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Bibliographic Notebooks For Organometallic Chemistry��2005, 23, ( 1)

[Li(THF) 3cyclo-(P4tBu4CH)]: Synthesis, Molecular Structure and Dynamic BehaviourLi

WOLF, R. ; HEY-HAWKINS, E.

MVI

PPP P

t-But-Bu

t-But-Bu

HH

RLi PPP P

t-But-Bu

t-But-Bu

H

Li (THF)3R = Me, n-Bu

Chem. Commun. 2626 26272004 -, , 22 ,

Bent Metal Carbene Geometries in Amido N-Heterocyclic Carbene ComplexesLi

Similar Mg and U complexes are also studied

MUNGUR, S. A. ; LIDDLE, S. T. ; WILSON, C. ; SARSFIELD, M. J. ; ARNOLD, P. L.

MVI

N

NNH

Rt-Bu

N

N

Nt-Bu

N

N

Nt-Bu R

R

Li Li

R = t-Bu, Mes

BuLi, THF

MgU

Chem. Commun. 2738 27392004 -, , 23 ,

Co-Condensation in Gaseous PhaseLi

No reaction occurred with X=NMe while oxazoles gave dilithiated species.

MENDOZA, O.; REHMANN, F.-J.K.; CUFFE, L.P.; TACKE, M.

GP

X X SiMe3(g)

1) Li(g), THF (g)77K

2) Me3SiCl, THF, r.t.X=NMe, O, S

25-45%

Eur. J. Inorg. Chem. 4525 45322004 -, , 22 ,

A-Ring of Sparteine: Essential for High Enantioselective Lithiation-Substitution.Li

DFT-QSSR analyses and DFT calculations are provided.

PHUAN, P.-W. ; IANNI, J. C.; KOZLOWSKI, M. C.

BP

N

Boc

N

Boc

SiMe3(S)

A

NNLi

HH

HH

HH

HH

H NNLi

H

CH3

HHH

H

H

H

1) s-BuLi, L*

2) TMSCl

Sparteine complex Minimal sparteine analog

L* =

1

76% of 1, 95% ee (S) 45% of 1, 35% ee (R)

J. Am. Chem. Soc. 15473 154792004 126 -, , 47 ,

1


An Experimental and Computational Study of the Enantioselective Lithiation.Li

Various sparteine-like diamines are studied, using sec-butyllithium and isopropyllithium.

O’BRIEN, P., WIBERG, K. B. ; BAILEY, W. F. ; HERMET, J.-P. ; MCGRATH, M. J.

BP

N

NH

H

N

Boc

N

Boc

LiTMSCl

N

Boc

SiMe3

(-)-sparteine

Sparteineor analogs good yields

high eriPrLi

J. Am. Chem. Soc. 15480 154892004 126 -, , 47 ,

Diastereoselective Alkylation of ββββ-Amino Esters.Li

Structural and rate studies reveal alkylations of hexameric lithium enolates. 6Li NMR studies are reported.

MCNEIL, A. J. ; TOOMBES, G. E. S. ; GRUNER, S. M. ; LOBKOVSKY, E. ; COLLUM, D. B. ; CHANDRAMOULI, S. M. ;VANASSE, B. J. ; AYERS, T. A.

BP

H3C OCH3

H2N OLi

BnBr

THF H3C OCH3

H2N OLi

(THF) (BnBr)

6 6

__

J. Am. Chem. Soc. 16559 165682004 126 -, , 50 ,

Improved Access to AryltrialkoxysilanesLi

Good yield also obtained from arylmagnesim. No reaction with halopyridines.

MANOSO, A.S.; AHAN, C.; SOHEILI, A.; HANDY, C.J.; CORREIA, W.M.S.; DESHONG, P.

GP

Br

R

(EtO)3SiR

1) n-BuLi (1 eq.)Et2O, -78°C

2) Si(OEt)4

Et2O, -78°C

25-85%

J. Org. Chem. 8305 83142004 69 -, , 24 ,

Enantioselective Reactions of αααα-Selenoorganolithium/Bis(oxazoline) ComplexesLi

Preparation of enantioenriched benzylidencyclohexanes is also described

NAKAMURA, S. ; AOKI, T. ; OGURA, T. ; WANG, L. ; TORU, T

MVI

Ph

ArSe SeAr

Ph

ArSe Li-Ln*

Ph

ArSe EN

O O

N

R R

1) n-BuLi2) chiral ligand

cumene

electrophile *

up to 95% ee Ln*

J. Org. Chem. 8917 89232004 69 -, , 25 ,

2


αααα-Allenic EstersLi

Role of base, base concentration, electrophile and additive is discussed. Mechanism is proposed.

LEPORE, S. D.; HE, Y.; DAMISSE, P.

CC

R

H

CO2Me

Li

OLi

R OMe

R

H E

CO2Me

LiNR2 (2eq), THF (0.1M)

30 min., -98°C, LiCl (1eq)

Electrophile (3eq)

-98°C to RT

J. Org. Chem. 9171 91752004 69 -, , 26 ,

Hydrogen-Metal Interconversions in DichloroarenesLi

Thanks to a proposed buttressing effect, lithiation affected the disfavoured C-4 position.

GORECKA, J.; HEISS, C.; SCOPELLITI, R.; SCHLOSSER, M.

GP

Cl Cl

I

SiEt3Cl Cl

SiEt3

Li

Cl Cl

Li

SiEt3Cl Cl

SiEt3

I

+ +-100°C

Org. Lett. 4591 45932004 6 -, , 24 ,

Optically Pure AlkylidenecyclopropanesLi

GARCIA RUANO, J. L.; ALONSO DE DIEGO, S. A.; ROSARIO MARTIN, M.; TORRENTE, E.; MARTIN CASTRO, A. M.

CC

R' R

SO2TolH

CNHR' R

CNH

1) BuLi, THF, -78°C

2) CH2I2 (1.8eq), iPrMgCl, THF -78°C to rt

R = nBu, tBuR' = H, Me Yields : 55 - 73%

4 Examples

Mg

Org. Lett. 4945 49482004 6 -, , 26 ,

Reductive Alkylation of AziridinesLi

ROSSER, C. M.; COOTE, S. C.; KIRBY, J. P.; O’BRIEN, P.; CAINE, D.

CC

NTs

R

OMe

n

n

NHTsR

R'

R = H, Men = 0, 1

R'Li (2.5 eq), Et2O

5 min. at -78°Cthen 1h at RT

15 examplesR' = CH2SiMe3, Yields : 47 - 67%R' = nBu, Yields : 22 - 54%R' = sBu, Yields : 32 - 67%R' = Me, Yields : 6 - 22%

Org. Lett. 4817 48192004 6 -, , 26 ,

3


Selective Bromide-Lithium Exchange ReactionLi

Effects of F-Li chelation, temperature, solvent and additives on selectivity are reported.

LI, Y.; LU, L.; ZHAO, X.

CC

F3C

RO

Br

Br

F3C

RO

E

Br

F3C

RO

Br

H

major product

High stereoselectivity9 examples Yields : 63 - 95%

2 examples Yields : 58 - 83% Moderate stereoselectivity

major product

nBuLi (1 eq) (slow addition)

THF, -78°C, (additive)

then Electrophile

R = MOM, MEMnBuLi, Hexane

-78°C then MeOH

Org. Lett. 4467 44702004 6 -, , 24 ,

Cyclopropene Carboxylic Acid Dilithium SaltsLi

LIAO, L.-A.; YAN, N.; FOX, J. M.

CC

R H

R' CO2H

R Li

R' CO2Li

R E

R' CO2H

R Ar

R' CO2H

MeLi

R, R' = H, alkyl, aryl,cycloalkyl, heteroaryl

Electrophilethen H+

9 examplesYields : 67 - 89%

ZnCl2,Pd(PPh3)4, ArI

2 examplesYields : 63 - 67%

ZnPd

Org. Lett. 4937 49392004 6 -, , 26 ,

Asymmetric Synthesis of αααα-Amino Carbonyl CompoundsLi

For extension of this procedure, see also reference : Org. Lett. 2004, 6, 24, 4427-4429.

DIXON, D. J.; HORAN, R. A. J.; MONCK, N. J. T.

