, 201. (b) Blaser, H. U.; Schmidt, E. Chem.

Commum. 2003, 293. (23) (a) Noyori, R.; Ohkuma, T. Angew. Chem. Int. Ed. 2001, 40, 40. (b) Kumobayashi, H.; Miura, T.; Sayo, N.;

Saito, T.; Zhang, X. Synlett 2001, 1055. (c) Knowles, W. S. Angew. Chem. Int. Ed. 2002, 41, 1998. (d) Noyori, R. Angew. Chem. Int. Ed. 2002, 41, 2008. (e) Tang, W.; Zhang, X. Chem. Rev. 2003, 103, 3029. (f) Sumi, K. Kumobayashi, H. Topics Organomet. Chem. 2004, 6, 63.

(24) (a) Nozaki, H.; Moriuti, S.; Takaya, H.; Noyari, R. Tetrahedron Lett. 1966, 5239. (b) Nozaki, H.; Takaya, H.; Moriuti, S.; Noyari, R. Tetrahedron 1968, 24, 3655.

(25) Knowles, W. S.; Sabacky, M. J. Chem. Commun. 1968, 1445. (26) Horner, L.; Siegel, H.; Bűthe, H. Angew. Chem. Int. Ed. 1968, 7, 942. (27) Dang, T. P.; Kagan, H. B. Chem. Commun. 1971, 481. (28) Vineyard, B. D.; Knowles, W. S.; Sabacky, M. J.; Bachman, G. L.; Weinkauff, D. J. J. Am. Chem. Soc. 1977,

99, 5946. (29) Ohkuma, T.; Ooka, H.; Hashiguchi, S.; Ikariya, T.; Noyari, R. J. Am. Chem. Soc. 1995, 117, 2675. (30) Nobel Lectures of winners of Nobel Prize in chemistry in 2001; (a) Professor William S. Knowles; ref. 23c.

(b) Professor Ryoji Noyori; ref. 23d. (c) Professor K. Barry Sharpless; Angew. Chem. Int. Ed. 2002, 41, 2024.

(31) Shimizu, H.; Nagasaki, I.; Saito, T. Tetrahedron 2005, 61, 5405. (32) (a) SEGPHOS; Unpublished data. (b) BINAP; Noyori, R.; Ohkuma, T.; Kitamura, M.; Takaya, H.; Sayo, N.;

Kumobayashi, H.; Akutagawa, S. J. Am. Chem. Soc. 1987, 109, 5856. (33) (a) from 24c; Yuasa, Y.; Sano, N.; Konno, M. (Takasago Int. Corp.), patent, JP H9-77759A, 1997. (b) from

24b; Sotoguchi, T.; Matsumoto, T. (Takasago Int. Corp.), patent, JP 2003-34687A, 2003. (34) (a) Mitsuhashi, S.; Kumobayashi, H. (Takasago Int. Corp.), patent, JP H9-208558A, 1997. (b) Mitsuhashi,

S.; Sumi, K.; Moroi, T. (Takasago Int. Corp.), patent, JP H11-286479A, 1999. (35) Sakurai, K.; Mitsuhashi, S.; Kumobayashi, H. (Takasago Int. Corp.), patent, JP H6-65226A, 1994. (36) Noyori, R.; Kitamura, M.; Ohkuma, T.; Sayo, N. (Takasago Int. Corp.), patent, JP H4-108782A, 1992. (37) (a) Kitamura, M.; Tokunaga, M.; Noyori, R. J. Am. Chem. Soc. 1993, 115, 144. (b) Kitamura, M.; Tokunaga,

M.; Noyori, R. Tetrahedron 1993, 49, 1853. (c) Noyori, R.; Tokunaga, M.; Kitamura, M. Bull. Chem. Soc. Jpn. 1995, 68, 36.

(38) Unpublished data. (39) Murahashi, S.-I.; Naota, T.; Kuwabara, T.; Saito, T.; Kumobayashi, H.; Akutagawa, S. J. Am. Chem. Soc.

1990, 112, 7820. (40) (a) Sakurai, K.; Ishida, K. (Takasago Int. Corp.), patent, JP H9-59229A, 1997. (b) Sakurai, K.; Tachikawa,

A.; Harada, T. (Takasago Int. Corp.), patent, JP H9-235259A, 1997. (c) Sakurai, K.; Ishida, K. Ogura, S. (Takasago Int. Corp.), patent, JP H10-114732A, 1998. (d) Sakurai, K.; Ishida, K. Ogura, S. (Takasago Int. Corp.), patent, JP H10-218851A, 1998.

(41) Kitamura, M.; Ohkuma, T.; Inoue, S.; Sayo, N.; Kumobayashi, H.; Akutagawa, S.; Ohta, T.; Takaya, H.; Noyori, R. J. Am. Chem. Soc. 1988, 110, 629.

(42) Atarashi, S.; Yokahama, S.; Yamazaki, K.; Sakano, K.; Imamura, M.; Hayakawa, I. Chem. Pharm. Bull. 1987, 35, 1896.

(43) Kitamura, M.; Yoshimura, M.; Kanda, N.; Noyori, R. Tetrahedron 1999, 55, 8769. (44) Kitamura, M.; Tokunaga, M.; Noyori, R. J. Am. Chem. Soc. 1995, 117, 2931. (45) (a) See ref. 29. (b) Ikariya, T.; Ohkuma, T.; Ooka, H.; Hashiguchi, S.; Seido, N.; Noyori, R. (JST), patent, US

005763688A, 1995. (46) (a) Hashiguchi, S.; Fujii, A.; Takehara, J.; Ikariya, T.; Noyori, R. J. Am. Chem. Soc. 1995, 117, 7562. (b)

Fujii, A.; Hashiguchi, S.; Uematsu, N.; Ikariya, T.; Noyori, R. J. Am. Chem. Soc. 1996, 118, 2521. (c) Ikariya, T.; Hashiguchi, S.; Takehara, J.; Uematsu, N.; Matsumura, K.; Noyori, R.; Fujii, A. (JST), patent, WO97/20789, 1997

(47) For Hydrogenation; (a) Sandval, C. A.; Ohkuma, T.; Muňiz, K.; Noyori, R. J. Am. Chem. Soc. 2003, 125, 13490.

For Transfer hydrogenation; (b) Noyori, R.; Yamakawa, M.; Hashiguchi, S. J. Org. Chem. 2001, 66, 7931. (48) Takenaka, M. (Takasago Int. Corp.), patent, JP 2006-63028A, 2006. (49) (a) XylBINAP - DAIPEN; Ohkuma, T.; Koizumi, M.; Doucet, H.; Pham, T.; Kozawa, M.; Murata, K.; Katayama, E.; Yokozawa, T.; Ikariya, T.; Noyori, R. J. Am. Chem. Soc. 1998, 120, 13529. (b) TolBINAP - DPEN; See ref. 9. (50) Ohkuma, T.; Koizumi, M.; Yoshida, M.; Noyori, R. Org. Lett. 2000, 2, 1749. (51) (a) Ohkuma, T.; Koizumi, M.; Ikehira, H.; Yokozawa, T.; Noyori, R. Org. Lett. 2000, 2, 659. (b) see ref. 23f.

29

(52) (a) Ohkuma, H.; Ikehira, H.; Ikariya, T.; Noyori, R. Synlett. 1997, 467. (b) See ref. 9. (53) Matsumoto, T.; Murayama, T.; Mitsuhashi, S.; Miura, T. Tetrahedron Lett. 1999, 40, 5043. (54) Ohkuma, T.; Ooka, H.; Yamakawa, M.; Ikariya, T.; Noyori, R. J. Org. Chem. 1996, 61, 4872. (55) Ohkuma, T.; Koizumi, M.; Muňiz, K.; Hilt, G.; Kabuto, C.; Noyori, R. J. Am. Chem. Soc. 2002, 124, 6508. (56) (a) Zhang, X.; Uemura, T.; Matsumura, K.; Sayo, N.; Kumobayashi, H.; Takaya, H. Synlett 1994, 501. (b) Uemura, T.; Zhang, X.; Matsumura, K.; Sayo, N.; Kumobayashi, H.; Ohta, T.; Nozaki, K.; Takaya, H. J. Org.

Chem. 1996, 61, 5510. (c) see ref. 23b. (57) Takaya, H.; Ohta, T.; Sayo, N.; Kumobayashi, H.; Akutagawa, S.; Inoue, S.; Kasahara, I.; Noyori, R. J. Am. Chem. Soc. 1987, 109, 1596. (58) SEGPHOS / Ru; (a) Okeda, Y.; Hashimoto, T.; Hori, Y.; Hagiwara, T. (Takasago Int. Corp.), patent, US 006043380A, 1999. BINAP / Ru; (b) Ohta, T.; Miyake, T.; Takaya, H. J. Chem. Soc. Chem. Commun. 1992, 1725. (c)Ohta, T.; Miyake, T.; Seido, N.; Kumobayashi, H.; Takaya, H. J. Org. Chem. 1995, 60, 357. (59) Griesbeck, A.; Seebach, D. Helvetica Chim. Acta 1987, 70, 1326. (60) Schmidt, U.; Langner, J.; Kirchbaum, B.; Braun, C. Synthesis 1994, 1138. (61) Direct Reductive Amination; (a) Matsumura, K.; Saito, T. (Takasago Int. Corp.), patent, WO 2005/028419 A3, 2004. (b) Bunlaksananusorn, T.; Rampf, F. Synlett 2005, 2682. Hydrogenation of Enamino Esters; (c) Matsumura, K.; Zhang, X.; Saito, T. (Takasago Int. Corp.), patent, US 2004/0023344 A1, 2003. (d) Hsiao, Y.; Rivera, N. R.; Rosner, T.; Krska, S. W.; Njolito, E.; Wang, F.; Sun, Y.; Armstrong, J. D. III; Grabowski, E. J. J.; Tillyer, R. D.; Spindler, F.; Malan, C. J. Am. Chem. Soc. 2004,

126, 9918. (62) Zhang, X.; Takenaka, M.; Kuriyama. W. (Takasago Int. Corp.), patent, JP 2005-281144A, 2005. (63) Mashima, K.; Yamagata, T.; Osada, M.; Matsumura, K. (Takasago Int. Corp.), patent, JP 2004-256460A, 2004. (64) Mashima, K.; Yamagata, T. patent, WO 2006/022020 A1, 2006. (65) Suto, Y.; Tsuji, R.; Kanai, M.; Shibasaki, M. Org. Lett. 2005, 7, 3757. (66) Tomita, D.; Wada, R.; Kanai, M.; Shibasaki, M. J. Am. Chem. Soc. 2005, 127, 4138. (67) Hamashima, Y.; Sasamoto, N.; Hotta, D.; Somei, H.; Umebayashi, N.; Sodeoka, M. Angew. Chem. Int. Ed. 2005, 44, 1525. (68) Suto, Y.; Kanai, M.; Shibasaki, M. J. Am. Chem. Soc. 2007, 129, 500. (69) (a) Hamashima, Y.; Yagi, K.; Takano, H.; Tamás, L.; Sodeoka, M. J. Am. Chem. Soc. 2002, 124, 14530. (b) Suzuki, T.; Goto, T.; Hamashima, Y.; Sodeoka, M. J. Org. Chem. 2007, 72, 246. (70) Sodeoka, M.; Hamashima, Y. JP2005-60340. (71) (a) Lipshutz, B. H.; Lower, A.; Noson, K. Org Lett. 2002, 4, 4045. (b) Lipshutz, B. H.; Noson, K.; Chrisman, W.; Lower, A. J. Am. Chem. Soc. 2003, 125, 8779. (c) Lipshutz, B. H.; Lower, A.; Kucejko, R. J.; Noson, K. Org. Lett. 2006, 8, 2969. (72) (a) Lipshutz, B. H.; Servesko, J. M.; Petersen, T. B.; Papa, P. P.; Lover, A. A. Org. Lett. 2004, 6, 1273. (b) Lipshutz, B. H.; Servesko, J. M.; Taft, B. R. J. Am. Chem. Soc. 2004, 126, 8352. (73) Lipshutz, B. H.; Shimizu, H. Angew. Chem. Int. Ed. 2004, 43, 2228. (74) Lam, H. W.; Joensuu, P. M. Org. Lett. 2005, 7, 4225. (75) Zhao, D.; Oisaki, K.; Kanai. M.; Shibasaki, M. J. Am. Chem. Soc. 2006, 128, 14440. (76) (a) Kitagawa, O.; Takahashi, M.; Yoshikawa, M.; Taguchi, T. J. Am. Chem. Soc. 2005, 127, 3676. (b) Kitagawa, O.; Yoshikawa, M.; Tanabe, H.; Morita, T.; Takahashi, M.; Dobashi, Y.; Taguchi, T. J. Am. Chem. Soc. 2006, 128, 12923. (77) For 3-(Triplebonds); (a) Nishida, G.; Suzuki, N.; Noguchi, K.; Tanaka, K. Org. Lett. 2006, 8, 3489.; For 2- (Triplebonds) + 1-(Doublebond); (b) Shibata, T.; Arai, Y.; Tahara, Y.-K. Org. Lett. 2005, 7, 4955. (c) Tanaka, K.; Wada, A.; Noguchi, K. Org. Lett. 2005, 7, 4737.; For 1-(Triplebond) + 1-(Doublebonds); (d) Shibata, T.; Tahara, Y.-K. J. Am. Chem. Soc. 2006, 128, 11766. (78) Daidouji, K.; Fuchibe, K.; Akiyama, T. Org. Lett. 2005, 7, 1051. (79) Oderaotoshi, Y.; Cheng, W.; Fujitomi, S.; Kasano, Y.; Minakata, S.; Komatsu, M. Org. Lett. 2003, 5, 5043. (80) Yamamoto, Y.; Yamamoto, H. J. Am. Chem. Soc. 2004, 126, 4128. (81) Hatano, M.; Terada, M.; Mikami, K. Angew. Chem. Int. Ed. 2001, 40, 249. (82) Mikami, K.; Aikawa, K.; Kainuma, S.; Kawakami, Y.; Saito, T.; Sayo, N.; Kumobayashi, H. Tetrahedron Asymmetry 2004, 15, 3885. (83) Corkey, B. K.; Toste, F. D. J. Am. Chem. Soc. 2005, 127, 17168. (84) (a) Ogasawara, M.; Ueyama, K.; Nagano, T.; Mizuhara, Y.; Hayashi, T. Org. Lett. 2003, 5, 217. (b) Imada, Y,; Nishida, M,; Kutsuwa, K,; Murahashi, S.-I.; Naota, T, Org. Lett. 2005, 7, 5837. (85) Chen, G.; Tokunaga, N.; Hayashi, T. Org. Lett., 2005, 7 2285. (86) Hayashi, T.; Tokunaga, N.; Inoue, K. Org. Lett. 2004, 6, 305 (87) Hayashi, T.; Kawai, M.; Tokunaga, N. Angew. Chem. Int. Ed. 2004, 43, 6125. (88) Johansson, M. J.; Gorin, D. J.; Staben, S. T.; Toste, F. D. J. Am. Chem. Soc. 2005, 127, 18002. (89) Matsuda, T.; Shigeno, M.; Makino, M.; Murakami, M. Org. Lett. 2006, 8, 3379

30

Products Referenced in the Article PHOSPHORUS (Compounds)

15-0066

(R)-(-)-5,5'-Bis[di(3,5-di-t-butyl-4- methoxyphenyl)phosphino]-4,4'- bi-1,3-benzodioxole, min. 98% (R)-DTBM-SEGPHOS [566940-03-2] C74H100O8P2; FW: 1179.53; off-white pwdr. Note: Manufactured under license of Takasago patent. Takasago SEGPHOS Ligand Kit component see (page 52).

50mg250mg

Technical Notes: 1. Biaryl bisphosphine ligand with a narrow dihedral angle. The DTBM SEGPHOS ligand, as the

ruthenium complex, gives superior enantioselectivity and diastereoselectivity through dynamic kinetic resolution in the asymmetric hydrogenation of α-substituted-β-ketoesters useful in the synthesis of carbapenum antibiotics.

2. With rhodium, preferential enantioselective hydrogenation of more reactive olefin of extended enone structure.

3. With copper, enantioselective 1,2-reduction of heteraromatic ketones. 4. Rhodium-catalyzed chemo-, regio, and entantioselective [2 + 2 + 2] cycloaddition of alkynes with

isocyanates. 5. With copper, enantioselective cross Aldol-type reaction of acetonitrile. 6. With copper, enantioselective vinylsilane alkenylation of aldehydes 7. Gold carbene mediated stereoselective cyclopropanation of propargyl esters. 8. With copper, enantioselective 1,4-reduction of α,β-unsaturated esters. 9. Enantioselective fluorination of β-keto esters with Sodeoka's Pd-aqua complex and a fluorinating reagent. Tech. Note (1) Ref. (1)

Tech. Note (2) Ref. (2) Tech. Note (3) Ref. (3) Tech. Note (4) Ref. (4) Tech. Note (5) Ref. (5)

O

O

O

O

P

P

C(CH3)3

C(CH3)3

C(CH3)3

C(CH3)3

OCH3

OCH3

2

2

H2 30 Atm, 50° 18 hr

0.02mol% (+)L, Rh(COD)2THF, R4PBr

O O

89%, 98% ee

O

CO2CH3H2, Ru-(+)L*

99.4% ee, 98.6% deNHCOC6H5

CO2CH3

NHCOC6H5

OH

NH

OAc

O

OTBS

Toluene, -50° 4 hr; NaOH

0.05 mol% (-)L, CuClNaO-t-Bu, -(MeHSiO)n-

N

SO

N

SH OH

94%, 99% ee

Cl

*

O

NBz

N

Cl

O

Bz

5% [Rh(cod)2]BF4(-)L, CH2Cl2, -20°C, 12-36 h

81%, 87%ee

+

O

HCH3CN, 19 equiv.10 mol% CuO-t-Bu

(-)L 15 mol%, HMPA

OH

CN

91%, 75% ee

31

Products Referenced in the Article

PHOSPHORUS (Compounds)

15-0066 (cont.)

(R)-(-)-5,5'-Bis[di(3,5-di-t-butyl-4-methoxyphenyl)phosphino]-4,4'-bi-1,3-benzodioxole, min. 98% (R)-DTBM-SEGPHOS [566940-03-2]

Tech. Note (6) Ref. (6)


Tech. Note (8) Ref. (8) Tech. Note (9)

Ref. (9)

References: 1. Adv. Synth. Cat., 2001, 343, 264. 2. U.S. Pat. 6342644. 3. Org. Lett. 2002, 4, 4045. 4. Org. Lett. 2005, 7, 4737. 5. Org. Lett. 2005, 7, 3757. 6. J. Am. Chem. Soc., 2005, 127, 4138. 7. J. Am. Chem. Soc., 2005, 127, 18002. 8. J. Am. Chem. Soc., 2004, 126, 8352. 9. J. Am. Chem. Soc., 2002, 124, 14530.

15-0067

(S)-(+)-5,5'-Bis[di(3,5-di-t-butyl-4-methoxyphenyl) phosphino]-4,4'-bi-1,3-benzodioxole, min. 98% (S)-DTBM-SEGPHOS [210169-40-7] C74H100O8P2; FW: 1179.53; off-white pwdr. Note: Manufactured under license of Takasago patent. Takasago SEGPHOS Ligand Kit component see (page 52).

50mg250mg

Technical Note: 1. See 15-0066 (page 30).

15-0136

(R)-(+)-5,5'-Bis(diphenylphosphino)- 4,4'-bi-1,3-benzodioxole, min. 98% (R)-SEGPHOS [244261-66-3] C38H28O4P2; FW: 610.57; off-white pwdr. Note: Manufactured under license of Takasago patent. Takasago SEGPHOS Ligand Kit component see (page 52).

50mg250mg

Technical Notes: 1. Biaryl bisphosphine ligand with narrow dihedral angle. The SEGPHOS ligand has been applied to a

variety of metal-catalyzed reactions. In many cases, yields and enantioselectivities, exceed results obtained earlier using BINAP. (Ref 1, 2)

2. As the ruthenium complex, SEGPHOS generally gives higher levels of chiral induction in asymmetric hydrogenations of α, β, and γ functionalized ketones. See ruthenium complexes 44-0096 (page 41),

44-0518 (page 48), 44-0168 (page 43).

P(C6H5)2

P(C6H5)2

O

O

O

O

OPiv

ArAr=2,6-Me-4-t-Bu-Ph

2.5% L(AuCl)2,5% AgSbF6, MeNO2, rt

ArPivO

+

71%, 94%ee

CHO + ViSi(OMe)3

OH1) 3 mol% CuF2.2H2O6 mol% (-)L, DMF, 40°, 8 h;

2) TBAF

99%, 99%ee

PhPh

O

OEt

O

OEt

H

0.7 mol% [Ph3PCuH]60.2 mol% L, PMHS

t-BuOH, 0°, 19 h

97%, 99%ee

*

O

CO2-t-Bu

O

CO2-t-Bu

1.5Eq PhSO2NHF,5 mol% [LPd(OH2)2]2+ 2TfO-

acetone, 10° 2d

93%, 92%ee

F*

32



15-0136 (cont.)

(R)-(+)-5,5'-Bis(diphenylphosphino)-4,4'-bi-1,3-benzodioxole, min. 98% (R)-SEGPHOS [244261-66-3]

3. As ruthenium complex, asymmetric hydrogenation of α-substituted-β-ketoesters accompanied by dynamic kinetic resolution.

4. Copper-catalyzed asymmetric 1,3-dipolar cycloaddition of azomethine ylides. 5. Rhodium-catalyzed 1,4-addition of arylboronic acids to coumarins. 6. Palladium-catalyzed enantioselective cycloaddition of a 1,6-enyne. 7. Rhodium-catalyzed asymmetric addition of aryl titanium reagents to imines. 8. Copper-catalyzed nitroso Diels-Alder reaction. 9. Iridium-catalyzed asymmetric hydrogenation of quinolines activated by chloroformates. 10. Enantioselective copper-catalyzed reductive aldol condensation to produce β-hydroxylactones








O O

OMe

O

OMe

OH

H2, Ru-L

99.5% ee, 97.7% de

Ph N CO2Me

PhN OO

+

HN

NPh

Ph CO2Me

O O

L, Cu(OTf)2, NEt3CH2Cl2, -40 °

78%, 72%ee, 85/15 exo/endo

Rh(acac)(C2H4)2/L

88%, 99.6% eeO O

+ PhB(OH)2

O O

Ph

O O

CO2Me

CO2Me5% Pd(CO2CF3)2/ LC6D6, 37 h, 100°

>99%, >99%ee

NSO2{C6H2(iPr)3}

H

F3C+ PhTi(OiPr)3

RhCl(C2H4)2/ (-)L3 mol% Rh

THF, 1h 20°

HNSO2Ar

Ph

F3C

98%, 93%ee

N

IrCl(COD)2/(-)LClCO2Bn/Li2CO3/THF

H2 600 psi, rt NCO2Bn

90%, 90%ee

NN

O

+

CuPF6(MeCN)4/(-)L10 mol%, CH2Cl2

-85° to -20° 5 h NN

O

99%, 92% ee

33

R1O R2

OO

R1O R2

O OH>98% ee

R

OOH R OH

OH92% ee

Products Referencd in the Article


15-0136 (cont.)

(R)-(+)-5,5'-Bis(diphenylphosphino)-4,4'-bi-1,3-benzodioxole, min. 98% (R)-SEGPHOS [244261-66-3]

Tech Note (10) Ref. (9)

References: 1. Tetrahedron, 2005, 61, 5405. 2. Topics Organometal. Chem., 2004, 6, 63. 3. Org. Lett., 2003, 5, 5043. 4. Org. Lett., 2005, 7, 2285. 5. Angew. Chem. Int. Ed., 2001, 40, 249. 6. Angew. Chem. Int. Ed., 2004, 43, 6125. 7. J. Am. Chem. Soc., 2004, 126, 4128. 8. Angew. Chem. Int. Ed., 2006, 45, 2260. 9. Org. Lett., 2005, 7, 4225.

15-0137

(S)-(-)-5,5'-Bis(diphenylphosphino)-4,4'-bi-1,3-benzodioxole, min. 98% (S)-SEGPHOS [210169-54-3] C38H28O4P2; FW: 610.57; off-white pwdr. Note: Manufactured under license of Takasago patent. Takasago SEGPHOS Ligand Kit component see (page 52).

50mg250mg


15-0150 (R)-(+)-2,2'-Bis(diphenylphosphino)-1, 1'-binaphthyl, 98% (R)-BINAP [76189-55-4] C44H32P2; FW: 622.70; white to light yellow xtl.; [α]D +224.5° (c 0.7, C6H6); m.p. 240.5-242° Note: Manufactured under license of Takasago patent. Takasago BINAP Ligand Kit component see (page 53).

250mg 1g 5g

Technical Notes: 1. (R)-BINAP or (R)-Tol-BINAP can be combined with dichloro(1,5-cyclooctadiene)ruthenium to form

precursors to NOYORI CATALYST SYSTEMS. These systems exhibit very high catalytic activity and enantioselectivity in the hydrogenation of a wide range of substrates. NOYORI CATALYST SYSTEMS have been shown to effect highly enantioselective hydrogenation of functionalized ketones where the substituents are dialkylamino, hydroxy, siloxy, carbonyl, ester, amide or thioester.

2. Useful ligand in asymmetric Heck processes. 3. Useful as a ligand in Pd-catalyzed asymmetric arylation of ketones. (Ref. 7) 4. Useful as a ligand in Rh-catalyzed asymmetric 1,4-additions to enones. (Ref. 8) 5. Catalyst for the hydroamination of styrene derivatives. 6. Ligand employed in silver-catalyzed asymmetric Sakurai-Hosomi allylation and Mukaiyama Aldol

reaction. 7. Ligand used in rhodium-catalyzed kinetic resolution of enynes. 8. Ligand used in asymmetric, rhodium-catalyzed hydroboration of cyclopropenes. 9. Ligand employed in the silver-catalyzed α-hydroxylation of stannyl enol ethers.

10. Ligand used in palladium-catalyzed synthesis of axially chiral allenes. 11. Ligand for Palladium-catalyzed enantioselective hetero Michael addition to form β-amino acid

derivatives. Tech. Note (1) Ref. (1-5)

P(C6H5)2

P(C6H5)2

5 mol% Cu(OAc)2.H2O, (S)-L

TMDS, THF, rt, 24 h

73%, 82%ee

ClC6H4

O

O

O

ClC6H4

O

OHO

34

I

N

MeO

Me

O

Me

OTIPS

NO

CHOMeMeO1) 10% Pd2(DBA)3 CHCl323% (S)-BINAP

Base, DMA, 100o C2) 3N HCl Me

CF3F3C

NHAr

MeArNH2 +10% [(R)-BINAP]Pd(OTf)2

80% yield81% ee

t-Bu

OSi(OMe)3t-Bu

O OH

PhPhCHO

cat. AgOTf BINAP

KF18-crown-6 MeOH

**+

84% yield>99/1 syn/anti97% ee

R

O

OH R OH

OH98% ee

Si(OMe)3Ph

OHPhCHO

cat. AgOTf BINAP

KF18-crown-6 MeOH

+

61% yield90% ee

*

OH

O OO OH

OAgSbF6

[Rh(cod)Cl]2 BINAP

+

99% ee 99% ee(racemic)

OSnBu3

Ph NO

OO NPh

H

OHOCuSO4

MeOH

cat. AgClO4 BINAP

THF-78o C

+ * *

OB

OH

OB O

Hcat. [Rh(cod)Cl]2 BINAP

THF, rt+ *

96% yield94% ee

CO2MeMe MeO2CMe

PhBr H N

EtO2C CO2Et

O

CH3 Ph

CO2EtEtO2C

NH

Ac

cat. Pd2(dba)3 BINAP

CsOtBuCH2Cl2

+

75% yield89% ee


15-0150 (cont.)

(R)-(+)-2,2'-Bis(diphenylphosphino)-1,1'-binaphthyl, 98% (R)-BINAP [76189-55-4]

Tech. Note (1) Ref. (1-5) Tech. Note (2) Ref. (5) Tech. Note (5) Ref. (9) Tech. Note (6) Ref. (10) Tech. Note (6) Ref. (10) Tech. Note (7) Ref. (11) Tech. Note (8) Ref. (12) Tech. Note (9) Ref. (13) Tech. Note (10) Ref. (14)

35


15-0150 (cont.)

(R)-(+)-2,2'-Bis(diphenylphosphino)-1,1'-binaphthyl, 98% (R)-BINAP [76189-55-4]

Tech. Note (11) Ref. (15) References:

1. CHEMTECH, 1992, 360. 2. Asymmetric Catalysis in Organic Synthesis, 1993, 61. 3. J. Am. Chem. Soc., 1988, 110, 629.

4. Science, 1990, 248, 1194. 5. J. Am. Chem. Soc., 1998, 120, 6477; 6488. 6. Encyclopedia of Reagents for Organic Synthesis, 1995, Vol. 1, 509. 7. J. Am. Chem. Soc., 1998, 120, 1918. 8. J. Am. Chem. Soc., 1998, 120, 5579. 9. J. Am. Chem. Soc., 2000, 122, 9547.

10. J. Org. Chem., 2003, 68, 5593. 11. J. Am. Chem. Soc., 2003, 125, 11472. 12. J. Am. Chem. Soc., 2003, 125, 7198. 13. J. Am. Chem. Soc., 2003, 125, 6038. 14. J. Am. Chem. Soc., 2001, 123, 2089. 15. US Patent Application US2006/0205968.

15-0151 (S)-(-)-2,2'-Bis(diphenylphosphino)-1,1'-binaphthyl, 97% (S)-BINAP [76189-56-5] C44H32P2; FW: 622.70; white to light yellow xtl.; [α]D -228° (c 0.68, C6H6); m.p. 241-242° Note: Manufactured under license of Takasago patent. Takasago BINAP Ligand Kit component see (page 53).

250mg 1g 5g


15-2972

(R)-(+)-2,2'-Bis(diphenylphosphino)- 5,5',6,6',7,7',8,8'-octahydro-1,1'- binaphthyl (R)-H8-BINAP [139139-86-9] C44H40P2; FW: 630.74; off-white pwdr. Note: Manufactured under license of Takasago patent. Takasago BINAP Ligand Kit component see (page 53).

50mg 250mg

Technical Notes: 1. Biaryl bisphosphine ligand. The H8-BINAP ligand, as the ruthenium complex, catalyzes hydrogenation

of unsaturated carboxylic acids to a higher ee than does BINAP. (Ref. 1,2) 2. The ruthenium-catalyzed hydrogenation of aryl propenoic acid to produce the drug Ibuprofen. 3. Rhodium-catalyzed asymmetric regioselective 1,4-addition of arylboronic acids to 3-substituted

maleimides.

Tech. Note (1,2) Ref. (1,2)

P(C6H5)2

P(C6H5)2

anisidine triflate0.5 mol% [PdL(OH)2]2(OTf)2N O

O O

ON

OOMeOC6H4NH

THF, rt, 12 h

*

92%, 98%ee

0.5 mol% [(S)-L]Ru(OAc)2100 atm H2, MeOH, 8 h, rt

COOH COOH

97%, 97%ee

36

Br

OH

R R'( )n O R'

R( )n

Pd(OAc)2 (5 mol%), tol-BINAP (6 mol%)

K2CO3, 100oC

t-Bu Br

O O

t-Bu

1.5 mol%Pd2(dba)3

3.6 mol%tol-BINAPNaO-t-Bu

+

CH2CH2Ph

O O

CH2CH2Ph

5% CuCl, 5% NaO-t-Bu,5% (S)-p-tol-BINAP

1.05 eq. PMHS, 0o C

86%, 94% ee



15-2972 (cont.)