CC

O NN

Cbz O

O NN

Cbz O

R

CbZHNR'

O

R

1) LiHMDS, -78°C, THF

2) RX, -78°C to RT

10 examples, Yields : 46 - 94%High diastereoselectivity, d.e.: 90 - 99%

1) TFA/H2O : 9/1 24h, RT

2) R'Li, THF, -78°Cor R'MgX, THF, 0°C

Org. Lett. 4423 44262004 6 -, , 24 ,

αααα-Alkylation of ββββ-Substituted ββββ-LactamsLi

PALOMO, C.; AIZPURUA, J. M.; GANBOA, I.; BENITO, A.; CUERDO, L.; FRATILA, R. M.; JIMENEZ, A.; LOINAZ, I.;MIRANDA, J. I.; PYTLEWSKA, K. R.; MICLE, A.; LINDEN, A.

CC

N

N

O

O

RO

R'

PhCH(TMS)2 N

N

O

O

RO

R'

Ph HR"

CH(TMS)2

R = H, Ph R' = alkylsyn

LDA, THF, -78°C, few minutes

then R"X, THF, -78°C to RT

R" = aryl, alkyl, benzyl, allyl

19 examples

Yields : 67 - 92%

Org. Lett. 4443 44462004 6 -, , 24 ,

4


Crystal structures of RLi/(+)-Sparteine Surrogate AggregatesLi

STROHMANN, C.; STROHFELDT, K.; SCHILDBACH, D.; MCGRATH, M.J; O’BRIEN, P.

VE

NN

Me

N N

(-)-sparteine (+)-sparteine surrogate

21

Crystal structures of [MeLi.(+)-2]2 and [(PhLi)4.{(+)-2}2] are given

Organometallics 5389 53912004 23 -, , 23 ,

Unusual Ortholithiation Versus Halogen-Lithium Exchange in BromopyridinesLi

The regiochemistry depends on the nature of electrophiles and reaction conditions

PIERRAT, P.; GROS, P.; FORT, Y.

VE

1) tBuLi (1 eq.)

THF, -78°C, 5 min

2) TMSCl, -78°C

1) 1 (1 eq.)THF, -78°C, 5 min

2) TMSCl, -78°CN

Br

1 N

Br

SiMe3

N

SiMe3

70%

tBuLi

92%

compare with

Si

Synlett 2319 23222004 -, , 13 ,

Solvent Effect in Diastereoselective Addition of Lithioacetonitrile to 2-Phenyl propanalLi

LiCH2CN was generated from CH3CN using different bases : LDA, LiHMDS, n-BuLi

CAINELLI, G. ; GALLETTI, P. ; GIACOMINI, D. ; GUALANDI, A. ; QUINTAVALLA, A

MVI

O

Ph

LiCH2CN

Ph

OHCN

Ph

OHCN+

solventtemperature

+

anti syn

solvent : benzene, toluene, n-hexane, cyclohexane, methylcyclohexane, THF, diethyl ether

Tetrahedron 69 752005 61 -, , 1 ,

Substituted[1.1.1.]propellanesLi

STULGIES, B.; PIGG, D. P.; KASZYNSKI, P.; KUDZIN, Z. H.

CC

O OO O

1) nBuLi (2.2eq), Et2O, RT, 6h

2) ICH2Cl (1.2eq), -30°C, then RT, 2h

Yields : 30 - 40% Yield : 25%

1) nBuLi (1.1eq), Et2O, RT then 4h, RT

2) CH2O then 1h RT

3) nBuLi (2.3 eq), Et2O, RT then 5h, RT

4) TsBr (1.2 eq), 0°C then 1h, RT

5) PPh3 (2.1eq), CCl4, 10h, 80°C

6) MeLi (1.2eq), Et2O/pentane, -30°C then 2h, RT

Tetrahedron 89 952005 61 -, , 1 ,

5


AllenesLi

Review, 107 references.

KRAUSE, N.; HOFFMANN-RÖDER, A.

CC

X

R

R'

R R R

R'HR'Li

then H+

SN'2

R'Li

1,4-addition

MgZnAlInTiCu

Tetrahedron 11671 116942004 60 -, , 51 ,

Reaction of 1-Chlorovinyl p-Tolyl Sulfoxides with Lithium EnolateLi

SATOH, T.; KAMIDE, Y.; SUGIYAMA, S.

CC

R

R' Cl

S(O)Tol R

R'

CH2CONMe2

S(O)Tol

Cl

R

R'

CH2CONMe2

CH3

O

R

R'

O

8 examples

LiCH2CONMe2 (5eq)

Yields : 22 - 99%

THF, -78°C

Tetrahedron 11805 118122004 60 -, , 51 ,

Ortholithiation of CyanopyridinesLi

Ortholithiations also proceed with CN at C-2 an C-3.

CAILLY, T.; FABIS, F.; LEMAÎTRE, S.; BOUILLON, A.; RAULT, S.

GP

N

NNLi

N

CN

N

CNFG

1) LiTMP (2 eq.)THF, -78°C Electrophile

then NH4Cl 54-75%

6 examples

Tetrahedron Lett. 135 1372005 46 -, , 1 ,

Cyclopropane-1,2-dianion Synthetic EquivalentsLi

HEUREUX, N.; MARCHANT, M.; MAUDILE, N.; BERTHON-GELLOZ, G.; HERMANS, C.; HERMANT, S; KISS, E.;WASNAIRE, P.; MARKO, I.E.

GP

Bu3Sn

SnBu3

H

H

Bu3Sn

FG

H

H

1) n-BuLi (1.3 eq.)THF, -78°C

2) ElectrophileTHF, -78°C

9 examples37-99%

Sn


6


Catalytic Intramolecular HydroaminationLi

3 examples.

VAN OTTERLO, W.A.L.; PATHAK, R.; DE KONIG, C.B.; FERNANDES, M.A.

GP

N

H(Me)OiPr

RH

MeO

N

H(Me)

Me

OiPr

R

MeO

n-BuLi (2x16%)

r.t., 6h then 60°C, 18h

63-87%


Enantioselective ProtonationLi

A reversal of enantioselectivity was observed using lithiated sulfonamides.

BOYD, E.; COUMBARIDES, G.S.; EAMES, J.; HAY, A.; JONES, R.V.H; STENSON, R.A.; SUGGATE, M.J.

GP

OAc

Me

O

MeH

O

Me H

N NX X

SO2R SO2R

1) MeLi-LiBrTHF, -78°C

2) S*H, -78°C3)Me3SiCl

1) MeLi-LiBrTHF, -78°C2) S*Li, -78°C

3) AcOH3)Me3SiCl

R=Naphtyl

S*H, X=HS*Li, X=Li

54%S, ee%45

57%R, ee%64


Insights into the Cerium Chloride-Catalyzed Grignard Addition to EstersMg

CONLON, D. A.; KUMKE, D.; MOEDER, C.; HARDIMAN, M.; HUTSON, M.; HUTSON, G.; SAILERZ, L.

LF

N

O OMeOH

Cl

MeMgCl, THF/toluene, < 5 °C

CeCl3N

OH

Cl

HO

> 99% selectivity

Ce

Adv. Synth. Catal. 1307 13152004 346 -, , 11 ,

Synthesis of Tetrahydro-1,2-OxazinesMg

The yields of the cycloadducts obtained with catalytic MgI2 were superior to those obtained with Yb(OTf)3 as catalyst.

GANTON, M. D.; KERR, M. A.

OS

N

Ph

p-TolO

O

CO2Me

CO2Me

O

NO

MeO2C CO2MePh

P-Tol+

+MgI2 10 mol%

THF, r.t.

86% (5 : 1)

J. Org. Chem. 8554 85572004 69 -, , 24 ,

7


C- versus O-AlkylationMg

O-Alkylation reaction between vinyl Grignard and carbonyl compounds can no longer be considered as a rare case.

BOGA, C.; STENGEL, R.; ABDAYEM, R.; DEL VECCHIO, E.; FORLANI, L.; TODESCO, P. E.

OS

S

N

S

N

O

S

N

S

N

OH

MgBrS

N

S

N

H O

++

50% 50%

THF, -70 °C, 15 mn

J. Org. Chem. 8903 89092004 69 -, , 25 ,

Electrophilic Amination of Grignard reagents with 1,3-Dioxolanone O-SulfoximeMg

KITAMURA, M.; SUGA, T.; CHIBA, S.; NARASAKA, K.

PJP

OO

NOSO2Ph

OO

NR

R-NH3+Cl-R-MgBr+

CH2Cl2or PhCl

(in Et2O)

HCl aq.

R = aryl, alkyl

64-97%

Org. Lett. 4619 46212004 6 -, , 24 ,

Synthesis and Application of α α α α-Arylsulfanyl- αααα-fluoro CarbenoidsMg

POHMAKOTR, M.; IEAWSUWAN, W; TUCHINDA, P.; KONGSAEREE, P; PRABPAI, S. ; REUTRAKUL, V.

OC

ArS Br

FF

ArS F

MgClF

ArS

RR

MgCl

2 RMgCl

ArS

RR

E

ERMgCl

Org. Lett. 4547 45502004 6 -, , 24 ,

Formation of CF3-Containing Quaternary Carbons via Stereospecific SN2’ ReactionMg

KIMURA, M.; YAMAZAKI, T.; KITAZUME, T.; KUBOTA, T.

OC

F3C

R1

OP(OEt)2

OR1

F3C R

CHOR1

F3C R

RMgXCuCN

TMSCl

1) O3

2) Me2S

R1 = CH2CH2Ph, n-C8H17, Ph

Cu

Org. Lett. 4651 46542004 6 -, , 25 ,

8


Synthesis of Functionalized Pyridines from 5-Bromo-pyridyl-2-magnesium ChlorideMg

SONG, J. J.; YEE, N. K.; TAN, Z.; XU, J.; KAPADIA, S. R.; SENANAYAKE, C. H.

OC

Br

I

Br

MgCl

Br

E

i-PrMgCl

0 °C

Electrophile

Org. Lett. 4905 49072004 6 -, , 26 ,

Aldol Addition of Ketones with Aldehydes Using MgI2 as PromoterMg

WEI, H.-X.; JASONI, R.L.; SHAO, H.; HU, J.; PARE, P.W.

PL

Ph

O

Ph

O

R

OH

Ph

O

R

OH

+ RCHO + MgI2/CH2Cl2piperidine

+

anti synR = Ph, 4-FC6H4, 4-BrC6H4, 4-MeC6H4PhCH=CH, CH3CH=CH, (CH3)3C anti/syn 84:16 to 100:0. Yields 82-92%

Tetrahedron 11829 118352004 60 -, , 51 ,

Chiral Sulfinyl Transfer ReagentsMg

The synthesis of chiral N-benzylsulfinyl derivatives is also reported.

CLARA-SOSA, A.; PEREZ, L.; SANCHEZ, M.; MELGAR-FERNANDEZ, R.; JUARISTI, E.; QUINTERO, L.; ANAYA DEPARRODI, C.

PL

N

O

O

SPhCH2

OPhCH2

SMe

OMeMgBr / THF

- 78°C

Yields 70-75%e.e. >98 %

Tetrahedron 12147 1121522004 60 -, , 52 ,

Highly Efficient and Recyclable Silica-Based Scandium(III) Catalyst.Sc

Catalyst could be recovered and reused for at least 10 reaction cycles without loss of reactivity.

KARIMI, B.; MA’MANI, L.

VWP

R R'

O TMSO

R R'

CNN

(TfO)2ScO

H

20 examples catyield > 70%

4.5 mol% cat, 1.2 equiv. TMSCN

CH2Cl2, rt, 2 - 24 h

Org. Lett. 4813 48152004 6 -, , 26 ,

9


Lewis-Acid Catalysed Diastereoselective Glyoxylate-Ene Reaction.Sc

High catalysts loadings (>30%) are required to reach interesting yields.

PAN, J.-F.; VENKATESHAM, U.; CHEN, K.

GR

N

N

Ph

O O

O

R

N

N

Ph

O O

R

OH

Ln(OTf)3+

7 examples, yields: 64-87%, de:75-94 %

SmLaEuYb


Alkene-Pinacolborane HydroborationsLa

HORINO, Y.; LIVINGHOUSE, T.; STAN, M.

OS

OH

B

OO

HTMS = trimethylsilyl

+

2) H2O2, OH-90 °C, 6 days

98% (regioisomeric ratio >99:1)

1) La[N(TMS)2]3 (3 mol%)

Synlett 2639 26412004 -, , 14 ,

Thioacetalization of Aldehydes Catalyzed by Praseodymium TriflatePr

27 examples, yields: 78-92%; recyclable catalyst; no reaction with ketones.

DE, S.K.

GJ

H

OSH

SH

S

S+

Pr(OTf)3 (5 mol%)

MeCN, rt, 1h82%

Synthesis 2837 28402004 -, , 17 ,

Stereoselectivity of the SmI2-Promoted Ketyl-Olefin CyclisationSm

Chelation of samarium with neighbouring groups controls the stereochemistry of the final ring.

KAN, T.; HOSOKAWA, S.; NARA, S.; TAMIYA, H.; SHIRAHAMA, H.; MATSUDA, F.

AS

RO

OBn

OBn

BnO

CHO

XPh

OHRO

OBn

OBn

BnO

SmI2 (2.5 equiv.)

THF/MeOH-78 °C

R= X=

H S

Ac S(O)

MeOCH2 S(O)

78-81%de=33-100%

J. Org. Chem. 8956 89582004 69 -, , 25 ,

10


Asymmetric Meerwein-Pondorf-Verley Reaction.Sm

OHNO, K.; KATAOKA, Y.; MASHIMA, K.

VWP

NN

OHOH

OHOH

Ph Ph

PhPh

O

R

OH

R

45 to 99% ee 17 to 99% conversion

5 mol% (R)-L10 mol% SmI(η8-C8H8)(THF)

2-propanol (20 - 25 equiv.)25 °C, 24 h

(R)-L

Org. Lett. 4695 46972004 6 -, , 25 ,

Reductive Homocoupling of Chiral N-ter-Butanesulfinyl Imines.Sm

Easy access to enantiopure C2-symmetrical 1,2-diamines.

ZHONG, Y.-W.; IZUMI, K.; XU, M.-H.; LIN, G.-Q.

VWP

H

NSO

R

NH

NH

S(O)tButBu(O)S

R R

2 equiv. SmI2, THF

2 equiv. HMPA, -78 °C25 to 99%

10 examples

Org. Lett. 4747 47502004 6 -, , 25 ,

Synthesis of Medium Sized RingsSm

The ketyl-alkyne coupling is favored when an aryl or/and a heteroatom spacer are present.

HÖLEMANN, A.; REISSIG, H. -U.

OS

O

R

CO2Me

OHR

CO2Me

R = H, n-Bu, CH2OMe THF, r.t. 12 h

SmI2 (2.2 equiv.) HMPA (18.0 equiv.)

t-BuOH (2.0 equiv.) 61-78%

Synlett 2732 27352004 -, , 15 ,

Rearrangement of Epoxides to Aldehydes and KetonesEr

Erbium triflate is efficient catalyst for this reaction because of its regioselectivity and its easy recoverability.

PROCOPIO, A.; DALPOZZO, R.; DE NINO, A.; NARDI, M.; SINDONA, G.; TAGARELLI, A.

OS

O O

CHO +

82% (14/86)

CH2Cl2, 3 h, reflux

Er(OTf)3 (1 mol%)Ce

Synlett 2633 26352004 -, , 14 ,

11


Endo-Regioselective Polyepoxide Oxacyclizations.Yb

BRAVO, F.; MCDONALD, F. E.; NEIWERT, W. A.; HARDCASTLE, K. I.

VWP

OO

OO

Me

H

OHH

Me

MeBOCO

H

Me

HOO

3 equiv. Yb(OTf)3

CH2Cl2, 20 °C, 1 h

73%

Org. Lett. 4487 44892004 6 -, , 24 ,

Preparation of 1,3-OxathiolanesYb

The catalyst immobilized in ionic liquid can be recycled and reused several times without loss of activity.

KUMAR, A.; JAIN, N.; RANA, S.; CHAUHAN, S. M. S.