(R)-(+)-2,2'-Bis(diphenylphosphino)-5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthyl (R)-H8-BINAP [139139-86-9]


References: 1. J. Org. Chem., 1996, 61, 5510. 2. Topics Organometal. Chem. 2004, 6, 63 (review). 3. J. Am. Chem. Soc., 2006, 128, 5628.

15-2973

(S)-(-)-2,2'-Bis(diphenylphosphino)-5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthyl (S)-H8-BINAP [139139-93-8] C44H40P2; FW: 630.74; off-white pwdr. Note: Manufactured under license of Takasago patent. Takasago BINAP Ligand Kit component see (page 53).

50mg 250mg


15-0152 (R)-(+)-2,2'-Bis(di-p-tolylphosphino)-1,1'-binaphthyl, 98% (R)-Tol-BINAP [99646-28-3] C48H40P2; FW: 678.79; white pwdr.; [α]D +156° (c 0.5, C6H6); m.p. 255-257° Note: Manufactured under license of Takasago patent. Takasago BINAP Ligand Kit component see (page 53).

250mg 1g

Technical Notes: 1. See 15-0150 (page 33). 2. Useful ligand for palladium-catalyzed carbon-oxygen bond formation. 3. Ligand for palladium-catalyzed α-arylation of ketones. 4. Ligand for Cu-catalyzed asymmetric conjugate reduction. 5. Ligand for Cu-catalyzed asymmetric dienolate addition to aldehydes. 6. Enantioselective conjugate reduction of lactones and lactams. 7. Ligand used in the enantioselective cycloaddition of allenylsilanes with α-Imino esters. 8. Catalytic Aldol reaction to ketones. 9. Ligand with rhodium catalyses [2+2+2] cycloaddition reaction of alkenes and alkynes.




P(C6H4CH3)2

P(C6H4CH3)2

2.5 mol% [RhCl(C2H4)2]2L, KOH, dioxane/H2O 10:1

87%, >97%ee

+ PhB(OH)2

3h, 50°

NBn

Et

O

O

NBn

O

OEt

Ph

37

O

O

Bu

O

O

Bu

CuCl2.H2O, (S)-p-Tol-BINAPt-BuONa, PMHS

Toluene, i-PrOH -20o C

OMe

SiMe3

N

EtO2C

TsN

Ts OMeSiMe3

EtO2C

(R)-Tol-BINAP[Cu(MeCN)4]BF4

THF, MS4A+

MeO

Me Me OMe

O

Ph

OH

Me

OMe

OTMS

Ph

1) CuF 3PPh3 2EtOH (S)-p-Tol-BINAP

THF, -20o C, 24 h

2) 3HF.NEt3 99%, 82% ee

, (EtO)3SiF

O O

OSiMe3

MeMeO O

O

MeMe

Ph

OHPhCHO

2% (S)-p-tol-BINAP CuF2 THF, -78o C

+

92%, 94% ee



15-0152 (cont.)

(R)-(+)-2,2'-Bis(di-p-tolyl-phosphino)-1,1'-binaphthyl, 98% (R)-Tol-BINAP [99646-28-3]


Tech. Note (6) Ref. (5) Tech. Note (7) Ref. (6) Tech. Note (8) Ref. (7)


References: 1. J. Am. Chem. Soc., 1996, 118, 10333.

2. J. Am. Chem. Soc., 1997, 119, 11108. 3. J. Am. Chem. Soc., 2000, 122, 6797. 4. J. Am. Chem. Soc., 1998, 120, 837. 5. J. Am. Chem. Soc., 2003, 125, 11253. 6. Org. Lett., 2003, 5(20), 3691. 7. J. Am. Chem. Soc., 2003, 125, 5644. 8. Org. Lett., 2005, 7(22), 4955.

15-0153 (S)-(-)-2,2'-Bis(di-p-tolylphosphino)-1,1'-binaphthyl, 98% (S)-Tol-BINAP [100165-88-6] C48H40P2; FW: 678.79; white pwdr.; [α]D -160° (c 0.5, C6H6); m.p. 255-257° Note: Manufactured under license of Takasago patent. Takasago BINAP Ligand Kit component see (page 53).

250mg 1g

Technical Notes: 1. See 15-0150 (page 33). 2. See 15-0152 (page 36).

TsN +

OMe

OMe

10 mol% [Rh(cod)2]BF4, L,

DCE, 12h 60° OMe

OMeTsN

81% 97% ee

*

38


15-0478

(R)-(+)-5,5'-Bis[di(3,5-xylyl) phosphino]-4,4'-bi-1,3-benzodioxole, min. 98% (R)-DM-SEGPHOS [850253-53-1] C46H44O4P2; FW: 722.79; off-white to pale yellow pwdr. Note: Manufactured under license of Takasago patent. Takasago SEGPHOS Ligand Kit component see (page 52).

50mg250mg

Technical Notes: 1. Biaryl bisphosphine ligand with narrow dihedral angle. The DM-SEGPHOS ligand, as the ruthenium

complex, gives superior enantioselectivity and diastereoselectivity in the asymmetric hydrogenation of α-substituted-β-ketoesters. See 15-0066 (page 30).

2. Copper-catalyzed enantioselective [3 + 2] cycloaddition as a route to γ–amino ketones and 3-pyrrolidinones.

3. Palladium-catalyzed enantioselective addition of malonates to dihydroisoquinolines. 4. Ruthenium-catalyzed enantioselective synthesis of β amino acids by hydrogenation. 5. Ruthenium-catalyzed asymmetric hydrogenation of 3-quinuclidinone. See 44-0098 (page 42) for Ru

catalyst.





References: 1. Org. Lett., 2005, 7, 1051. 2. J. Am. Chem. Soc., 2006, 128, 14010. 3. WIPO Pat. WO2005028419. 4. U.S. Pat. App. 2006047122.

15-0479

(S)-(-)-5,5'-Bis[di(3,5-xylyl)phosphino]-4,4'-bi-1,3-benzodioxole, min. 98% (S)-DM-SEGPHOS [210169-57-6] C46H44O4P2; FW: 722.79; off-white to pale yellow pwdr. Note: Manufactured under license of Takasago patent. Takasago SEGPHOS Ligand Kit component see (page 52).

50mg250mg


P[C6H3(CH3)2]2P[C6H3(CH3)2]2

O

O

O

O

∗Si(t-Bu)Me2

CH3

EtO2C H

NTs

+NEtO2C

Ts

Si(t-Bu)Me2

10 mol% [Cu(MeCN)4]BF4/(+)L; Bz, reflux, 3h

90%, 75% ee

N

OMe

MeONH

OMe

MeO

CO2RRO2C

1) (Boc)2O2) H2C(CO2R)2

(+L)Pd(OH2)2(OTf)2 1h, 0°, CH2Cl2

92%, 97%ee

OCH3

OO

OCH3

ONH20.1 mol% [RuCl2(p-cymene)]20.2 mol% L, NH4OAc, dioxane,H2 30 atm. 85°, 8 h

87%, 94% ee

+ H2 IPA/t-BuOK 30 Atm, 30° 15 hr

0.1% (LRuCyCl)+Cl-, 0.4% (R)-DAIPEN

N

O

N

OH

99%, 91% ee

39

Me

ONMe2 Me

OHNMe2H2

catalyst

*

NO

EtOO

Ph NO

EtOO

PhH

NuNu

Cu - cat. / L(10 mol %)

*

76-81% yield79-97% ee

N

Ph

O

BOC

catalystNFSI

NO

BOC

PhF



15-0476 (R)-(+)-2,2'-Bis[di(3,5-xylyl) phosphino]-1,1'-binaphthyl, 98% (R)-3,5-xylyl-BINAP [137219-86-4] C52H48P2; FW: 734.90; white to pale yellow xtl.; m.p. 203-206° Note: Manufactured under license of Takasago patent. Takasago BINAP Ligand Kit component see (page 53).

50mg 250mg

Technical Notes: 1. See 15-0150 (page 33). 2. Ligand used in the asymmetric hydrogenation of amino ketones. 3. Ligand used with ruthenium in the synthesis of β-amino acids by hydrogenation. See 44-0164

(page 45). Tech. Note (2)

Tech. Note (3)

References:

1. J. Am. Chem. Soc., 2000, 122, 6510. 2. World Patent WO2005/028419.

15-0477 (S)-(-)-2,2'-Bis[di(3,5-xylyl)phosphino]-1,1'-binaphthyl, 98% (S)-3,5-xylyl-BINAP [135139-00-3] C52H48P2; FW: 734.90; white to pale yellow xtl.; m.p. 203-206° Note: Manufactured under license of Takasago patent. Takasago BINAP Ligand Kit component see (page 53).

50mg 250mg

Technical Notes: 1. See 15-0150 (page 33). 2. See 15-0476 (page 39). 3. Ligand used in copper-catalyzed asymmetric Mannich-type reactions of N-acylimino esters. 4. Ligand used in the enantioselective fluorination of oxindoles.

Tech. Note (3) Ref. (1) Tech. Note (4) Ref. (2) References: 1. J. Am. Chem. Soc., 2003, 125, 2507. 2. J. Am. Chem. Soc., 2005, 127, 10164.

15-1005

Di-t-butyl(2,2-diphenyl-1-methyl- 1-cyclopropyl)phosphine Mo-Phos C24H33P; FW: 352.49; white pwdr. Note: Manufactured under license of Takasago patent.

250mg1g

P[C6H3(CH3)2]2P[C6H3(CH3)2]2

CH3

P C(CH3)3C(CH3)3

H3C OCH3

O O

H3C OCH3

NH2 O0.2 mol% LRu(OAc)2NH4OAc, MeOH,30 Atm H2 MeOH, 15 h 80°

86%, 82% ee

40



15-1005 (cont.)

Di-t-butyl(2,2-diphenyl-1-methyl-1-cyclopropyl)phosphine Mo-Phos

Technical Notes: 1. Ligand effective for many classes of palladium-catalyzed coupling of aryl halides, including the

Miyaura-Suzuki, Buchwald-Hartwig, Sonogashira, Heck, aryl etherification, and carbonylation reactions.

2. Ligand used in the palladium-catalyzed Suzuki-Miyaura coupling of aryl boronic acids. 3. Ligand employed in the palladium-catalyzed Buchwald-Hartwig aryl amination reaction.


Reference: Tech. Note (2) 1. US Patent 7129367. Ref. (1)

RUTHENIUM (Compounds)

44-0102

Chloro{(R)-(-)-5,5'-bis [di(3,5-di-t-butyl-4-methoxyphenyl)phosphino]-4,4'- bi-1,3-benzodioxole} (p-cymene) ruthenium(II) chloride [C84H114ClO8P2Ru]+Cl-; FW: 1485.72; orange to brown pwdr. air sensitive Note: Manufactured under license of Takasago patent. Takasago SEGPHOS Catalyst Kit component see (page 52).

50mg250mg


44-0103

Chloro{(S)-(+)-5,5'-bis[di(3,5-di-t-butyl-4-methoxyphenyl) phosphino]-4,4'-bi-1,3-benzodioxole}(p-cymene) ruthenium(II) chloride [C84H114ClO8P2Ru]+Cl-; FW: 1485.72; orange to brown pwdr. air sensitive Note: Manufactured under license of Takasago patent. Takasago SEGPHOS Catalyst Kit component see (page 52).

50mg250mg


O

O

O

O

P

P

H3CO

OCH3

OCH3

H3CO

t-But-Bu

t-Bu

t-Bu

t-But-Bu

t-Bu

t-Bu

Ru

H3C

CH(CH3)2Cl

+

+MeO (HO)2B MeOCl

2 mol% L, (C3H5PdCl)2K3(PO4)3, Toluene, 3 h, 80°

90%

+MeO H2NCl

2.0 mol% L, (C3H5PdCl)2Na-t-OBu, Toluene, 3 h, 100°

95%2

MeO NPh2

41



44-0096

Chloro[(R)-(+)-5,5'-bis(diphenylphosphino)-4,4'-bi- 1,3-benzodioxole] (p-cymene)ruthenium(II) chloride [C48H42ClO4P2Ru]+Cl- yellow pwdr. air sensitive Note: Manufactured under license of Takasago patent. Takasago SEGPHOS Catalyst Kit component see (page 52).

50mg250mg

Technical Notes: 1. Highly active highly enantioselective catalyst for hydrogenation of functionalized ketones. Slightly higher temperature is necessary to activate the cymene complexes. See 15-0136 (page 32).

2. Asymmetric hydrogenation of α-substituted-β-ketoesters accompanied by dynamic kinetic resolution.


Reference: 1. U.S. Pat. 7038087.

44-0097

Chloro[(S)-(-)-5,5'-bis(diphenylphosphino)-4,4'-bi-1,3-benzodioxole](p-cymene)ruthenium(II) chloride [C48H42ClO4P2Ru]+Cl-; FW: 916.77; yellow pwdr. air sensitive Note: Manufactured under license of Takasago patent. Takasago SEGPHOS Catalyst Kit component see (page 52).

50mg250mg


44-0084

Chloro[(R)-(+)-2,2'-bis(diphenylphosphino)-1,1'- binaphthyl](p-cymene) ruthenium(II) chloride [145926-28-9] [C54H46ClP2Ru]+Cl-; FW: 928.87; orange pwdr. air sensitive Note: Manufactured under license of Takasago patent. Takasago BINAP Ru Cymene Catalyst Kit component see (page 53).

250mg 1g


44-0086

Chloro[(S)-(-)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl] (p-cymene)ruthenium(II) chloride [130004-33-0] [C54H46ClP2Ru]+Cl-; FW: 928.87; orange pwdr. air sensitive Note: Manufactured under license of Takasago patent. Takasago BINAP Ru Cymene Catalyst Kit component see (page 53).

250mg 1g


P

PRu

H3C

CH(CH3)2Cl

+

P

PRu

H3C

CH(CH3)2Cl

+

O

O

O

O

+ H220 Atm, 60° 91 hr

0.1% cat., CH2Cl2

O O

OEt

O

OEt

OH

98%, 98% ee, 88%de

42



44-0094

Chloro[(R)-(+)-2,2'-Bis(diphenylphosphino)-5,5',6,6',7,7',8,8'- octahydro-1,1'-binaphthyl] (p-cymene)ruthenium(II) chloride [C54H54ClP2Ru]+Cl-; FW: 936.93; pale yellow pwdr. air sensitive Note: Manufactured under license of Takasago patent. Takasago BINAP Ru Cymene Catalyst Kit component see (page 53).

50mg 250mg


44-0095

Chloro[(S)-(-)-2,2'-bis(diphenylphosphino)-5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthyl](p-cymene)ruthenium(II) chloride [C54H54ClP2Ru]+Cl-; FW: 936.93; pale yellow pwdr. air sensitive Note: Manufactured under license of Takasago patent. Takasago BINAP Ru Cymene Catalyst Kit component see (page 53).

50mg 250mg


44-0088

Chloro[(R)-(+)-2,2'-bis(di-p-tolylphosphino)-1,1'-binaphthyl] (p-cymene)ruthenium(II) chloride [131614-43-2] C58H54Cl2P2Ru; FW: 984.97; brown pwdr. air sensitive Note: Manufactured under license of Takasago patent. Takasago BINAP Ru Cymene Catalyst Kit component see (page 53).

250mg 1g


44-0089

Chloro[(S)-(-)-2,2'-bis(di-p-tolylphosphino)-1,1'-binaphthyl](p-cymene)ruthenium(II) chloride [228120-95-4] [C58H54ClP2Ru]+Cl-; FW: 984.97; brown pwdr. air sensitive Note: Manufactured under license of Takasago patent. Takasago BINAP Ru Cymene Catalyst Kit component see (page 53).

250mg 1g


44-0098

Chloro{(R)-(+)-5,5'-bis[di(3,5-xylyl)phosphino]-4,4'-bi-1,3-benzodioxole}(p-cymene)ruthenium(II) chloride [C56H58ClO4P2Ru]+Cl-; FW: 1028.98; orange to brown pwdr. air sensitive Note: Manufactured under license of Takasago patent. Takasago SEGPHOS Catalyst Kit component see (page 52).

50mg250mg


44-0099

Chloro{(S)-(-)-5,5'-bis[di(3,5-xylyl)phosphino]-4,4'-bi-1,3-benzodioxole}(p-cymene)ruthenium(II) chloride [C56H58ClO4P2Ru]+Cl-; FW: 1028.98; orange to brown pwdr. air sensitive Note: Manufactured under license of Takasago patent. Takasago SEGPHOS Catalyst Kit component see (page 52).

50mg250mg


P

PRu

H3C

CH(CH3)2Cl

+

P

PRu

H3C

CH(CH3)2Cl

+

43

Products Referenced in the Article RUTHENIUM (Compounds)

44-0092

Chloro{(R)-(+)-2,2'-Bis[di(3,5-xylyl) phosphino]-1,1'-binaphthyl} (p-cymene)ruthenium(II) chloride [C62H62ClP2Ru]+Cl-; FW: 1041.08; orange to brown pwdr. air sensitive Note: Manufactured under license of Takasago patent. Takasago BINAP Ru Cymene Catalyst Kit component see (page 53).

50mg 250mg


44-0093

Chloro{(S)-(-)-2,2'-bis[di(3,5-xylyl)phosphino]-1,1'-binaphthyl}(p-cymene)ruthenium(II) chloride [C62H62ClP2Ru]+Cl-; FW: 1041.08; orange to brown pwdr. air sensitive Note: Manufactured under license of Takasago patent. Takasago BINAP Ru Cymene Catalyst Kit component see (page 53).

50mg 250mg


44-0168

Diacetato[(R)-(+)-5,5'-bis(diphenylphosphino)-4,4'-bi-1,3-benzodioxole]ruthenium(II) C42H34O8P2Ru; FW: 829.73 dark yellow pwdr. air sensitive Note: Manufactured under license of Takasago patent. Takasago SEGPHOS Catalyst Kit component see (page 52).

50mg250mg

Technical Notes: 1. Highly active highly enantioselective catalyst for hydrogenation of functionalized ketones. The acetate salts are frequently used for hydrogenation of allyl alcohols, unsaturated carboxylic acids and reductive amination. See 15-0136 (page 31).

2. Asymmetric hydrogenation of substituted allyl alcohols.


Reference: 1. U.S. Pat. 6342644.

44-0169

Diacetato[(S)-(-)-5,5'-bis(diphenylphosphino)-4,4'-bi-1,3-benzodioxole]ruthenium(II) [373650-12-5] C42H34O8P2Ru; FW: 829.73; dark yellow pwdr. air sensitive Note: Manufactured under license of Takasago patent. Takasago SEGPHOS Catalyst Kit component see (page 52).

50mg250mg


P

PRu

H3C

CH(CH3)2Cl

+

P

PRu

O

O

O

O

O

O

OO

CH3

CH3

+ H2OH OH(S)-cat.

33%, 81% ee

44


44-0152

Diacetato[(R)-(+)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl] ruthenium(II) [325146-81-4] C48H38O4P2Ru; FW: 841.83; pale yellow pwdr. air sensitive Note: Manufactured under license of Takasago patent. Takasago BINAP Ru Acetate Catalyst Kit component see (page 54).

250mg 1g


44-0153

Diacetato[(S)-(-)-2,2'-bis(diphenylphosphino)-1,1'- binaphthyl]ruthenium(II) [261948-85-0] C48H38O4P2Ru; FW: 841.83; pale yellow pwdr. air sensitive Note: Manufactured under license of Takasago patent. Takasago BINAP Ru Acetate Catalyst Kit component see (page 54).

250mg 1g


44-0166

Diacetato[(R)-(+)-2,2'-bis(diphenylphosphino)-5,5',6,6', 7,7',8,8'-octahydro-1,1'- binaphthyl]ruthenium(II) [374067-51-3] C48H46O4P2Ru; FW: 849.89; pale orange pwdr. air sensitive Note: Manufactured under license of Takasago patent. Takasago BINAP Ru Acetate Catalyst Kit component see (page 54).

50mg 250mg


44-0167

Diacetato[(S)-(-)-2,2'-bis(diphenylphosphino)-5,5',6,6', 7,7',8,8'-octahydro-1,1'-binaphthyl]ruthenium(II) [142962-95-6] C48H46O4P2Ru; FW: 849.89; pale orange pwdr. air sensitive Note: Manufactured under license of Takasago patent. Takasago BINAP Ru Acetate Catalyst Kit component see (page 54).

50mg 250mg


44-0162

Diacetato[(R)-(+)-2,2'-bis(di-p- tolylphosphino)-1,1'-binaphthyl] ruthenium(II) [116128-29-1] C52H46O4P2Ru; FW: 897.94 brown pwdr. air sensitive Note: Manufactured under license of Takasago patent. Takasago BINAP Ru Acetate Catalyst Kit component see (page 54).

250mg 1g


P

PRu

O

O

OO

CH3

CH3

P

PRu

O

O

OO

CH3

CH3

P

PRu

O

O

OO

CH3

CH3

45



44-0163

Diacetato[(S)-(-)-2,2'-bis(di-p-tolylphosphino)-1,1'-binaphthyl] ruthenium(II) [106681-15-6] C52H46O4P2Ru; FW: 897.94; brown pwdr. air sensitive Note: Manufactured under license of Takasago patent. Takasago BINAP Ru Acetate Catalyst Kit component see (page 54).

250mg 1g


44-0174

Diacetato{(R)-(+)-5,5'-bis[di(3,5- xylyl)phosphino]-4,4'-bi-1,3- benzodioxole}ruthenium(II) C50H50O8P2Ru; FW: 941.95; orange pwdr. air sensitive Note: Manufactured under license of Takasago patent. Takasago SEGPHOS Catalyst Kit component see (page 52).

50mg250mg


44-0176

Diacetato{(S)-(-)-5,5'-bis[di(3,5-xylyl)phosphino]-4,4'-bi-1,3-benzodioxole}ruthenium(II) C50H50O8P2Ru; FW: 941.95; dark brown pwdr. air sensitive Note: Manufactured under license of Takasago patent. Takasago SEGPHOS Catalyst Kit component see (page 52).

50mg250mg


44-0164

Diacetato{(R)-(+)-2,2'-bis[di(3,5- xylyl)phosphino]-1,1'- binaphthyl}ruthenium(II) [374067-50-2] C56H54O4P2Ru; FW: 954.04 dark brown pwdr. air sensitive Note: Manufactured under license of Takasago patent. Takasago BINAP Ru Acetate Catalyst Kit component see (page 54).

50mg 250mg


44-0165

Diacetato{(S)-(-)-2,2'-bis[di(3,5-xylyl)phosphino]-1,1'-binaphthyl}ruthenium(II) [374067-49-9] C56H54O4P2Ru; FW: 954.04; dark brown pwdr. air sensitive Note: Manufactured under license of Takasago patent. Takasago BINAP Ru Acetate Catalyst Kit component see (page 54).

50mg 250mg


P

P

O

O

O

O

Ru

O

O

OO

CH3

CH3

P

PRu

O

O

OO

CH3

CH3

46


44-0214

Dichloro{(R)-(+)-5,5'-bis[di (3,5-xylyl)phosphino]-4, 4'-bi-1,3-benzodioxole} [(2R)-(-)-1,1-bis(4-methoxyphenyl)-3-methyl-1, 2-butanediamine] ruthenium(II) C65H70Cl2N2O2P2Ru; FW: 1145.19; yellow pwdr. air sensitive Note: Manufactured under license of Takasago patent. Takasago SEGPHOS Catalyst Kit component see (page 52).

50mg250mg

Technical Note: 1 See 15-0478 (page 38).

44-0215

Dichloro{(S)-(-)-5,5'-bis[di(3,5-xylyl)phosphino]-4,4'-bi-1,3-benzodioxole}[(2S)-(+)-1,1-bis(4-methoxyphenyl)-3-methyl-1,2-butanediamine]ruthenium(II) C65H70Cl2N2O2P2Ru; FW: 1145.19; yellow pwdr. air sensitive Note: Manufactured under license of Takasago patent. Takasago SEGPHOS Catalyst Kit component see (page 52).

50mg250mg


44-0228

Dichloro{(R)-(+)-5,5'-bis[di (3,5-xylyl)phosphino]-4,4'- bi-1,3-benzodioxole}[(1R, 2R)-(+)-1,2-diphenylethylenediamine]ruthenium(II) C60H58Cl2N2O2P2Ru; FW: 1073.04; yellow pwdr. air sensitive Note: Manufactured under license of Takasago patent. Takasago SEGPHOS Catalyst Kit component see (page 52).

50mg250mg


44-0229

Dichloro{(S)-(-)-5,5'-bis[di(3,5-xylyl)phosphino]-4,4'-bi-1,3-benzodioxole}[(1S,2S)-(-)-1,2-diphenylethylenediamine] ruthenium(II) C60H58Cl2N2O2P2Ru; FW: 1073.04; yellow pwdr. air sensitive Note: Manufactured under license of Takasago patent. Takasago SEGPHOS Catalyst Kit component see (page 52).

50mg250mg


P

PRu

Cl

Cl N

NH H

H H

O

O

O

O

CH(CH3)2

OCH3

OCH3

P

PRu

Cl

Cl N

NH H

H H

O

O

O

O

47


44-0212

Dichloro{(R)-(+)-2,2'-bis[di (3,5-xylyl)phosphino]-1,1'- binaphthyl}[(2R)-(-)-1,1-bis (4-methoxyphenyl)-3-methyl- 1,2-butanediamine] ruthenium(II) [220114-32-9] C71H74Cl2N2O2P2Ru; FW: 1221.28; orange pwdr. air sensitive Note: Manufactured under license of Takasago patent. Takasago BINAP Ru Diammine Catalyst Kit component see (page 54).

50mg 250mg

Technical Notes: 1. Highly active catalyst for hydrogenation of simple ketones giving high enantioselectivity when sterically unsymmetrical ketones such as acetophenone, heteroaryl ketones, benzophenones, cyclopropyl ketones, and cyclohexyl ketones are substrates. Ee's are enhanced with XylBINAP relative to BINAP. The otherwise poorly bonded ketone is held in the transition state by hydrogen bonding to the protic bidentate amine. 2. Carbonyl groups are selectively reduced even when olefins exist in the same molecule. 3. In the presence of strong base, and catalyst, simple ketones, having substituents at the α-position, may be induced to undergo dynamic kinectic resolution during their hydrogenation to produce two chiral carbon centers in high yield.

Tech. Note (1) Ref. (1-4)



References: 1. Angew Chem. Int. Ed., 2001, 40, 40. (review article) 2. Org. Lett., 2000, 2, 1749. 3. Org. Lett., 2000, 2, 659. 4. J. Am. Chem. Soc., 1998, 120, 13529. 5. J. Am. Chem. Soc., 2000, 122, 6510.

44-0213

Dichloro{(S)-(-)-2,2'-bis[di(3,5-xylyl)phosphino]-1,1'-binaphthyl}[(2S)-(+)-1,1-bis(4-methoxyphenyl)-3-methyl-1,2-butanediamine]ruthenium(II) [220114-01-2] C71H74Cl2N2O2P2Ru; FW: 1221.28; orange pwdr. air sensitive Note: Manufactured under license of Takasago patent. Takasago BINAP Ru Diammine Catalyst Kit component see (page 54).

50mg 250mg


P

PRu

Cl

Cl N

NH H

H H

CH(CH3)2

OCH3

OCH3

O

+ H28 atm, rt 15 hr

0.001 mol% (S,S)-cat., IPA, K2CO3

98%, 97% ee

OH

O

Ph+ H2

8 atm, rt 60 hr

0.001 mol% (S,S)-cat.,IPA, KOC(CH3)

Ph

OH

97%, 99% ee

H2 8 Atm, rt 5 hr

0.30 mol% (R,S)cat.,KOH, i-PrOH

98%, 82% ee

O

NHCO2C(CH3)3

OH

NHCO2C(CH3)3

48


44-0226

Dichloro{(R)-(+)-2,2'-bis[di (3,5-xylyl)phosphino]-1, 1'-binaphthyl}[(1R,2R)-(+)- 1,2-diphenylethylenediamine]ruthenium(II) [220114-38-5] C66H64Cl2N2P2Ru; FW: 1119.15; yellow pwdr. air sensitive Note: Manufactured under license of Takasago patent. Takasago BINAP Ru Diammine Catalyst Kit component see (page 54).

50mg 250mg

Technical Note: 1. See 44-0220 (Visit www.strem.com for details).

44-0224

Dichloro{(S)-(-)-2,2'-bis[di(3,5-xylyl)phosphino]-1,1'-binaphthyl}[(1S,2S)-(-)-1,2-diphenylethylenediamine] ruthenium(II) [220114-03-4] C66H64Cl2N2P2Ru; FW: 1119.15; yellow pwdr. air sensitive Note: Manufactured under license of Takasago patent. Takasago BINAP Ru Diammine Catalyst Kit component see (page 54).

50mg 250mg


44-0518

Dimethylammonium dichlorotri(µ-chloro)bis[(R)-(+)-5,5'-bis(diphenylphosphino)-4,4'-bi-1,3-benzodioxole] diruthenate(II) [346457-41-8] (CH3)2NH2

+[C76H48Cl5O8P4Ru2]-; FW: 1637.57; light brown pwdr. air sensitive Note: Manufactured under license of Takasago patent. Takasago SEGPHOS Catalyst Kit component see (page 52).

50mg250mg

Technical Notes: 1. Highly enantioselective, highly active catalyst for hydrogenation of functionalized ketones. The chlororuthenate salts show catalytic activity at relatively low temperature. See 15-0136 (page 31). 2. Catalyst for enantioselective hydrogenation of enamines.



P

PRu

Cl

Cl N

N

H H

H H

P

PRu

P

PRu

Cl Cl

Cl

Cl

O

O

O

O O

O

O

O

Cl

O

OEt

H2 50 Atm, 50° 17 hr

0.07% cat., EtOH OEt

OH

Ph

O O

Ph

100%, 93.7% ee

O

OH + H230 Atm, 65° 7 hr

0.03% cat., MeOHOH

OH

100%, 99.5% ee

49


44-0518 (cont.)

Dimethylammonium dichlorotri(µ-chloro)bis[(R)-(+)-5,5'-bis(diphenylphosphino)- 4,4'-bi-1,3-benzodioxole]diruthenate(II) [346457-41-8]



References: 1. Adv. Synth. Catal., 2001, 343, 264. 2. U.S. Pat.6608214. 3. U.S. Pat. App. 2006122225.

44-0519

Dimethylammonium dichlorotri(µ-chloro)bis[(S)-(-)-5,5'-bis(diphenylphosphino)-4,4'-bi-1,3-benzodioxole] diruthenate(II) [488809-34-3] (CH3)2NH2

+[C76H48Cl5O8P4Ru2]-; light brown pwdr. air sensitive Note: Manufactured under license of Takasago patent. Takasago SEGPHOS Catalyst Kit component see (page 52).