OS

OSH

OH

O

S

+

Ionic liquid, r.t., 5 h

Yb(OTf)3 (5 mol%)

82%

Synlett 2785 27872004 -, , 15 ,

Synthesis of αααα,αααα’-Bis(substituted benzylidene)cycloalkanonesYb

20 examples, yields: 88-97%; solvent-free conditions; crossed aldol condensation of aldehydes with ketones.

WANG, L.; SHENG, J.; TIAN, H.; HAN, J.; FAN, Z.; QIAN, C.

GJ

O

PhCHO

O

PhPh+

(2 equiv)

Yb(OTf)3 (0.5 mol%)

90°C, 6 h92%

Synthesis 3060 30642004 -, , 18 ,

Ti-Catalyzed tandem Sulfoxidation-Kinetic Resolution ProcessTi

JIA, X.; LI, X.; XU, L.; LI, Y.; SHI, Q.; AU-YEUNG, T. T.-L.; YIP, C. W.; YAO, X.; CHAN, A. S. C.

CFR

SCH3 (S)-BINOL/Ti(IV)/H2O/TBHP

1) 0°C, 2) 25°C

SCH3

O:

up to 99.9% ee

Adv. Synth. Catal. 723 7262004 346 -, , 7 ,

12


Unprecedented Barbier-Type Reaction Catalysed by Titanocene(III)Ti

First attempts for assymmetric catalysis were also described.

ROSALES, A.; OLLER-LOPEZ, J.L.; JUSTICA, J.; GANSAUER, A.; OLTRA, J.E.; CUERVA, J.M.

MO

O

BrOH

MePh+

(86%)Cp2TiCl2 (0.2 eq),

Mn dust, Me3SiCl, 2,4,6-collidine

8 examples 4 examples

Chem. Commun. 2628 26292004 -, , 22 ,

Chiral Salen/Ti(OiPr)4 Catalyst in the Enantioselective Cyanosilylation of KetonesTi

Activation of the Chiral Salen/Ti(OiPr)4 catalyst with achiral phenolic N-oxides as additives

HE, B.; CHEN, F.-X.; LI, Y.; FENG, X.; ZHANG, G.

OC

R1 R2

OTMSCN+

10 mol% Salen-Ti(OiPr)4

1 mol% OH

NO

tBu

R1 R2

OTMSNC

up to 82% eeup to 96% yield

Eur. J. Org. Chem. 4657 46662004 -, , 22 ,

Dihalogenation of gem-Aryl-Disubstituted MethylenecyclopropanesTi

SHAO, L.-X.; ZHAO, L.-J.; SHI, M.

OC

R2R1

XX

TiX4+DIAD or DEAD

DCEX = Cl, Br, I

R2R1

Eur. J. Org. Chem. 4894 49002004 -, , 23 ,

Polymerisation Catalysts: Kinetic and Mechanistical AspectsTi

A review

BOCHMANN, M.

BPH

R RR [M]( )n M = Ti, Zr, Hf

ZrHf

J. Organomet. Chem. 3982 39982004 689 -, , 24 ,

13


Methylenation of Ketones and Aldehydes with CH2Cl2 Promoted by Mg/TiCl4/THFTi

YAN, T.-H.; TSAI, C.-C.; CHIEN, C.-T.; CHO, C.-C.; HUANG, P.-C.

OC

CH2Cl2Mg/TiCl4

THF0 °C

TiCl

MgCl

THF

R'

RFG

R' R' = H, Alkyl, Aryl

R'

R

O

FG

Mg

Org. Lett. 4961 49632004 6 -, , 26 ,

Photochemical Intramolecular Cycloaddition of Bridged Bis-azulenyl ZirconocenesTi

The rac isomer is stable toward photoirradiation

IWAMA, N.; KATO, T.; SUGANO, T.

MA

HR

Me2Si

HR

Me2Si

HR

HR

ZrCl2 ZrCl2

R

SiMe2

H

HR

ZrCl2+

rac meso

hνrac +

X ray structureR = Ph, 2-F-BiPh

in NMR tube

ZrSi


Stable Methylene- and Oxo-Bridged Monocyclopentadienyl Titanium CompoundsTi

“Wittig-type” reaction of the methylene dititanium complex with benzophenone is also reported

BUITRAGO, O.; DE ARELLANO, C.R.; JIMÉNEZ, G.; CUENCA, T.

MA

Si

Me Me

Ti MeMe

O

TiMeMe

OSi

MeMe

Si

Ti

MeC

TiMe

SiO O

H

MeMeMe

H

Si

Ti

MeO

TiMe

SiO O

MeMeMeMe

H2O

Me

80°Ctoluene

- CH4 - CH4

X ray structure

62 % yield 54 % yield

Si


Thermal Decomposition Routes for the Cationic Catalyst L2TiMe +Ti

DFT has been used to investigate the various decomposition pathways involving the cationic systems

WONDIMAGEGN, T.; VANKA, K.; XU, Z.; ZIEGLER, T.

MA

TiH3C N

SiCH3

CH3

CH3C CH3

CH3

methyl transferTi

H3CN

SiCH3

CH3

C

H3C CH3

H3C

Si


14


Effect of Tether Length on Cyclization of Epoxyalkenes and Unsaturated Epoxyketones.Ti

Study of Ti(III)-Mediated Cyclization.

FERNANDEZ-MATEOS, A. ; MATEOS-BURON, L. ; MARTIN DE LA NAVA, E. M. ; RABANEDO CLEMENTE, R. ; RUBIOGONZALEZ, R. ; SANZ GONZALEZ, F.

BP

O OO

n nor

n = 1 - 4

Cp2TiClSeveral mono- and bicyclic products (8 - 90 % yield)

Synlett 2553 25572004 -, , 14 ,

2,2’-Dibenzothiazolyl Disulfide (MBTS), Reagent for the Synthesis of 2-Azetidinones.Ti

MBTS forms a thioester with the acid groups. Then the titanium enolates of the thioesters condense with the imines.

SHARMA, S. D. ; KANWAR, S.

BP

R1 OH

R O

NR3

R2

N

R1 HR R2

O R3

N

R1 HR R2

O R3

MBTS/TPPTiCl4/Et3N

Dry CH2Cl2

cis trans

Good yields

cis:trans ratio depends on Rn groups

Synlett 2824 28262004 -, , 15 ,

Enantioselective Addition of Diethylzinc to Aromatic AldehydesTi

Various ligands were synthesized and tested.

LI, Z.; LIANG, X.; WAN, B.; WU, F.

GJ

H

O

H

OHC2H5

(C2H

5)2Zn

Ti(OiPr)4

OH

OH

+(R)-SPINOL

CH2Cl20°C, 12 h conversion > 99%

ee 88% (R)-SPINOL

Zn

Synthesis 2805 28082004 -, , 17 ,

Nucleophilic Ring-Opening Reactions of Chiral AcetalsTi

5 examples, yields: 62-89% (ee > 96).

MORELLI, C.F.; DURI, L.; SALADINO, A.; SPERANZA, G.; MANITTO, P.

GJ

O

OCF

3

Me

(CH2 )6CH3

TiCl4 (cat), Et

3SiD

O (CH2)6CH

3

OH

CF3

Me DH

CH2Cl2, -78°C, 2 h86% (R:S 96:4)

Si

Synthesis 3005 30102004 -, , 18 ,

15


Diastereoselective Synthesis of ββββ-Hydroxy Amides from ββββ-Keto AmidesTi

Practical synthetic procedure.

BARTOLI, G.; BOSCO, M.; MARCANTONI, E.; MASSACCESI, M.; RINALDI, S.; SAMBRI, L.

GJ

CH3 N

CH3

O

CH3

O

PhCH3 N

CH3

O

CH3

Ph

OHCH3

a) TiCl4, CH

2Cl

2

b) CH3MgX, CeCl

3

99% (de > 98%)-30°C

THF, -78°C

CeMg

Synthesis 3092 30962004 -, , 18 ,

Hydroamination-based Fischer Indole SynthesisTi

ACKERMANN, L.; BORN, R.

PJL

NR

NH2N

Ar

Alk

RAlk

ArTiCl4, tBuNH2

Toluene, 105 °C+


A novel Propargyltitanation of AcetylenesTi

Heteroatom substituent-dependent manifold in intermolecular coupling of allene and acetylene

TANAKA, R.; SASAKI, M.; SATO, F.; URABE, H.