50mg250mg


44-0510

Dimethylammonium dichlorotri(µ-chloro)bis[(R)-(+)-2,2'-bis (diphenylphosphino)-1,1'-binaphthyl]diruthenate(II) [199684-47-4] (CH3)2NH2

+[C88H64Cl5P4Ru2]-; FW: 1669.83; orange pwdr. air sensitive Note: Manufactured under license of Takasago patent. Takasago BINAP Ru Dimer Catalyst Kit component see (page 53).

250mg 1g


44-0511

Dimethylammonium dichlorotri(µ-chloro)bis[(S)-(-)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl]diruthenate(II) [199541-17-8] (CH3)2NH2

+[C88H64Cl5P4Ru2]-; FW: 1669.83; orange pwdr. air sensitive Note: Manufactured under license of Takasago patent. Takasago BINAP Ru Dimer Catalyst Kit component see (page 53).

250mg 1g


P

PRu

P

PRu

Cl Cl

Cl

Cl

Cl

F3C

NH

Et

CO2Me F3C

NH

Et

CO2Me

Hcat. 0.0005 molH2 5MPa 2 h

100%, 96%ee

OEt

H2 10 Atm, 90° 7 hr

0.10 mol (-)cat., EtOH OEt

O O

BzO

O

BzO

OH87%, 99.1% ee

50


44-0516

Dimethylammonium dichlorotri(µ-chloro)bis[(R)-(+)-2,2'-bis (diphenylphosphino)-5,5',6,6',7,7',8,8'-octahydro-1,1'- binaphthyl]diruthenate(II) [204933-84-6] (CH3)2NH2

+[C88H80Cl5P4Ru2]-; FW: 1685.96; red-brown pwdr. air sensitive Note: Manufactured under license of Takasago patent. Takasago BINAP Ru Dimer Catalyst Kit component see (page 53).

50mg 250mg


44-0517

Dimethylammonium dichlorotri(µ-chloro)bis[(S)-(-)-2,2'-bis(diphenylphosphino)-5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthyl]diruthenate(II) (CH3)2NH2


50mg 250mg


44-0512

Dimethylammonium dichlorotri(µ-chloro)bis[(R)-(+)-2,2'-bis (di-p-tolylphosphino)-1,1'-binaphthyl]diruthenate(II) [749935-02-2] (CH3)2NH2

+[C96H80Cl5P4Ru2]-; FW: 1782.05; brown pwdr. air sensitive Note: Manufactured under license of Takasago patent. Takasago BINAP Ru Dimer Catalyst Kit component see (page 53).

250mg 1g


44-0513

Dimethylammonium dichlorotri(µ-chloro)bis[(S)-(-)-2,2'-bis(di-p-tolylphosphino)-1,1'-binaphthyl]diruthenate(II) [309735-86-2] (CH3)2NH2

+[C96H80Cl5P4Ru2]-; FW: 1782.05; brown pwdr. air sensitive Note: Manufactured under license of Takasago patent. Takasago BINAP Ru Dimer Catalyst Kit component see (page 53).

250mg 1g


P

PRu

P

PRu

Cl Cl

Cl

Cl

Cl

P

PRu

P

PRu

Cl Cl

Cl

Cl

Cl

51


44-0520

Dimethylammonium dichlorotri(µ-chloro)bis{(R)-(+)-5,5'- bis[di(3,5-xylyl)phosphino]-4,4'-bi-1,3-benzodioxole} diruthenate(II) (CH3)2NH2


50mg250mg


44-0521

Dimethylammonium dichlorotri(µ-chloro)bis{(S)-(-)-5,5'-bis[di(3,5-xylyl)phosphino]-4,4'-bi-1,3-benzodioxole}diruthenate(II) (CH3)2NH2


50mg250mg


44-0514

Dimethylammonium dichlorotri(µ-chloro)bis{(R)-(+)-2,2'-bis [di(3,5-xylyl)phosphino]-1,1'-binaphthyl}diruthenate(II) (CH3)2NH2


50mg 250mg


44-0515

Dimethylammonium dichlorotri(µ-chloro)bis{(S)-(-)-2,2'-bis[di(3,5-xylyl)phosphino]-1,1'-binaphthyl}diruthenate(II) (CH3)2NH2


50mg 250mg


P

P

O

O

O

O

P

P

O

O

O

O

Ru Ru

Cl Cl

Cl

Cl

Cl

P

PRu

P

PRu

Cl Cl

Cl

Cl

Cl

52

Kits Containing Products Referenced in the Article SEGPHOS CATALYST and LIGAND KITS manufactured under license of Takasago patent.

O

O

O

O

P

P

SEGPHOSes

Ar

Ar

Ar

Ar

OMe

SEGPHOS DM-SEGPHOS DTBM-SEGPHOS

Ar;

96-6900 Takasago SEGPHOS Ligand Kit kit contains 50mg unit of the 6 R- and S- items listed below Individual items available for sale

R- CAS# S- CAS# Size Size

SEGPHOS 15-0136 244261-66-3 15-0137 210169-54-3 50mg 250mg

DM-SEGPHOS 15-0478 850253-53-1 15-0479 210169-57-6 50mg 250mg

DTBM-SEGHOS 15-0066 566940-03-2 15-0067 210169-40-7 50mg 250mg

96-6901 Takasago SEGPHOS Ru Catalyst Kit Metal Catalysts in the kit are the following type

kit contains 50mg unit of the 18 R- and S- items listed below Individual items available for sale

Metal Catalyst = RuCl[(P-cymene)(L)]Cl

Ligand L= R- CAS# S- CAS# Size Size

SEGPHOS 44-0096 None 44-0097 None 50mg 250mg

DM-SEGPHOS 44-0098 None 44-0099 None 50mg 250mg

DTBM-SEGHOS 44-0102 None 44-0103 None 50mg 250mg

[{RuCl(L)}2(u-Cl)3][NH2Me2]

SEGPHOS 44-0518 346457-41-8 44-0519 488809-34-3 50mg 250mg


Ru(OAc)2(L)

SEGPHOS 44-0168 None 44-0169 373650-12-5 50mg 250mg


Diamine System

RuCl2 [(DM-SEGPHOS) (DAIPEN)]

44-0214 None 44-0215 None 50mg 250mg

RuCl2 [(DM-SEGPHOS) (DPEN)]

44-0228 None 44-0229 None 50mg 250mg

NH2Me2+

[NH2Me2][{RuCl(P^P)}2(μ-Cl)3] (II)

Ru

P

P

Cl

ClCl Cl

Ru

P

P

Cl -

Ru

Cl

PP

ClN

N


Ru

O

PP

OOO

[Ru(OAc)2(P^P)] (III)

RuPP

Cl

Cl-

+


53

Kits Containing Products Referenced in the Article BINAP CATALYST and LIGAND KITS manufactured under license of Takasago Patent.

96-6950 Takasago BINAP Ligand Kit kit contains smallest unit of the 8 R- and S- items listed below Individual items available for sale


BINAP* 15-0150 76189-55-4 15-0151 76189-56-5 250mg 1g

TolBINAP 15-0152 99646-28-3 15-0153 100165-88-6 250mg 1g

XylBINAP 15-0476 137219-86-4 15-0477 135139-00-3 50mg 250mg

H8-BINAP 15-2972 139139-86-9 15-2973 139139-93-8 50mg 250mg

*5g size also available

BINAP - Metal Catalyst Kits are of the following type:

96-6951 Takasago BINAP Ru Cymene Catalyst Kit kit contains smallest unit of the 8 R- and S- items listed below Individual items available for sale

RuCl[(P-cymene)(L)]Cl


BINAP 44-0084 145926-28-9 44-0086 130004-33-0 250mg 1g

TolBINAP 44-0088 131614-43-2 44-0089 228120-95-4 250mg 1g

XylBINAP 44-0092 None 44-0093 None 50mg 250mg

H8-BINAP 44-0094 None 44-0095 None 50mg 250mg

96-6952 Takasago BINAP Ru Dimer Catalyst Kit kit contains smallest unit of the 8 R- and S- items listed below Individual items available for sale

[{RuCl(L)}2(u-Cl)3][NH2Me2]


BINAP 44-0510 199684-47-4 44-0511 199541-17-8 250mg 1g

TolBINAP 44-0512 749935-02-2 44-0513 309735-86-2 250mg 1g

XylBINAP 44-0514 None 44-0515 None 50mg 250mg

H8-BINAP 44-0516 204933-84-6 44-0517 None 50mg 250mg

P

P

ArAr

ArAr

BINAPs

P

P

ArAr

ArAr

BINAP TolBINAP XylBINAP H8-BINAP

Ar;

RuPP

Cl

Cl-

+


NH2Me2+

[NH2Me2][{RuCl(P^P)}2(μ-Cl)3] (II)

Ru

P

P

Cl

ClCl Cl

Ru

P

P

Cl -

Ru

O

PP

OOO

[Ru(OAc)2(P^P)] (III)

Ru

Cl

PP

ClN

N


54

Kits Containing Products Referenced in the Article 96-6953 Takasago BINAP Ru Acetate Catalyst Kit kit contains smallest unit of the 8 R- and S- items listed below Individual items available for sale

Ru(OAc)2(L)


BINAP 44-0152 325146-81-4 44-0153 261948-85-0 250mg 1g

TolBINAP 44-0162 116128-29-1 44-0163 106681-15-6 250mg 1g

XylBINAP 44-0164 374067-50-2 44-0165 374067-49-9 50mg 250mg

H8-BINAP 44-0166 374067-51-3 44-0167 142962-95-6 50mg 250mg

96-6954 Takasago BINAP Ru Diammine Catalyst Kit kit contains smallest unit of the 4 R- and S- items listed below Individual items available for sale

Ru(P-P)(N-N)Cl2


RuCl2[(XylBINAP)(

DAIPEN)]

44-0212 220114-32-9 44-0213 220114-01-2 50mg 250mg

RuCl2[(XylBINAP)(

DPEN)]

44-0226 220114-38-5 44-0224 220114-03-4 50mg 250mg

KITS Introduced Since Catalog 21

96-5900

Chiral Quest Catalyst and Ligand Toolbox Kit for Asymmetric Hydrogenation Contains 100mg unit of each of the following:

1kit

15-0103 (R,R)-(-)-1,2-Bis{(R)-4,5-dihydro-3H-binaphtho[1,2-c:2',1'-e]phosphepino}benzene, 97% (R)-BINAPHANE

15-0106 (S,S)-(+)-1,2-Bis{(S)-4,5-dihydro-3H-binaphtho[1,2-c:2',1'-e]phosphepino}benzene, 97% (S)-BINAPHANE

15-0175 R-(-)-1,13-Bis(diphenylphosphino)-7,8-dihydro-6H-dibenzo[f,h][1,5]dioxonin, 97% (R)-C3-TUNEPHOS

15-0176 (S)-(+)-1,13-Bis(diphenylphosphino)-7,8-dihydro-6H-dibenzo[f,h][1,5]dioxonin, 95% (S)-C3-TUNEPHOS

15-1015 (1S,1'S,2R,2'R)-(+)-1,1'-Di-t-butyl-[2,2']-diphospholane, 97% (S,S,R,R)-TANGPHOS 15-1053 (3S,3'S,4S,4'S,11bS,11'bS)-(+)-4,4'-Di-t-butyl-4,4',5,5'-tetrahydro-3,3'-bi-3H-dinaphtho

[2,1-c:1',2'-e]phosphepin, 97% (S)-BINAPINE 15-1060 (1R,1'R,2S,2'S)-(+)-2,2'-Di-t-butyl-2,3,2',3'-tetrahydro-1,1'-bi-1H-isophosphindole,

min. 98% (R,R,S,S)-DUANPHOS 45-0653 (1S,1'S,2R,2'R)-(+)-1,1'-Di-t-butyl-[2,2']-diphospholane(1,5-cyclooctadiene)rhodium (I)

tetrafluoroborate, min. 98% (S,S,R,R)-TANGPHOS-Rh 45-0663 (1R,1'R,2S,2'S)-(+)-2,2'-Di-t-butyl-2,3,2',3'-tetrahydro-1,1'-bi-1H-isophosphindole

(1,5-cyclooctadiene)rhodium (I) tetrafluoroborate, min. 98% (R,R,S,S)-DUANPHOS-Rh 45-0795 (R,R)-(-)-1,2-Bis{(R)-4,5-dihydro-3H-binaphtho[1,2-c:2',1'-e]phosphepino}benzene

(1,5-cyclooctadiene)rhodium (I) tetrafluoroborate (R)-BINAPHANE-Rh 45-0657 (3S,3'S,4S,4'S,11bS,11'bS)-(+)-4,4'-Di-t-butyl-4,4',5,5'-tetrahydro-3,3'-bi-3H-dinaphtho

[2,1-c:1',2'-e]phosphepin(1,5-cyclooctadiene)rhodium (I) tetrafluoroborate (S)-BINAPINE-Rh

44-0109 Chloro{(R)-(-)-1,13-bis(diphenylphosphino)-7,8-dihydro-6H-dibenzo[f,h][1,5]dioxonin} (p-cymene)ruthenium (II) chloride (R)-C3-TUNEPHOS-Ru

Note: For patent information visit www.strem.com. Sold in collaboration with Chiral Quest for research purposes only. Items available for individual sale. Visit our searchable catalog at www.strem.com for details.

55

KITS Introduced Since Catalog 21

96-1525

Long-Chain n-Alkylphosphonic Acid Kit Contains 1g unit of each of the items listed below:

1 kit

15-0958 n-Decylphosphonic acid, min. 97% See page 68 15-1835 n-Dodecylphosphonic acid, min. 97% See page 70 15-2400 n-Hexadecylphosphonic acid, min. 97% See page 70 15-2410 n-Hexylphosphonic acid, min. 97% See page 70 15-3510 n-Octadecylphosphonic acid, min. 97% See page 70 15-3520 n-Octylphosphonic acid, min. 97% See page 70 15-5145 n-Tetradecylphosphonic acid, min. 97% See page 70

96-3655 Solvias (R)-MeO-BIPHEP Ligand Kit 1 kit

Sold in collaboration with Solvias for research purposes only. Contains 100mg unit of each of the items listed below:

15-9570

15-0042

15-0044

15-0652

15-0112

15-0178

15-0654

15-0156

15-0158

15-0488

See next page for product description listing.

H3CO

H3CO

P

P

H3CO

H3CO

P

P

C(CH3)3

OCH3

C(CH3)3

C(CH3)3

OCH3

C(CH3)3

2

2

H3CO

H3CO

P

P

C(CH3)3

C(CH3)3

C(CH3)3

C(CH3)3

2

2

H3CO

H3CO

P

P

OCH3

OCH3

OCH3

OCH3

2

2

OCH3

OCH3

H3CO

H3CO

P

P

O

O

O

O

P

PH3CO

H3CO

H3CO

H3CO

P

P

P

PH3CO

H3CO

H3CO

H3CO

P

P

CH(CH3)2

CH(CH3)2

CH(CH3)2

CH(CH3)2

2

2

N(CH3)2

N(CH3)2

P

PH3CO

H3CO

56

Kits Introduced Since Catalog 21

96-3655 (cont.)