PJL

Ti(OiPr)2

R2

R1R

•

XR1

R2X

R1

R2

R R1

R2

X

R1, R2 = Bu Bu; Ph Ph; SiMe3 C6H13 ; TBS C6H13; Ph Bu; SiMe3 Ph; SiMe3 CO2Bu-t X = SPh, Br

or or+Et2O

Mg


Water-Tolerant and Reusable Catalysts for Direct Ester CondensationZr

NAKAYAMA, M.; SATO, A.; ISHIHARA, K.; YAMAMOTO, H.

LF

O CO2HBnOH

O CO2Bn

Zr(OAc)x(OH)y

(O.1 mol %)

Octane, Azeotropic reflux

1 M HCl(1.o mL)

rt, 0.5 h

100 mmol scale TON > 4000

Adv. Synth. Catal. 1275 12792004 346 -, , 11 ,

16


Butadiene-Zirconocene ChemistryZr

Review

ERKER, G.; KEHR, G.; FROHLICH, R.

BPH

Cp2Zr Cp2ZrCp2Zr

J. Organomet. Chem. 4305 43182004 689 -, , 24 ,

Terminal Zirconium Imides Prepared by Reductive C-N Bond CleavageZr

X-ray diffraction analysis is reported for each.

BASULI, F.; KILGORE, U.J.; BROWN, D.; HUFFMAN, J.C.; MINDIOLA, D.J.

MA

Zr

NAr

CX

XN

Ar

Zr

NAr

C

NAr

Zr

NAr

CX

THFNAr

X- = Cl

(Nacnac)ZrX3

Nacnac- = [Ar]NC(tBu)CHC(tBu)N[Ar]

Ar = 2,6-[CH(CH3)2]2C6H3)

2 e-2 e-

1/2

X- = OTf


Heterocyclized Carbometalation of AlkynesZr

ZHOU, S.; LIU, D.; LIU, Y.

MA

NCp2Zr

R1R1

R1 R1

ArCN

R2 R2

"Cp2Zr"R1=Pr, Ph, Bu, Ar = 2-BrC6H42,6-Cl2C6H3

2-ClC6H42-FC6H4


Diastereoselective Synthesis of 2,5-Disubstituted DecahydroquinolinesZr

Preparation via ring-rearrangement metathesis (not shown) followed via zirconium-mediated cyclization.

NEIDHOFER, J.; BLECHERT, S.

GJ

N

H

CH2Ph

Pr N

H

CH2Ph

Pr

Me

Cp2ZrCl2, BuLi

N

H

CH2Ph

Pr

MeH

HTHF, -78°C to rt, 5 h

+

74% 20%

RuLi

Synthesis 3047 30542004 -, , 18 ,

17


Synthesis, Molecular Structure, and Olefin Polymerisation Activity of anOxovanadium(V) Alkoxide with Unprecedented Chloride Bridging Ligands

V

X-ray structure given; used as precatalyst for the polymerisation of ethene and styrene.

ROSENTHAL, E. C. E.; CUI, H.; LANGE, K. C. H.; DECHERT, S.

EG

HOOMe

LiOOMe

2 VOCl3, pentane, rt VCl

VCl

ClO

Cl OO

OO

O2

2

Eur. J. Inorg. Chem. 4681 46852004 -, , 23 ,

Efficient Asymmetric Oxidation of Sulfides and Kinetic Resolution of Sulfoxides Catalyzed bya Vanadium-Salan System

V

SUN, J.; ZHU, C.; DAI, Z.; YANG, M.; PAN, Y.; HU, H.

EG

RS

R'R

SR'

O

NH HN

OH HOR

SR'

O

RS

R'

O

RS

R'

O O

VO(acac)2 cat., Salan

H2O2, CHCl3

51<ee< 95%Salan =

VO(acac)2 cat., Salan

H2O2, CHCl378<ee< 98%

+

J. Org. Chem. 8500 85032004 69 -, , 24 ,

Vanadium-Catalyzed Sulfenylation of Indoles and 2-Naphtols with Thiols under MolecularOxygen

V

MAEDA, Y.; KOYABU, M.; NISHIMURA, T.; UEMURA, S.

EG

NH

ROH

RNH

SR'

ROH

SR'

R+ R'SH

VO(acac)2, O2

or or

J. Org. Chem. 7688 76932004 69 -, , 22 ,

Titanium and Niobium Imido Complexes Stabilized by Heteroscorpionate Ligands.Nb

The first examples of heteroscorpionate imido group 5 complexes are described.

OTERO, A.; FERNÁNDEZ-BAEZA, J.; ANTIÑOLO, A. ; TEJEDA, J.; LARA-SÁNCHEZ, A.; SÁNCHEZ-BARBA, L.;RODRÍGUEZ, A. M.

GR

N

NN

N

XC

O

NbClNR

Cl

H

N

NN

N

CE

TiPyNR

Cl

EH

X = O, H2R = tBu, p-Tol, 2,6-iPr2C6H3

E = O, SR = tBu, p-Tol, 2,6-iPr2C6H3

Ti

Dalton Trans 3963 39692004 -, , 23 ,

18


Diene Complexes of Early Transition MetalsTa

Review of the author’s works with >121 references.

NAKAMURA, A.; MASHIMA, K.

BPH

[M] [M]

Zr...

J. Organomet. Chem. 4552 45632004 689 -, , 24 ,

Involvement of an Oxydation-Reduction Equilibrium in Nozaki-Hiyama ReactionsCr

SCHREKKER, H. S.; MICSKEI, K.; HADJU, C.; PATONAY, T.; DE BOLSTER, M. W. G.; WESSJOHANN, L. A.

CFR

O

PhH

CrIIIO

HPh

rac

racemic

N N

n-Pr

O

PhH

CrIIIO

HPh

up to 32%

Adv. Synth. Catal. 731 7362004 763 -, , 7 ,

Carbene Complexes: DimerizationCr

BARLUENGA, J.; BARRIO, P.; VICENTE, R.; LOPEZ, L.A.; TOMAS, M.

RF

(CO)5Cr R1

X

Cu(I° catal ystX

X

R1

R1

X

O

R1

R1

R1

R1

X

XX = OMe

X = NR2

J. Organomet. Chem. 3793 37992004 689 -, , 23 ,

Cyclopentadienyl Chromium ComplexesCr

Cyclopentadienylchromium complexes and their use as catalyst for olefin polymerization

ZHANG, H.; MA, J.; QIAN, Y.; HUANG, J.

RE

N1

R1

R2

R

CrCl

Cl

R = H, R1 = 2 = CH3


19


Arenetricarbonylchromium Complexes: Mercurated and Ruthenated DerivativesCrRu

Synthesis of (+) and (-) mercurated and ruthenated (η6-arene)tricarbonyl chromiumDJUKIC,JP.BERGER,A.;DUQUENNE,M.;PFEFFER,M;DE CIAN,A;KYRITSAKAS-GRUBER,N.;VACHON,J;LACOUR,J

RE

N

Hg Cl(OC)3Cr

HgRu


Fischer Carbene ComplexesCr

X=O, S; M=Cr,W

BERNASCONI, C.F.; ALI, M.

RF

(CO)5M CXR

Ar

-CH(CN)2 (CO)5M CCH(CN)2

ArRX

ρ = 0.69 for (CO)5 Cr = (SMe) C6H4Zρ = 2.88 for (CO)5 Cr = (OMe) C6H4Z

W


Double Nucleophilic Addition of Hydride of ηηηη3-Allyl Mo LigandMo

Unprecedented double addition of a hydride ; 1,2-hydrogen migration and doube hydride

MINATO, M.; SEKIMIZU, R.; UCHIDA, D.; ITO, T.

RF

Cp2Mo+LiD

THF

CD2

Dalton Trans 3695 36982004 -, , 21 ,

New Mo(VI) Catalysts for the Epoxidation of CyclohexeneMo

Best results with X = Cl and L = OPMePh2.

WANG, G.; CHEN, G.; LUCK, L. L.; WANG, Z.; MU, Z.; EVANS, D. G.; DUAN, X.

BS

MoO2X2L2 (5% mol)

Ot-BuOOH (x? eq.), 1 h, RT

Conv. : 30-83%Selectivity : 65-86%

X = F, Cl, Br and L = OPMePh2, OPPh3

Inorg. Chim. Acta 3223 32292004 357 -, , 11 ,

20


Novel Polyaniline-Supported Molybdenum Catalyst.Mo

Alcohols were oxidized to aldehydes and ketones with cat in toluene using molecular oxygen.

VELUSAMY, S.; AHAMED, M.; PUNNIYAMURTHY, T.

VWP

MoO2(acac)2Polyaniline + MoO2(acac)2

CH3CN

rt, 50 hPolyaniline

cat

Org. Lett. 4821 48242004 6 -, , 26 ,

Olefin EpoxidationMo

KÜHN, FE.; ZHAO,.J.; ABRANTES, M.; SUN, W.; AFONSO, CAM.; BRANCO, LC.; GONÇALVES, IS.; PILLINGER, M.;ROMAO, CC.

RF

O

Cp'Mo(CO)3XTBHPRTIL, 55°C

Kühn, F.E.; Zhao, J.; Abrantes, M.; Sun, W.; Afonso, C.A.M.; Branco, L.C.; Gonsalves, J.S.; Pillinger, M.; Romao, C.C.


Preparation and Reactivity of Novel Tungsten ComplexesW

Preparation of cyclopropane-γ-lactones and -carboxylates.FLORIO, S.; PERNA, F. M.; LUISI, R.; BARLUENGA, J.; FANANAS, F. J.; RODRIGUEZ, F.

DCE

O

N

O

Li Ph

Ph

(CO)5W Ph

OMe

N

O

O W(CO)5

H

PhPh

Ph

Et2O, -98 to 20 °C

2) SiO2

80%

1)+

J. Org. Chem. 9204 92072004 69 -, , 26 ,

Steroids and Planar ChiralityMn

this complex has been obtained via a Sonogashira cross coupling reaction

FERLIER, B.; TOP, S.; JAOUEN, G.

RE

OH

Mn(CO)3

CO H

HO

CHO

(OC)3Mn

J. Organomet. Chem. 4872 48762004 689(25)

-, , 25 ,

21


Cross-Coupling Reaction Between o-Chloroaryl Ketones and Organo-Mn ReagentsMn

CAHIEZ, G.; LUART, D.; LECOMTE, F.

AB

Cl

R1

O R2

R1

OR2MnCl

THF, -60°C to 40°C30 min to 4h

R1, R2 = Alkyl or Aryl Y = 63-97%

Org. Lett. 4395 43982004 6 -, , 24 ,

Vilsmeier-Haack-Arnold Acylation of Activated Benzene Ligand.Mn

Hydrolysis generates the acylated benzene complex [Mn(CO)3{ η5-C6H6C(iPr)=O}].SHAO, L.; BADGER, P. D.; GEIB, S. J.; COOPER, N. J.

HJR

MnOC

CO

CO

H

NMe2iPr+

Mn-

OC CO

CO

OSO2CF3

N++THF, -78°C

Pale yellow, 10%


Catalytic Coupling of Carbon Dioxide and Epoxides.Mn

TON (mol epoxide consumed/mol Mn) = 50 for 24 h; Mn-O = 2.037(3) Å (X-ray).

DARENSBOURG, D. J.; GANGULY, P.; BILLODEAUX, D. R.

HJR

O

+ CO2 O

O

O

O

m n

O O

O

+(CO)3(dppp)MnOEt (0.040 mol%), 80°C

dppp : Ph2P(CH2)3PPh2

m>>n


Non-heme Iron Catalysed Oxidation of Alkanes with PeracidsFe

Improved selectivity in the non-heme iron catalysed oxidation of alkanes with peracids.

VAN DEN BERG, T. A.; DE BOER, J. W.; BROWNE, W. R.; ROELFES, G.; FERINGA, B. L.

LF

OH O

[(N4Py)Fe(II)(CH3CN)]2+

mCPBA / CH3CN

Chem. Commun. 2550 25512004 -, , 22 ,

22


The Substituent-dependent Base-treatment of (ηηηη5-C5H5)Fe(CO)2SiR2SiR2ClFe

Disilametallacycles, polymers or substitution products are formed with bases, LDA or BuLi.

SHARMA, H. K.; PANNELL, K. H.

LF

FeOC CO

SiR2SiR'2X

LDA / THF

(1.) LDA(2.) Ph3SnCl BuLi

FeOC CO

FeOC CO

SiR2SiR'2BuSiR2SiR'2X

FeOC CO

SiR'2R2Si

n

FeOC CO

Si

SiR'

R

R'

R

SnLi

Chem. Commun. 2556 25572004 -, , 22 ,

Iron(III) Salen-type Catalysts for the Cross-coupling of Aryl GrignardsFe

Highly active catalysts in the coupling of aryl Grignard reagents with alkyl halides.

BEDFORD, R. B.; BRUCE, D. W.; FROST, R. M.; GOODBY, J. W.; HIRD, M.

LF

ArMgBr R X Ar R

N

FeN

OCl

O

Chem. Commun. 2822 28232004 -, , 24 ,

Bioorganometallic Chemistry of FerroceneFe

VAN STAVEREN, D.R.; METZLER-NOLTE, N.

EJ

Review, 549 references

Chem. Rev. 5931 59862004 104 -, , 12 ,

Iron-Catalyzed Reactions in Organic SynthesisFe

BOLM, C.; LEGROS, J.; LE PAIH, J.; ZANI, L.

EJ


Chem. Rev. 6217 62542004 104 -, , 12 ,

23


C-H Activation by the Chelate (P,N) ComplexFe

x

LIPTAU, P.; CARMONA, D.; ORO, L. A.; LAHOZ, F.; KEHR, G.; ERKER, G.

GV

Ph2PN

Ru

PPh2N

Ph2PHN

RuCl

Cl

Fe

Fe Fe

[Ru(p-cymene)Cl2]2

+

Ru

Eur. J. Inorg. Chem. 4586 46012004 -, , 23 ,

New Iron Catalysts for the Oxydation of Alkane with Hydrogen peroxideFe

PAP = 1,4-di-(2’-pyridyl)aminophthalazine

BALOGH-HERGOVICH, E.; SPEIER, G.; RÉGLIER, M.; GIORGI, M.; KUZMANN, E.; VERTES, A.

BS

Fe2(µ-OMe)2(PAP)Cl4 or Fe2(µ-OMe)2(PAP)(OAc)4

OH2O2 (1-3 eq.), MeCN, 4-10 h, RT

Conv. up to 40%

+

OH(10-3% mol)

Selectivity : 1/1 to 1/3

Inorg. Chim. Acta 3683 36962004 357 -, , 12 ,

Iron tricarbonyl stabilized Pentadienyl Cation for Cascade Polycyclizations.Fe

PEARSON, A. J.; GHIDU, V. P.

VWP

(CO)3Fe

OMe

OMe

(CO)3Fe

OMe

(CO)3Fe

+

HCOOH, 50 °C

35%

J. Org. Chem. 8975 89782004 69 -, , 25 ,

Polymerization and Schulz-Flory OligomerizationFe

BIANCHINI, C.; GIAMBASTIANI, G.; GUERRERO, I. R.; MELI, A., PASSAGLIA, E.; GRAGNOLI, T.

GV

N FeCl

NCl

N

/ MAO

n n+

toluenecat.

cat.


24


[2]-Ferrocenonane with C-Ge and C-Sn BridgesFe

BARTOLE-SCOTT, A.; RESENDES, R.; JAKLE, F.; LOUGH, A. J.; MANNERS, I.

GV

R = Me, Ph R = tBu, Mes, Me

GeR2

CH2

MeMe

Me

Me

SnR2

CH2

MeMe

Me

MeFe Fe

SnGe


Synthesis of αααα-Substituted Iminodiacetate LigandsFe

The synthesis of α-hexadienyl side chain of imidodiacetic acid has been presented.KALITA, B.; NICHOLAS, K.M.

PL

F3CCOHN

OMe

OSiMe3

AcO

Fe(CO)3

TMSOTf

Fe(CO)3

F3CCOHN

CO2Me86%

diastereomeric ratio = 1:1

Tetrahedron 10771 107782004 60 -, , 47 ,

FeCl3-Promoted Synthesis of a BisindolineFe

NMR spectroscopy and mass spectrometry studies were presented.