Solvias (R)-MeO-BIPHEP Ligand Kit Sold in collaboration with Solvias for research purposes only. Contains 100mg unit of each of the items listed below:

1 kit

15-9570 (R)-(+)-2,2'-Bis(dicyclobutylphosphino)-6,6'-dimethoxy-1,1'-biphenyl, min. 97%

See page 62

15-0042 (R)-(-)-2,2'-Bis[di(3,5-di-t-butyl-4-methoxyphenyl)phosphino]-6,6'-dimethoxy-1,1'-biphenyl, min. 97%

See page 62

15-0044 (R)-(+)-2,2'-Bis[di(3,5-di-t-butylphenyl)phosphino]-6,6'-dimethoxy-1,1'-biphenyl, min. 97%

See page 63

15-0652 (R)-(-)-2,2'-Bis[di(3,5-di-i-propyl-4-dimethylaminophenyl) phosphino]-6,6'-dimethoxy-1,1'-biphenyl, min. 97%

See page 64

15-0112 (R)-(+)-2,2'-Bis(di-2-furanylphosphino)-6,6'-dimethoxy-1,1'-biphenyl, min. 97%

See page 64

15-0178 (R)-(+)-2,2'-Bis(diphenylphosphino)-6,6'-dimethoxy-1,1'-biphenyl, min. 97% (R)-MeO-BIPHEP

See page 65

15-0654 (R)-(+)-2,2'-Bis(di-i-propylphosphino)-6,6'-dimethoxy-1,1'-biphenyl, min. 97%

See page 66

15-0156 (R)-(+)-2,2'-Bis(di-p-tolylphosphino)-6,6'-dimethoxy-1,1'-biphenyl, min. 97%

See page 67

15-0158 (R)-(+)-2,2'-Bis[di(3,4,5-trimethoxyphenyl)phosphino]-6,6'-dimethoxy-1,1'-biphenyl, min. 97%

See page 67

15-0488 (R)-(+)-2,2'-Bis[di(3,5-xylyl)phosphino]-6,6'-dimethoxy-1,1'-biphenyl, min. 97%

See page 67

96-3656

Solvias (S)-MeO-BIPHEP Ligand Kit Sold in collaboration with Solvias for research purposes only. Contains 100mg unit of each of the items listed below:

1 kit

15-9571 (S)-(-)-2,2'-Bis(dicyclobutylphosphino)-6,6'-dimethoxy-1,1'-biphenyl, min. 97%

See page 62

15-0043 (S)-(+)-2,2'-Bis[di(3,5-di-t-butyl-4-methoxyphenyl)phosphino]-6,6'-dimethoxy-1,1'-biphenyl, min. 97%

See page 63

15-0045 S)-(-)-2,2'-Bis[di(3,5-di-t-butylphenyl)phosphino]-6,6'-dimethoxy-1,1'-biphenyl, min. 97%

See page 63

15-0653 (S)-(+)-2,2'-Bis[di(3,5-di-i-propyl-4-dimethylaminophenyl)phosphino]-6,6'-dimethoxy-1,1'-biphenyl, min. 97%

See page 64

15-0113 (S)-(-)-2,2'-Bis(di-2-furanylphosphino)-6,6'-dimethoxy-1,1'-biphenyl, min. 97%

See page 64

15-0179 (S)-(-)-2,2'-Bis(diphenylphosphino)-6,6'-dimethoxy-1,1'-biphenyl, min. 97% (S)-MeO-BIPHEP

See page 66

15-0655 (S)-(-)-2,2'-Bis(di-i-propylphosphino)-6,6'-dimethoxy-1,1'-biphenyl, min. 97%

See page 66

15-0157 (S)-(-)-2,2'-Bis(di-p-tolylphosphino)-6,6'-dimethoxy-1,1'-biphenyl, min. 97%

See page 67

15-0159 (S)-(-)-2,2'-Bis[di(3,4,5-trimethoxyphenyl)phosphino]-6,6'-dimethoxy-1,1'-biphenyl, min. 97%

See page 67

15-0489 (S)-(-)-2,2'-Bis[di(3,5-xylyl)phosphino]-6,6'-dimethoxy-1,1'-biphenyl, min. 97%

See page 67

57

New Products Introduced Since Catalog 21 COPPER (Compounds)

29-4050

Chloro[1,3-bis(2,6-di-i-propylphenyl) imidazol-2-ylidene]copper(I), 98% [578743-87-0] C27H36ClCuN2; FW: 487.59 air sensitive

500mg 2g

Technical Notes: 1. Reduction of olefin in a conjugated α,β-unsaturated ketone. 2. Reduction of carbonyl in an unconjugated unsaturated ketone. 3. Catalysis of ethyldiazoacetate carbene transfer reactions without diazo coupling side reactions. 4. Catalyst for the aziridination of olefins. 5. Mild catalyst, superior to CuCl, in the methylenetriphenylphosphorane methyleneation of aldehydes

and ketones.





Tech. Note (5) Ref. (5) References: 1. Org. Lett., 2003, 5, 2417. 2. Organometallics, 2004, 23, 1157. 3. J. Am. Chem. Soc., 2004, 126, 10846.

4. J. Am. Chem. Soc., 2006, 128, 6054. 5. J. Org. Chem., 2007, 72,144.

GOLD (Compounds)

79-0740

Chlorotri-t-butylphosphinegold(I), 99% [69550-28-3] AuClP(C4H9)3; FW: 434.74; white microxtl.

250mg 1g

Cu

NN

Cl

0.1 mol% cat., Toluene, t-BuOHPMHS, NaOt-Bu, 3h, rt

95%

Ph

O

Ph

O

3 mol% cat., Toluene, t-BuOHEt3SiH, NaOt-Bu, 1h, rt

97%

O OSiEt3

R2R1N NR3R4 R2R1N NR3R4

NTs

PhI=NTs, cat.C6H6, 4 h, rt

52%

Ph N2

CO2Et

H

+

CO2Et

Ph

4 mol% cat. 13h rt

93% yieldcis/trans 32:68

93%

O

CO2Et CO2Et

5 mol% cat., TMSCHN2Ph3P, IPA, THF, reflux

58

Cl (HO)2BR2 R2

+IMesPd(OAc)2

R2 = aryl, alkenyl, alkylR1 R1

E

R3 R4

E

R3 R4

CHPhRu(IMes)(PCy3)Cl2( )

New Products Introduced Since Catalog 21

IRIDIUM (Compounds)

77-1115

3-Di-i-propylphosphino-2-(N,N-dimethylamino)-1H-indene(1,5-cyclooctadiene) iridium(I) hexafluoro-phosphate, min. 98% [870077-94-4] [IrC25H38NP]+PF6

-; FW: 720.73; orange pwdr. Note: Sold under license from Dalhousie for research purposes only. Provisional US patents 60/778,368 and 60/778,358.

250mg 1g


NITROGEN (Compounds)

07-0600

HAZ

1,3-Bis(2,4,6-trimethyl-phenyl) imidazol-2-ylidene, min. 98% [141556-42-5] C21H24N2; FW: 304.43; white to off-white pwdr. air sensitive, moisture sensitive

500mg 2g

Technical Notes: 1. Nucleophilic carbene that serves as a bulky, electron-rich "phosphine mimic" for metal-catalyzed

reactions. (a) Palladium-catalyzed Suzuki-Miyaura cross-coupling of aryl chlorides.

Ref. (1-5)

(b) Ruthenium-carbene complexes serve as more reactive catalysts for ring-closing metathesis.

Ref. (6-12)

2. Nucleophilic carbene that serves as a bulky, electron-rich organocatalyst. (a) Efficient Transesterification catalyst. Ref. (13)

References: 1. J. Org. Chem., 1999, 64, 3804. 2. Org. Lett,, 2005, 7, 1829. 3. Ann. Rpts. Prog. Chem. B. 2006, 102, 168. 4. Organometallics, 2002, 21, 5470. 5. J. Organometal. Chem., 2002, 653, 69. 6. See 44-7775 (Visit www.strem.com for details). 7. Organometallics 1999,121, 2674. 8. Org. Lett., 2000, 2, 1517. 9. J. Org. Chem., 2000, 65, 2204.

10. Organometallics, 1999, 18, 3760. 11. Angew. Chem. Int. Ed., 2002, 41, 1290. 12. J. Am. Chem. Soc., 1999, 121, 2674. 13. J. Org. Chem., 2003, 68, 2812.

Ir

P

N

+

CH(CH3)2(H3C)2HC

CH3H3C

NN

CH3

H3C

CH3 H3C

CH3

H3C

O

OMe

O

O Ph+ + CH3OH

2.5% Imes

1 Hr, 25 °C

59

New Products Introduced Since Catalog 21 NITROGEN (Compounds)

07-0380

(R)-4,4-Dibutyl-2,6-bis(3,4,5-trifluorophenyl)- 4,5-dihydro-3H-dinaphtho[7,6,1,2-cde] azepinium bromide [887938-70-7] [C42H36F6N]+Br-; FW: 748.64; brown pwdr. Note: Sold in collaboration with Nagase for research purposes only. US Patent 6,340,753.

50mg 250mg

Technical Notes: 1. Second Generation Maruoka chiral phase transfer catalyst, for enantioselective alkylation of α-amino acid derivatives, that is easily recovered for recycle by extraction with fluorous solvent. 2. Catalyst for asymmetric conjugate addition of α-substituted-α-cyanoacetates to α,β-unsaturated

acetylenic esters.



References: 1. Tetrahedron Asymm., 2006, 17, 603. 2. J. Am. Chem. Soc., 2007, 129, 1038.

07-0381

(S)-4,4-Dibutyl-2,6-bis(3,4,5-trifluorophenyl)-4,5-dihydro-3H-dinaphtho[7,6,1,2-cde]azepinium bromide [851942-89-7] [C42H36F6N]+Br-; FW: 748.64; brown pwdr. Note: Sold in collaboration with Nagase for research purposes only. US Patent 6,340,753.

50mg 250mg


PALLADIUM (Compounds)

46-0045

Allylchloro[1,3-bis(2,4,6-tri- methylphenyl)imidazol-2- ylidene]palladium(II), 98% [478980-04-0] C24H29ClN2Pd; FW: 487.37; white pwdr. Note: Sold in collaboration with Umicore for research purposes only. Patent WO 2004014550, US 6,316,380 and EP 721 953 A1.

250mg 1g

Technical Note: 1. See 46-0040 (Visit www.strem.com for details).

F

F

F

F

F

F

N+

Br-

Pd

NN

CH3

CH3 H3C

H3C

Cl

CH3H3C

N CO2(t-Bu)ClPh+ Nap-(1)-CH2Br

H2N COOH

-(1)-Nap

CsOH, H2O, Toluene

[ 96%, 99%ee]

NC CO2(t-Bu)

CH2CH2Ph+ CO2Et

NC CO2(t-Bu)

PhH2CH2C CO2Et

1 mol% cat., Cs2CO3Tol., 2h, 0°

[99%, 1.7:1 E/Z, 55/72% ee]

60

New Products Introduced Since Catalog 21

PALLADIUM (Compounds)

46-0274

Chloro[(1,2,3-η)-3-phenyl-2- propenyl][1,3-bis(2,6-di-i-propylphenyl)-4,5-dihydroimidazol-2- ylidene]palladium(II), min. 97% [884879-24-7] C36H47ClN2Pd; yellow microxtls. Note: Sold in collaboration with Umicore. WO 2004014550, US 6,316,380, EP 721 953 A1.

250mg 1g

Technical Note: 1. Catalyst used for the room temperature Buchwald-Hartwig amination of hindered aryl chlorides.

References: 1. J. Am. Chem. Soc., 2006, 128, 4101. 2. Chem. Eur. J., 2006, 12, 5142.

46-0860

Dichloro(di-µ-chloro)bis[1,3-bis (2,6-di-i-propylphenyl)imidazol- 2-ylidene]dipalladium (II), 97% [444910-17-2] C54H72Cl4N4Pd2; FW: 1131.83; orange to tan pwdr. Note: Sold in collaboration with Umicore for research purposes only. Patent WO 2004014550, US 6,316,380 and EP 721 953 A1.

250mg 1g

Technical Notes: 1. Catalyst used for the intramolecular direct arylation reaction with aryl chlorides. 2. Catalyst used for aerobic oxidative kinetic resolution of secondary alcohols. 3. Catalyst used for aryl amination.

Tech. Note (1) Ref. (1) Tech. Note (2) Ref. (2)


References: 1. Org. Lett., 2005, 7, 1857. 2. Org. Lett., 2003, 5, 63. 3. Org. Lett., 2002, 4, 2229.

46-0900

Dichloro(norbornadiene)palladium (II), 99% [12317-46-3] C7H8PdCl2; FW: 269.46; yellow to orange pwdr.

250mg 1g

N

NPd

Cl

ClClPd

Cl

N

N

Cl H2NHN+

(SIPr)Pd(cin)Cl0.1 mole%

KO-t-Bu, 22 hr 25°C98% yield

O

Cl

Pd complexK2CO3, DMA, 130°C

18hO

R Me

OH(±)

1.5 mol% Pd complex1.5 mol% (-) sparteine

DCE, O2, 65°C20h (3A Mol Sieves) R Me

OH

R Me

O

+

Ar X + NRR'HPd complex

1.5 eq. KOtAmDME, 80°C, air

Ar NRR'

Pd

NN

Cl

61

New Products Introduced Since Catalog 21 PHOSPHORUS (Compounds)

15-0057

(R,R)-(-)-6,6'-[(1,1'-Biphenyl-2,2'-diyl)bis(oxy)]bis[4,8-di-t-butyl-1,2,10,11-tetramethyl]dibenzo[d,f][1,3,2]dioxa- phosphepin bisacetonitrile adduct, min. 95% (R,R)-Kelliphite [729572-46-7] C60H72O6P2

.2CH3CN; FW: 951.16 (1033.26); white to off-white pwdr.; [α]D -365° (c 1.0, CH2Cl2); m.p. 149-155° air sensitive, moisture sensitive Note: Sold in collaboration with Chirotech for research purposes only. US Patent 7015360B2.

100mg500mg

Technical Note: 1. Ligand used with rhodium to catalyze asymmetric hydroformylation of prochiral functional olefins under mild conditions. High substrate concentrations and a wide variety of functional groups are tolerated. High enantioselectivities and regioselectivities have been demonstrated. Ref. (1, 2) Ref. (3)

References: 1. Org. Lett., 2004, 6, 3277. 2. J. Am. Chem. Soc., 2005, 127, 5040. 3. J. Org. Chem., 2004, 69, 4031.

15-0058

(S,S)-(+)-6,6'-[(1,1'-Biphenyl-2,2'-diyl)bis(oxy)] bis[4,8-di-t-butyl-1,2,10,11-tetramethyl]dibenzo[d,f][1,3,2]dioxa-phosphepin bisacetonitrile adduct, min. 95% (S,S)-Kelliphite [729572-33-2] C60H72O6P2∙2CH3CN; FW: 951.16 (1033.26); white to off-white pwdr.; [α]D +365° (c 1.0, CH2Cl2); m.p. 149-155° air sensitive, moisture sensitive Note: Sold in collaboration with Chirotech for research purposes only. US Patent 7015360B2.

100mg500mg


15-0052

(R)-(-)-1,1'-Binaphthyl-2,2'-diyl hydrogenphosphate, min. 98% [39648-67-4] C20H13O4P; FW: 348.30; white pwdr.; [α]D -605° (c 1.35, CH3OH)

1g 5g

O

OP

O

OH

P P

O

O

t-Bu

t-Bu

CH3

CH3

CH3

CH3O

O

t-Bu

t-Bu

H3C

H3CH3C

H3C

O O

10 atm (1:1 H2/CO) , 30° 5 hr

0.066 mol% Rh(CO)2(acac),0.073 mol% (R,R)-L

CHO99%, 20 b/l, 80% ee

NC NC

AcO 10 atm (1:1 H2/CO) , 70° 3 hr

0.2 mol% Rh, 0.4 mol% (S,S)-L,Toluene

AcO CHO97%, 56 b/l, 77% ee

62


15-0052 (cont.)

(R)-(-)-1,1'-Binaphthyl-2,2'-diylhydrogenphosphate, min. 98% [39648-67-4]

Technical Notes: 1. Asymmetric hetero Diels-Alder reaction catalyzed by chiral lanthanide(III) complex. 2. Acidic Resolving agent for certain amine racemic mixtures. (Ref. 2,3)

Ref. (1) References:

1. Org. Lett.., 2000, 2, 49. 2. J. Org. Chem., 1991, 56, 485. 3. US 6,162,919.

15-0053

(S)-(+)-1,1'-Binaphthyl-2,2'-diyl hydrogenphosphate, min. 98% [35193-64-7] C20H13O4P; FW: 348.30; white pwdr.; [α]D +595° (c 1.35, CH3OH)

1g 5g

Technical Note: 1. See 15-0052 (page 61) .