THOMAS, N.F.; VELU, S.S.; WEBER, J.-F.F.; LEE, K.C.; HADI, A.H.A.; RICHOMME, P.; RONDEAU, D.; NOORBATCHA, I.;AWANG, K.

PL

NHAc

OMe

OMe

NAc

OMe

OMe

AcN

OMe

MeO

NAc

OMe

OMe

H H

+38% 15%FeCl3.6H2O

CH2Cl2

Tetrahedron 11733 117422004 60 -, , 51 ,

Biocatalytic Procedure for Synthesis of Ferrocenyl DerivativesFe

The lipase recognises only the two isomers possessing an (R) central-configuration.

D’ANTONA, N.; LAMBUSTA, D.; MORRONE, R.; NICOLOSI, G.; SECUNDO, F.

PL

Fe Fe OH FeHO

1) CH3COCl AlCl3

2) LiAlH4

+

4 diastereomers

C. antarcticavinyl acetateTBME

Separation of isomers

Tetrahedron Asymm. 3835 38402005 15 -, , 24 ,

25


Grubbs’ Catalyst Obtained from an Indenylidene ComplexRu

DORTA, R.; KELLY III, R.A.; NOLAN, S.P.

AF

RuCl2(PPh3)3 +Ph

PhOH

1) THF, ∆

2) 2-3 equiv. PCy3

90 - 95 %

Cy3P

Ru

PCy3

Cl

Cl

Ph Cy3P

Ru

PCy3

Cl

ClPh

+

Ph

THF

styrene(20 equiv.)

70 ºC, 90 min 88 % overall

Adv. Synth. Catal. 917 9202004 346 -, , 8 ,

New Biaryl Phosphanes for Enantioselective HydrogenationRu

R: Ph, p-fluorophenyl, xylyl, 2-furyl, 2,5-dimethoxyphenyl

DRIESSEN-HÖLSCHER, B.; KRALIK, J.; AGEL, F.; STEFFENS, C.; HU, C.

AF

CO2Me

CO2Me+ H2

1 bar

{L*}Ru(OOCCF3)2(1 mol %)

MeOH50 ºC, 1 h

generally 100 %

CO2Me

CO2Me

92 - 97 % ee

Cl

MeO

MeO

Cl

PR2

PR2L*:

Adv. Synth. Catal. 979 9822004 346 -, , 8 ,

New Route to the Tris(acetonitrile)-CpRu(II) ComplexRu

KÜNDIG, E.P.; MONNIER, F.R.

AF

RuCl3,nH2O Ru

96 %Ru

+PF6-

1) C10H8, AlCl3, Al, TiCl4 decalin 140 ºC

2) aq. KPF6

RuMeCN NCMe

NCMe

+PF6-

MeCN, r. t.

97 %80 %

Adv. Synth. Catal. 901 9042004 346 -, , 8 ,

Alkynes Metatheses in transition Metal Coordination SpheresRu

BAUER, E. B.; HAMPEL, F.; GLADYSZ, J. A.

CFR

RuCl

PPh3

Ph3P

3

Refluxing toluene

Ru

Cl Ph2P

PPh2

(t-BuO)3W( C t-Bu)

10 mol%

Ru

Cl Ph2P

PPh2

52%

ReWMo

Adv. Synth. Catal. 812 8222004 346 -, , 7 ,

26


A New Family of Carbazole-Based Diphosphine Ligands BICAPRu

BOTMAN, P. N. M.; FRAANJE, J.; GOUBITZ, K.; PESCHAR, R.; VERHOEVEN, J. W.; VAN MAARSEVEEN, J. H.;HIEMSTRA, H.

CFR

OMe

O ORu/H2

BICAP OMe

OOH

MeO2C OMe

O Rh/H2

BICAP MeO2C OMe

ORN

PPh2

NR

PPh2

BICAP

Conversion 100%ee up to 99%

Conversion 100%ee up to 55ù

Rh

Adv. Synth. Catal. 743 7542004 346 -, , 7 ,

Ru-Catalyzed O-Allylation of Phenols from Allylic ChloridesRu

MBAYE, M. D.; DEMERSEMAN, B.; RENAUD, J.-L.; TOUPET, L.; BRUNEAU, C.

CFR

R Cl + ArOHcat

(K2CO3)r.t.

R

OArCat. = [Cp*(MeCN)3Ru][5PF6]

R= Me, H 60-100%

Adv. Synth. Catal. 835 8412004 346 -, , 7 ,

Enantioselective Reduction of Ketones Catalyzed by Ruthenium ComplexesRu

SCHLATTER, A.; KUNDU, M.K.; WOGGON, W-D.

MA

R1 R2

O NH

OH

R1R2

DCO2Na

+ [{RuCl2(C6H6)}2]R1

R2HO D

cata/substrate/DCO2Na = 1/10/100R1=H, R2=CH3, C2H5 yields: 53-79 %

ee: 76-87 %

β

cata

amino alcoholβ-cyclodextrins

S

Angew. Chem. Int. Ed. 6731 67342004 43 -, , 48 ,

Unprecedented Intramolecular Coupling of o-Carboranyl and CyclopentadienylRu

A novel ruthenium-mediated coupling reaction of a carboranyl with a cyclopentadienyl.

SUN, Y.; CHAN, H.-S.; DIXNEUF, P. H.; XIE, Z.

LF

LiCl2Ru(PPh3)3

RuH

PPh3

PPh3

Chem. Commun. 2588 25892004 -, , 22 ,

27


Aminooxazolinate : a Chiral Amidinate AnalogueRu

High levels of diastereoselection are achieved for Ru and Zr complexes.

MUNSLOW, I. J.; WADE, A. R.; DEETH, R. J.; SCOTT, P.

LF

Pri

RuN Cl

NBut

HO

observed SRu isomer

Pri

RuN Cl

N

unobserved RRu isomerO

HtBu

dr > 95 : 5

Zr

Chem. Commun. 2596 25972004 -, , 22 ,

Synthesis of C-arylglycosides via Ru(II)-catalyzed [2 + 2 + 2] CycloadditionRu

[2 + 2 + 2] cycloaddition of a,ϖ-diynes with C-alkynylglycosides.YAMAMOTO, Y.; SAIGOKU, T.; OHGAI, T.; NISHIYAMA, H.; ITOH, K.

LF

O

AcO

AcOX

Cp*RuCl(COD)

DCE, rt

X = C(CO2Me)2, NTs, O, etc.

O

AcO

AcOX

Chem. Commun. 2702 27032004 -, , 23 ,

Ruthenium- and Gold-catalysed Sequential ReactionsRu

Straightforward synthesis of substituted oxazoles from propargylic alcohols and amides.

MILTON, M. D.; INADA, Y.; NISHIBAYASHI, Y.; UEMURA, S.

LF

Ph

OH

H2N

O

[Ru], NH4BF4, AuCl3, ClCH2CH2Cl,

80 °C, 18h

N

O

Ph

H2O Ru Ru

Cl Cl

*Cp Cp*

MeS SMe

[Ru] =

Au

Chem. Commun. 2712 27132004 -, , 23 ,

Propargylic Substitution and Isomerization Ru

CADIERNO, V.; DIEZ, J.; GARCIA-GARRIDO, S. E.; GIMENO, J.

LF

HOH

PhPh

[Ru]

THF / 75 °C

OH

H

Ph

Ph

[Ru]

ROH / 75 °CH

OR

PhPh

Ru

OCP

P P P = dppf

Me

[Ru] =

[SbF6]

Chem. Commun. 2714 27152004 -, , 23 ,

28


Mechanism of Hydrogen Transfer to Imines from a Hydroxycyclopentadienyl RuHRu

SAMEC, J. S. M.; ELL, A. E.; BÄCKVALL, J.-E.

LF

Ru

OCCO

H/D

PhPh

Ph Ph

OH/D

Ru

OCCO

N

PhPh

Ph Ph

O

H/DPh

H/DMe

Me

N PhMeO

MeO

-54 °C, CD 2Cl2

Chem. Commun. 2748 27492004 -, , 23 ,

Synthesis of Fused Polycyclic Compounds from Propargylic Alcohols and AlkenesRu

NISHIBAYASHI, Y.; YOSHIKAWA, M.; INADA, Y.; HIDAI, M.; UEMURA, S.