15-9570

(R)-(+)-2,2'-Bis(dicyclobutylphosphino)-6, 6'-dimethoxy-1,1'-biphenyl, min. 97% [150971-49-6] C30H40O2P2; FW: 494.60; white pwdr. Note: Sold in collaboration with Solvias for research purposes only. Solvias (R)-MeO-BIPHEP Ligand Kit component see (page 55).

100mg 500mg


15-9571

(S)-(-)-2,2'-Bis(dicyclobutylphosphino)-6,6'-dimethoxy-1,1'-biphenyl, min. 97% [150971-51-0] C30H40O2P2; FW: 494.60; white pwdr. Note: Sold in collaboration with Solvias for research purposes only. Solvias (S)-MeO-BIPHEP Ligand Kit component see (page 56).

100mg 500mg


15-0042

(R)-(-)-2,2'-Bis[di(3,5-di-t-butyl-4- methoxyphenyl)phosphino]-6,6'- dimethoxy-1,1'-biphenyl, min. 97% [352655-61-9] C74H104O6P2; FW: 1151.60; white xtl. Note: Sold in collaboration with Solvias for research purposes only. Solvias (R)-MeO-BIPHEP Ligand Kit Component see (page 55).

100mg 500mg

H3CO

H3CO

P

P

H3COH3CO

P

P

C(CH3)3

OCH3

C(CH3)3

C(CH3)3

OCH3

C(CH3)3

2

2

4-MeOPhCHO + OMe

OTMSO

O

Yb[(R)-BNP]32,6-lutidine 10 mol% H+

93% ee

63


15-0042 (cont.)

(R)-( )-2,2'-Bis[di(3,5-di-t-butyl-4-methoxyphenyl)phosphino]-6,6'-dimethoxy-1,1'-biphenyl, min. 97% [352655-61-9]

Technical Note: 1. Various asymmetric C-C coupling reactions such as Rh-catalyzed reductive coupling of acetylene to

aldehydes and "-ketoesters, Pt-catalyzed intramolecular hydroarylation of unactivated alkenes with indoles and glyoxylate-ene reaction or the Pd-catalyzed enantioselective Heck reaction of p-XC6H4OTf (X = OMe, H, CO2Me) with dihydrofuran.

2. See 15-0178 (page 63).

Reference: 1. Org. Lett. 2006, 8, 3801.

15-0043

(S)-(+)-2,2'-Bis[di(3,5-di-t-butyl-4-methoxyphenyl) phosphino]-6,6'-dimethoxy-1,1'-biphenyl, min. 97% [910134-30-4] C74H104O6P2; FW: 1151.60; white xtl. Note: Sold in collaboration with Solvias for research purposes only. Solvias (S)-MeO-BIPHEP Ligand Kit component see (page 56).

100mg 500mg


15-0044

(R)-(+)-2,2'-Bis[di(3,5-di-t-butylphenyl)phosphino]-6,6'-dimethoxy-1, 1'-biphenyl, min. 97% [192138-05-9] C70H96O2P2; FW: 1031.49; white pwdr. Note: Sold in collaboration with Solvias for research purposes only. Solvias (R)-MeO-BIPHEP Ligand Kit component see (page 55).

100mg 500mg

Technical Notes: 1. Various asymmetric C-C coupling reactions such as Rh-catalyzed reductive coupling of acetylene to aldehydes and "-ketoesters, Pt-catalyzed intramolecular hydroarylation of unactivated alkenes with

indoles and glyoxylate-ene reaction or the Pd-catalyzed enantioselective Heck reaction of p-XC6H4OTf (X = OMe, H, CO2Me) with dihydrofuran.

2. See 15-0178 (page 65).

Reference: 1. Organometallics 1999, 18, 670.

15-0045

(S)-(-)-2,2'-Bis[di(3,5-di-t-butylphenyl)phosphino]-6,6'-dimethoxy-1,1'-biphenyl, min. 97% [167709-31-1] C70H96O2P2; FW: 1031.49; white pwdr. Note: Sold in collaboration with Solvias for research purposes only. Solvias (S)-MeO-BIPHEP Ligand Kit component see (page 56).

100mg 500mg


NR

R"R'R'

NR

R"R'R'

56-96%, ee up to 90%

Pt(3.5-tBu2-4-MeO-Ph-MeOBIPHEP)Cl2AgOTf

MeOH, 25°C

H3COH3CO

P

P

C(CH3)3

C(CH3)3

C(CH3)3

C(CH3)3

2

2

ORAr

OR+ArOTfPd - (3,5-tBu2-Ph-MeOBIPHEP)

acetone, 40 °CNEt(i-Pr)2R = H, Me

+ isomer

ee >98%

64


15-0652

(R)-(-)-2,2'-Bis[di(3,5-di-i-propyl-4-dimethylaminophenyl)phosphino]-6, 6'-dimethoxy-1,1'-biphenyl, min. 97% [352655-40-4] C70H100N4O2P2; FW: 1091.55; white pwdr. Note: Sold in collaboration with Solvias for research purposes only. Solvias (R)-MeO-BIPHEP Ligand Kit component See (page 55).

100mg 500mg


15-0653

(S)-(+)-2,2'-Bis[di(3,5-di-i-propyl-4-dimethylaminophenyl) phosphino]-6,6'-dimethoxy-1,1'-biphenyl, min. 97% [919338-66-2] C70H100N4O2P2; FW: 1091.55; white pwdr. Note: Sold in collaboration with Solvias for research purposes only. Solvias (S)-MeO-BIPHEP Ligand Kit component see (page 56).

100mg 500mg


15-0112

(R)-(+)-2,2'-Bis(di-2-furanylphosphino)-6, 6'-dimethoxy-1,1'-biphenyl, min. 97% [145214-57-9] C30H24O6P2; FW: 542.47; off-white pwdr. Note: Sold in collaboration with Solvias for research purposes only. Solvias (R)-MeO-BIPHEP Ligand Kit Component see (page 55).

100mg 500mg


15-0113

(S)-(-)-2,2'-Bis(di-2-furanylphosphino)-6,6'-dimethoxy-1,1'-biphenyl, min. 97% [145214-59-1] C30H24O6P2; FW: 542.47; off-white pwdr. Note: Sold in collaboration with Solvias for research purposes only. Solvias (S)-MeO-BIPHEP Liand Kit component see (page 56).

100mg 500mg


15-0099

Bis(4,6-dimethyl-3-sulfonatophenyl)(2,4-dimethylphenyl)phosphine, disodium salt hydrate, min. 95% TXPDS C24H25Na2O6PS2; FW: 550.54; white pwdr.

250mg 1g

H3COH3CO

P

P

CH(CH3)2

CH(CH3)2

CH(CH3)2

CH(CH3)2

2

2

N(CH3)2

N(CH3)2

H3CO

H3CO

P

P

O

O

O

O

P

H3C

CH3

H3C CH3 CH3

CH3

SO3-Na+

SO3-Na+

65


15-0178

(R)-(+)-2,2'-Bis(diphenylphosphino)-6,6'-dimethoxy-1,1'-biphenyl, min. 97% (R)-MeO-BIPHEP [133545-16-1] C38H32O2P2; FW: 582.53; off-white xtl. Note: Sold in collaboration with Solvias for research purposes only. Solvias (R)-MeO-BIPHEP Ligand Kit component see (page 55).

100mg 500mg

Technical Notes: In many respects the catalytic profile of the

MeOBIPHEP ligands is similar to that of other atropisomeric diphosphines such as binap and its many analogs. The nature of the PR2 group strongly influences the catalytic performance of the metal complexes. The rhodium and ruthenium MeO-BIPHEP catalysts are highly effective for the hydrogenation of various C=O, C=C and C=N bonds and several synthetically useful CC coupling reactions.

1. Ru-catalyzed asymmetric hydrogenation of β-keto esters, β-keto sulfones and "-keto amides. 2. Ru and Ir-catalyzed dynamic kinetic resolution for the synthesis of β-hydroxy-"-amino acid

derivatives. 3. Ru-catalyzed hydrogenation of C=C bonds, especially ",β-unsaturated acids, allylic alcohols and with

other activated groups. 4. Ir-catalyzed enantioselective hydrogenation of heteroaromatic compounds. 5. Various asymmetric C-C coupling reactions such as Rh-catalyzed reductive coupling of acetylene to

aldehydes and "-ketoesters, Pt-catalyzed intramolecular hydroarylation of unactivated alkenes with indoles and glyoxylate-ene reaction or the Pd-catalyzed enantioselective Heck reaction of p-XC6H4OTf (X = OMe, H, CO2Me) with dihydrofuran.

Tech. Note (1) Ref. (1-3) Tech. Note (1) Ref. (4) Tech. Note (2) Ref. (5) Tech. Note (3) Ref. (6-9) Tech. Note (3) Ref. (10)

Tech. Note 4) Ref. (11)

P

PH3CO

H3CO

N R

R'

NH

R

R'[Ir(cod)2Cl]2 / MeOBIPHEP

toluene, I250 bar, 25°C

s/c 100, 18 h

y 80-99%, 86-96% eeR = (subst) alkyl

R' = H, F, Me, MeO

R

O

XR

OH

XRu - MeOBIPHEP

88-97% eeR = alkyl, (subst) Ph, NpX = COOR', SO2Ph

1-10 bar, 40-80 °C

O

ClO

HN

R

OH

ClO

HN

R

90 - 93% ee

MeOH, 1 N HCl80 bar, 60°C

[Ru(p-cymene)I2]2 (R)-MeOBIPHEP

s/c 4000, 20 h

COOH COOH

Ru - MeOBIPHEP

MeOH / NEt3130 bar, 0°C

s/c ~80, 24 h

100% conv., 98% ee

tBuOOC

OOMe

COONa tBuOOC

OOMe

COONa

Ru / MeOBIPHEP50 °C, 9 bar

ee 99%; ton 1'000; tof 300h-1

pilot process, PPG-Sipsy

Ar

O

NH2.HCl

COOMe Ar

OH

NHBz

COOMe1) [Ir-MeOBIPHEP]BARF

AcOH / NaOAc

92% ee, dr >992) Bz2O, TEA, THF

66


15-0178 (cont.)

(R)-(+)-2,2’-Bis(diphenylphosphino)-6,6’-di-methoxy-1,1’-biphenyl, min. 97% (R)-MeO-BIPHEP [133545-16-1]


References:

1. Adv. Synth. Catal. 2003, 345, 261. 2. J. Organomet. Chem. 2000, 603, 128. 3. Tetrahedron: Asymmetry 1999, 10, 1369. 4. Adv. Synth. Catal. 2004, 346, 842. 5. Org. Lett. 2006, 8, 4573. 6. Tetrahedron Lett. 2006, 47, 9261. 7. Comprehensive Asymmetric Catalysis, 1999, 1439. 8. Chimia 1997, 51, 303. 9. J. Am. Chem. Soc. 2003, 125, 8779.

10. Org. Process Res. Devel. 2001, 5, 438. 11. J. Am. Chem. Soc. 2003, 125, 10536. 12. J. Am. Chem. Soc. 2006, 128, 16040.

15-0179

(S)-(-)-2,2’-Bis(diphenylphosphino)-6,6’-dimethoxy-1,1’-biphenyl, min. 97% (S)-MeO-BIPHEP [133545-17-2] C38H32O2P2; FW: 582.53; white xtl. Note: Sold in collaboration with Solvias for research purposes only. Solvias (S)-MeO-BIPHEP Ligand Kit component see (page 56).

100mg 500mg


15-0430

Bis(1,5-diphenylphosphino)pentane, min. 98% [27721-02-4] (C6H5)2P(CH2)5P(C6H5)2; FW: 440.51; white to off-white solid; m.p. 46-49°

1g 5g

15-0654

(R)-(+)-2,2’-Bis(di-i-propylphosphino)-6,6’- dimethoxy-1,1’-biphenyl, min. 97% [150971-45-2] C26H40O2P2; FW: 446.56; white pwdr. Note: Sold in collaboration with Solvias for research purposes only. Solvias (R)-MeO-BIPHEP Ligand Kit component see (page 55).

100mg 500mg


15-0655

(S)-(-)-2,2’-Bis(di-i-propylphosphino)-6,6’-dimethoxy-1,1’-biphenyl, min. 97% [150971-43-0] C26H40O2P2; FW: 446.56; white pwdr. Note: Sold in collaboration with Solvias for research purposes only. Solvias (S)-MeO-BIPHEP Ligand Kit component see (page 56).

100mg 500mg


H3CO

H3CO

P

P

R R'

O

R

OH

R'2 +

y ~80%, ee 89%

Rh - MeOBIPHEP

DCE, Ph3CCOH, Na2SO4

1 bar, 25°C

67


15-0156

(R)-(+)-2,2'-Bis(di-p-tolylphosphino)-6, 6'-dimethoxy-1,1'-biphenyl, min. 97% [133545-24-1] C42H40O2P2; FW: 638.73; white pwdr. Note: Sold in collaboration with Solvias for research purposes only. Solvias (R)-MeO-BIPHEP Ligand Kit component see (page 55).

100mg 500mg


15-0157

(S)-(-)-2,2'-Bis(di-p-tolylphosphino)-6,6'-dimethoxy-1,1'-biphenyl, min. 97% [133545-25-2] C42H40O2P2; FW: 638.73; white pwdr. Note: Sold in collaboration with Solvias for research purposes only. Solvias (S)-MeO-BIPHEP Ligand Kit component see (page 56).

100mg 500mg


15-0158

(R)-(+)-2,2'-Bis[di(3,4,5-trimethoxyphenyl)phosphino]-6,6'-dimethoxy-1, 1'-biphenyl, min. 97% [256390-47-3] C50H56O14P2; FW: 942.94; off-white pwdr. Note: Sold in collaboration with Solvias for research purposes only. Solvias (R)-MeO-BIPHEP Ligand Kit component see (page 55).

100mg 500mg


15-0159

(S)-(-)-2,2'-Bis[di(3,4,5-trimethoxyphenyl)phosphino]-6,6'-dimethoxy-1,1'-biphenyl, min. 97% [256235-61-7] C50H56O14P2; FW: 942.94; off-white pwdr. Note: Sold in collaboration with Solvias for research purposes only. Solvias (S)-MeO-BIPHEP Ligand Kit component see (page 56).

100mg 500mg


15-0488

(R)-(+)-2,2'-Bis[di(3,5-xylyl)phosphino]- 6,6'-dimethoxy-1,1'-biphenyl, min. 97% [394248-45-4] C46H48O2P2; FW: 694.84; white pwdr. Note: Sold in collaboration with Solvias for research purposes only. Solvias (R)-MeO-BIPHEP Ligand Kit component see (page 55).

100mg 500mg


15-0489

(S)-(-)-2,2'-Bis[di(3,5-xylyl)phosphino]-6,6'-dimethoxy-1,1'-biphenyl, min. 97% [362634-22-8] C46H48O2P2; FW: 694.84; white pwdr. Note: Sold in collaboration with Solvias for research purposes only. Solvias (S)-MeO-BIPHEP Ligand Kit component See (page 56).

100mg 500mg


P

PH3CO

H3CO

H3COH3CO

P

P

OCH3

OCH3

OCH3

OCH3

2

2

OCH3

OCH3

P

PH3CO

H3CO

68


15-0958

n-Decylphosphonic acid, min. 97% [6874-60-8] CH3(CH2)9P(O)(OH)2; FW: 222.26; white to off-white pwdr.; m.p. 103-104° Note: Long-Chain n-Alkylphosphonic Acid Kit component see (page 55).

1g 5g

15-1017

amp HAZ

Di-t-butylneopentylphosphine, min. 95% [60633-21-8] (C4H9)2(C5H11)P; FW: 216.35; colorless to yellow liq. pyrophoric

1g 5g

Technical Notes: 1. The phosphine, used in combination with a palladium source, produces a highly effective catalyst for

the Buchwald-Hartwig amination of aryl bromides at room temperature. 2. Phosphine used in the palladium-catalyzed, Suzuki cross-coupling reaction.

Tech. Note (1) Ref. (1) Tech. Note (2) Ref. (2) References: 1. J. Org. Chem., 2006, 71, 5117. 2. Organometallics, 2006, 25, 2978.

15-1018

HAZ

Di-t-butylneopentylphosphine, min. 95% (10 wt% in hexane) [60633-21-8] (C4H9)2(C5H11)P; FW: 216.35; colorless to pale yellow liq. air sensitive

10g 50g


15-1019

Di-t-butylneopentylphosphonium tetrafluoroborate, min. 95% [886059-84-3] [(C4H9)2(C5H11)PH]+BF4

-; FW: 304.17; white solid

1g 5g


15-1748

1-Diphenylphosphino-2-(N,N-dimethylamino)-1H-indene, 99% [628323-64-8] C23H22NP; FW: 343.40; off-white xtl. Note: Sold under license from Dalhousie for research purposes only. Provisional US patents 60/778,368 and 60/778,358.

1g 5g


15-1765

2-[2-(Diphenylphosphino)ethyl] pyridine, min. 97% [10150-27-3] C19H18NP; FW: 291.33; white pwdr. air sensitive

250mg 1g

NCH3

CH3

P

N P

ArBr + Ar1 NH2

PhosphinePd2(dba)3

NaO-t-Bu, toluene rt 3-4h Ar

NAr1

H

Ar1Br + F B(OH)2 Ar1 F

69


15-1765 (cont.)

2-[2-(Diphenylphosphino)ethyl]pyridine, min. 97% [10150-27-3]

Technical Note: 1. Catalyst used for the room temperature cross-coupling of organozinc reagents with carboxylic

fluorides, chlorides, anhydrides and thioesters.

O +

O

O

ZnR2

COOH

O

R 86% yield

Ni(COD)2 ligandstyrene cat.

0-23°C

References: 1. Org. Lett., 2006, 8, 4307. 2. J. Am. Chem. Soc., 2004, 126,15964.

15-1784

(R)-(+)-4-[2-(Diphenylphosphino)-1- naphthalenyl]-N-[(R)-1-phenylethyl]-1- phthalazinamine, min. 97% (R)-N-PINAP [828927-97-5] C38H30N3P; FW: 559.64; colorless xtl.; [α]D +127.3° (c 0.39, CHCl3); m.p. 185-188° air sensitive Note: Sold under license from Sumitomo for research purposes. US application 11/149,643, PCT application PCT/JP2005/010746.

50mg 250mg

Technical Notes: 1. The PINAP family of P,N ligands is a synthetically more accessible but a similarly performing analog

of the QUINAP (15-1777, 15-1778) ligand in enantioselective hydroboration, alkyne addition, and azomethine cycloaddition reactions. (Ref. 1)

2. With copper, enantioselective addition of alkynes to aldehydes to synthesize propargylamines. 3. With copper, catalytic, enantioselective, conjugate alkyne addition in aqueous media.

Tech. Note (2) Ref. (1,2)


References: 1. Angew. Chem. Int. Ed., 2004, 43, 5971. 2. Org. Lett., 2006, 8, 2437. 3. J. Am. Chem. Soc., 2005, 127, 9682.

N

N

P(C6H5)2

NH

CH3

O O

O O

iPr

O O

O O

iPr

Ph

HPhCu(OAc)2.H2O5-20% (S)-L

H2O, 0°, 18 h[58%, 80%ee]

O

H

H

SiMe3

H

NH3.HCl1) 5.5 mol% L, CuBrNEt3, 4A MS, CH2Cl2,23h rt [82%, 99%ee]

2) Deprotect: PS-NH2;K2CO3; HCl [81%]N

H2 Cl

OHHO

+ +

70


15-1786

(S)-(-)-4-[2-(Diphenylphosphino)-1-naphthalenyl]-N-[(R)-1-phenylethyl]-1-phthalazinamine, min. 97% (S)-N-PINAP [828927-96-4] C38H30N3P; FW: 559.64; colorless xtl.; [α]D -162° (c 0.54, CHCl3); m.p. >210° air sensitive Note: Sold under license from Sumitomo for research purposes. US application 11/149,643, PCT application PCT/JP2005/010746.

50mg 250mg


15-1802

1-Di-i-propylphosphino-2-(N,N-dimethylamino)-1H-indene, 99% [540492-51-5] C17H26NP; FW: 275.37; off-white xtl. air sensitive Note: Sold under license from Dalhousie for research purposes only. Provisional US patents 60/778,368 and 60/778,358.

250mg 1g


15-1835

n-Dodecylphosphonic acid, min. 97% [5137-70-2] CH3(CH2)11P(O)(OH)2; FW: 250.31; white to off-white pwdr.; m.p. 96-98° Note: Long-Chain n-Alkylphosphonic Acid Kit component see (page 55).

1g 5g

15-2400

n-Hexadecylphosphonic acid, min. 97% [4721-17-9] CH3(CH2)15P(O)(OH)2; FW: 306.42; white to off-white pwdr.; m.p. 96-99° Note: Long-Chain n-Alkylphosphonic Acid Kit component see (page 55).

1g 5g

15-2410

n-Hexylphosphonic acid, min. 97% [4721-24-8] CH3(CH2)5P(O)(OH)2; FW: 166.16; white to off-white pwdr.; m.p. 105-106° Note: Long-Chain n-Alkylphosphonic Acid Kit component see (page 55).

1g 5g

15-3510

n-Octadecylphosphonic acid, min. 97% [4724-47-4] CH3(CH2)17P(O)(OH)2; FW: 334.47; white to off-white pwdr.; m.p. 100-101° Note: Long-Chain n-Alkylphosphonic Acid Kit component see (page 55).

1g 5g

15-3520

n-Octylphosphonic acid, min. 97% [4724-48-5] CH3(CH2)7P(O)(OH)2; FW: 194.21; white to off-white pwdr.; m.p. 102-103° Note: Long-Chain n-Alkylphosphonic Acid Kit component see (page 55).

1g 5g

15-5145

n-Tetradecylphosphonic acid, min. 97% [4671-75-4] CH3(CH2)13P(O)(OH)2; FW: 278.37; white to off-white pwdr.; m.p. 96-98° Note: Long-Chain n-Alkylphosphonic Acid Kit component see (page 55).

1g 5g

15-7830

Tris(2,4-dimethylphenyl)phosphine, 98% [49676-42-8] [(CH3)2C6H3]3P; FW: 346.45; white pwdr.; m.p. 157-158°

500mg 2g

RHODIUM (Compounds)

45-0213

(R)-(-)-4,12-Bis(di-3,5-xylylphosphino)[2.2] paracyclophane(1,5-cyclooctadiene) rhodium(I) tetrafluoroborate, min. 97% [619334-93-9] [C56H62P2Rh]+BF4

-; FW: 986.75; yellow-orange xtl. air sensitive Note: Sold in collaboration with JM for research purposes only. Patent WO 2006/067412, US5874629.

100mg 500mg


NCH3

CH3

P CH(CH3)2

(H3C)2HC

Rh

P

P

+

71

New Products Introduced Since Catalog 21 RHODIUM (Compounds)

45-0214

(S)-(+)-4,12-Bis(di-3,5-xylylphosphino)[2.2]paracyclophane (1,5-cyclooctadiene)rhodium(I) tetrafluoroborate, min. 97% [619334-93-9] [C56H62P2Rh]+BF4

-; FW: 986.75; yellow-orange xtl. air sensitive Note: Sold in collaboration with JM for research purposes only. Patent WO 2006/067412, US5874629.

100mg 500mg

Technical Note: 1. Catalyst for the enantioselective hydrogenation of unsaturated amino acid derivatives.



References: 1. Org. Lett., 2004, 6, 1927. 2. Org. Lett., 2005, 7, 1931.

45-0652

Cyclooctadiene(hydroquinone) rhodium(I) tetrafluoroborate [120967-70-6] [Rh(C8H12)(C6H6O2)]+BF4

-; FW: 408.00; yellow pwdr. Note: Sold in collaboration with Brown University for research purposes only. Commercial use requires a license. US Patent Application 11/454,760.

250mg1g

Technical Notes: 1. A phosphorous free pre-catalyst for the efficient 1,4-conjugate addition of arylboronic acids to enones. 2. A pre-catalyst for addition of arylboronic acids to aryl aldehydes. 3. With aluminum isopropoxide forms a self-supported heterogeneous catalyst for the stereoselective polymerization of phenylacetylene to cis-poly(phenylacetylene). (Ref. 3) Tech. Note (1) Ref. (1) Tech. Note (2) Ref. (2) References:

1. Organometallics, 2006, 25, 3548. 2. J. Am. Chem. Soc., 2005, 127, 12238. 3. J. Am. Chem. Soc., 2006, 128, 8740.

CO2Me

NHAc

cat., 0.02 mol%5.5 bar H2, MeOH, rt, 20 m

[100%, 96.7% ee]

CO2Me

NHAc

Boc

HN

CO2-Q+

N

NPr

Boc

HN

CO2-Q+

N

NPr

1 mol% cat. Q=quinidine10 bar H2, MeOH, 55°, 18h

[ 100%, 70%ee]

Rh+

OHHO

+DME, H2O, 50°, 1 h

0.5 mol% cat., 2.0 mol% LiOH

O

Cl B(OH)2

O

p-ClPh99%

+ PhB(OH)2

2.4 mol% cat., H2O, 75°, 3hH

O

Ph

OH

97%

72


45-0198

3-Di-i-propylphosphino-2-(N,N- dimethylamino)-1H-indene (1,5-cyclooctadiene)rhodium (I) hexafluorophosphate, min. 98% [RhC25H38NP]+PF6

-; FW: 631.42; orange pwdr. Note: Sold under license from Dalhousie for research purposes only. Provisional US patents 60/778,368 and 60/778,358.

250mg 1g


45-0197

3-Di-i-propylphosphoranylidene- 2-(N,N-dimethylamino)-1H- indene(1,5-cyclooctadiene) rhodium(I), min. 95% [540492-55-5] C25H37NPRh; FW: 485.45; orange-red xtl. Note: Sold under license from Dalhousie for research purposes only. Provisional US patents 60/778,368 and 60/778,358.

250mg 1g

Technical Note: 1. Zwitterionic hydrogenation, hydrosilylation and hydroboration catalyst soluble in non-polar solvents

Ph+ Ph

5% Cat.

toluene96% (Rh)

99% (Ir)

Et3SiHSiEt3

PhSiEt3

References: 1. Organometallics, 2007, 26, 594. 2. Organometallics, 2006, 25, 5965.

45-2110

(R)-(+)-2,2',6,6'-Tetramethoxy-4,4'-bis (diphenylphosphino)-3,3'-bipyridine (1,5-cyclooctadiene)rhodium(I) tetrafluoroborate, min. 97% [573718-56-6] [C46H46N2O4P2Rh]+BF4

-; FW: 942.53; yellow-orange xtl. air sensitive Note: Sold in collaboration with JM for research purposes only. Patent US5886182.

100mg 500mg

Technical Note: 1. See 15-5210, technical note 4 (Visit www.strem.com for details).

Rh

P

N

+

(H3C)2HC

CH3H3C

CH(CH3)2

Rh

P

N H

CH(CH3)2(H3C)2HC

H3C CH3

+

95% (Rh)

95% (Ir)

O

BH

O

2% Cat., THF, rt

Bpin

Bpin

N

N

OCH3

OCH3

OCH3

OCH3

Rh+

P

P

73


45-2111

(S)-(-)-2,2',6,6'-Tetramethoxy-4,4'-bis(diphenylphosphino)-3,3'-bipyridine(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate, min. 97% [573718-56-6] [C46H46N2O4P2Rh]+BF4

-; FW: 942.53; yellow-orange xtl. air sensitive Note: Sold in collaboration with JM for research purposes only. Patent US5886182.

100mg 500mg

Technical Note: 1. See 15-5210, technical note 4 (Visit www.strem.com for details).


44-7778

3-Phenyl-1H-inden-1-ylidene[bis(i-butylphoban)] ruthenium(II) dichloride Neolyst™ M3 C39H56Cl2P2Ru; FW: 758.78; red pwdr. Note: Sold in collaboration with Umicore for research purposes only.

250mg 1g

Technical Note: 1. This catalyst exhibits high selectivity as a general purpose metathesis catalyst for applications other than polymerization. It has improved air, moisture and heat resistance.

Reference: 1. Umicore studies to be published, 2007.

44-7777

Tricyclohexylphosphine[3-phenyl-1H- inden-1-ylidene][1,3-bis(2,4,6-tri- methylphenyl)-4,5-dihydroimidazol- 2-ylidene]ruthenium (II) dichloride, min. 95% Neolyst™ M2 [536724-67-1] C54H69Cl2N2PRu; FW: 949.09; dark red pwdr. Note: Sold in collaboration with Umicore for research purposes only. For use in lifescience applications and research purposes only.

100mg 500mg

Technical Note: 1. Catalyst used for the Atom Transfer Radical Polymerization (ATRP) of vinyl monomers.

Reference: 1. New J. Chem., 2003, 27, 257.

TUNGSTEN (Compounds)

74-2201

Tungsten carbonyl, 99% (<0.1%-Mo) [14040-11-0] W(CO)6; FW: 351.92; white to off-white pwdr.; m.p. 169-170° dec.

5g 25g

74-2202

Tungsten carbonyl, 99% (99.9+%-W) sublimed [14040-11-0] W(CO)6; FW: 351.92; white xtl.; m.p. 169-170° dec.

5g 25g

P

P

RuCl

Cl

Ph

Ru

PCy3

N N

Ph

Cl

Cl

EtO2C CO2Et

2 mol% Ru cat.

2 hr., rt, CH2Cl2 [98%]

EtO2C CO2Et

R'

R

+ R''XR''

XR'

nR

ST

REM

CH

EMIC

ALS

, IN

C.

7 M

ullik

en W

ay

New

bury

port,

MA

019

50-4

098

U.S

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Tel.:

(978

) 499

-160

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ax: (

978)

465

-310

4 (T

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num

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bel

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OF

RES

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CH

CH

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ALS

E

lect

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Che

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Fulle

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Pur

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s &

Chi

ral L

igan

ds

Met

al A

ceta

tes

& C

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nate

s M

etal

Alk

oxid

es &

bet

a-D

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Met

al A

lkyl

s &

Alk

ylam

ides

M

etal

Car

bony

ls &

Der

ivat

ives

M

etal

Cat

alys

ts &

Chi

ral C

atal

ysts

M

etal

Foi

ls, W

ires,

Pow

ders

& E

lem

ents

M

etal

Hal

ides

, Hyd

rides

& D

eute

rides

M

etal

Oxi

des,

Nitr

ates

, Cha

lcog

enid

es

Met

allo

cene

s N

ano

Mat

eria

ls

Org

anof

luor

ines

O

rgan

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allic

s O

rgan

opho

sphi

nes

& A

rsin

es

Por

phin

es &

Pht

halo

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reci

ous

Met

al &

Rar

e E

arth

Che

mic

als

Vol

atile

Pre

curs

ors

for M

OC

VD

& C

VD

B

ulk

Man

ufac

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g, C

usto

m S

ynth

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cG

MP

Faci

litie

s

Sea

rcha

ble

cata

log

at w

ww.s

trem

.com

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