CJM

R1

O

OH

R2R2

H

[Cp*RuCl(µ2-SiPr)2RuCp*Cl] 5%NH4BF4 10%PtCl2 10%

ClCH2CH2Cl, 60 °C

R114 examples38-90%

Pt

J. Am. Chem. Soc. 16066 160722004 12649

-, , 49 ,

Direct Aziridination of Alkenes by a Cationic (Salen)ruthenium(VI) Nitrido Complex.Ru

First example of direct nitrogen atom transfer from a metal nitride to alkenes. The molecular structure is given.

MAN, W.-L., LAM, W. W. Y. ; YIU, S.-M. ; LAU, T.-C. ; PENG, S.-M.

BP

RuVI

N+

K

py RuVI

N+

py

k2

RuIV

+

py

N k'

RuIII

+

py

NH

J. Am. Chem. Soc. 15336 153372004 126 -, , 47 ,

Anion-Templated Assembly of a [2]Catenane.Ru

SAMBROOK, M. R. ; BEER, P. D. ; WISNER, J. A. ; PAUL, R. L. ; COWLEY, A. R.

BP

ClRCM

ClGrubbs I, 10 wt %

45 %- -

J. Am. Chem. Soc. 15364 153652004 126 -, , 47 ,

29


Cycloisomerisation of o-(Ethynyl)phenylalkenes to Diene Derivatives.Ru

The reaction is an atypical enyne cycloisomerisation with skeletal rearrangement of starting enyne.

MADHUSHAW, R. J. ; LO, C.-Y. ; HWANG, C.-W. ; SU, M.-D. ; SHEN, H.-C. ; PAL, S. ; SHAIKH, I. R. ; LIU, R.-S.

BP

TpRu(PPh3)(CH3CN)2PF6, 10 mol %

Benzene, 80 ºC, 12-18 h+

major minor

J. Am. Chem. Soc. 15560 155652004 126 -, , 47 ,

Enyne Cycloisomerisations: Effect of Allylic Silyl Ether on Regioselectivity.Ru

TROST, B. M. ; SURIVET, J.-P. ; TOSTE, F. D.

BP

NCO2CH3

OTBDMS

Ts NTs

CO2CH3

OTBDMSNTs

CO2CH3

OTBDMS

CpRu(NCCH3)3PF6, 10 mol %

Cp*Ru(NCCH3)3PF6, 10 mol %

60 % E/Z, 4/1

81 % E/Z, 1/14

CH3COCH3, r.t.

J. Am. Chem. Soc. 15592 156022004 126 -, , 47 ,

Shape-Tunable Polymer Nodules Grown from Liposomes via ROMP.Ru

Liposomes are prepared with 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) and initiator.

JARROUX, N. ; KELLER, P. ; MINGOTAUD, A.-F. ; MINGOTAUD, C. ; SYKES, C.

BP

PCy2

RuCl

Cl

Ph

PCy2

CO2HROMP

5

5

and DOPC Liposomes +Initiator Polymer

J. Am. Chem. Soc. 15958 159592004 126 -, , 49 ,

Ru- and Pt-catalyzed Sequential reactions.Ru

Selective synthesis of fused polycyclic compounds from propargylic alcohols and alkenes.

NISHIBAYASHI, Y. ; YOSHIKAWA, M. INADA, Y. ; HIDAI, M. ; UEMURA, S.

BP

OH

O

[Cp*RuCl(µ2-SiPr)2RuCp*Cl], 5 mol %

and PtCl2, 10 mol % OHR R

synO

HR

anti

+

38-83 % yield, ratio of isomers syn:anti up to 94:6

Pt

J. Am. Chem. Soc. 16066 160722004 126 -, , 49 ,

30


RuO4-Catalyzed Ketohydroxylation of Alkenes.Ru

Exploration of scope and limitaion. A catalytic cycle is proposed.

PLIETKER, B.

VWP

RR'

RR'

OH

OR

R'O

OH

yields up to 96%numerous examples

1 mol% RuCl35 equiv. oxone

2.5 equiv. NaHCO3

AcOEt/CH3CN/H2O

J. Org. Chem. 8287 82962004 69 -, , 24 ,

Ru-Catalyzed [2+2] Cycloadditions between Norbornadienes and Alkynes.Ru

A mecanism is proposed and ab initio studies were developped.

JORDAN, R. W.; KHOURY, P. R.; GODDARD, J. D.; TAM, W.

VWP

Y Ph

CO2Et

YPh

CO2Et+

5 eq. 1 eq.

anti-exo

Y = OAc, OTBS, OtBu, H, Hexyl, Ph

yield > 68%

5-10 mol% Cp*RuCl(COD)

Et3N, 80-95 °C

J. Org. Chem. 8467 84742004 69 -, , 24 ,

[2+2] Cycloadditions Between Bicyclic Alkenes and Alkynyl HalidesRu

The presence of the halide greatly enhances the reactivity of the alkyne component. A variety of products are obtained.

VILLENEUVE, K. ; RIDDELL, N. ; JORDAN, R. W. ; TSUI, G. C. ; TAM, W.

BP

Cp*RuCl(COD)

THF

X

R

R'

R

X = Cl, Br, I - R = alkyl, aryl, ester, sulfone - R' = H, alkyl, SiMe3, Ar, alkynyl.

32 - 89%

RX

Org. Lett. 4543 45462004 6 -, , 24 ,

Synthesis by Cross-Metathesis of Ligands Bearing Mannose 6-Phosphate Surrogates.Ru

BERKOWITZ, D. B. ; MAITI, G. ; CHARETTE, B. D. ; DREIS, C. D. ; MACDONALD, R. G.

BP

OHO

HO

O

O

HPO

OO

OHO

HO

O

O

HPO

OO

2 XO

P'OP'O

OP'

O

PP''O

P''OO

Grubbs I cat.

67 - 84 % depending on P' and P''

Org. Lett. 4921 49242004 6 -, , 26 ,

31


New Mechanism for the Intermolecular Hydroamination of Alkynes by Ru ComplexesRu

New type of hydroamination mechanism

KLEIN, D.P.; ELLERN, A.; ANGELICI, R.J.

MD

Ru Ru

Ph H

COOC

Si Si

O+ HBF4

Ph H + H2N p-tolyl[Catalyst, 10 mol%] Catalyst :N

p-tolyl

Ph CH329% yield


Reaction of Ruthenium(0) Phosphine Complexes with DiphenylacetyleneRu

HILL, A.F.; SCHULTZ, M.; WILLIS, A.C.

MD

RuPh3PPPh3

OC CO

∆

O

RuOC

PPh3

PPh3


Silane-Induced Polymerization of Vinyl Ethers Catalyzed by a Triruthenium ClusterRu

NAGASHIMA, H.; ITONAGA, C.; YASUHARA, J.; MOTOYAMA, Y.; MATSUBARA, K.

MD

OR

Cat.

R3Si-H ORR3Si

ROR3Si

H

Mn = 2,000-25,000Mw/Mn = 1.2 - 3.4

Ru

RuRu(CO)2

CO

(CO)2

(CO)2

Catalyst :

n


Ruthenium-Catalyzed Allylation of Aromatic Compounds and Allylic Ether FormationRu

Allylation of various aromatic compounds and allylation of simple alcohols

ONODERA, G.; IMAJIMA, H.; YAMANASHI, M.; NISHIBAYASHI, Y.; HIDAY, M.; UEMURA, S.

MD

R'' OH

R'

R'''OH

Catalyst

R''R'

R'' OR'''

Ru RuRS SR

Cp*Cp*

OH2Cl

OTf

R = Me, iPr

Catalyst :

17 examples

5 examples

11-99% yield

21-99% yield


32


Ru-Azirinyl Complexes and Reversed Regiospecificity of Carbonyl Insertion ReactionRu

Formation of oxazolinyl complexes by insertion of cetones, aldehydes, esters and amides

LO, Y.-H.; HSU, S.-C.; HUANG, S.-L.; LIN, Y.-C.; LIU, Y.-H.; WANG, Y.

MD

[Ru] NR

[Ru]N

HR

N

O[Ru]

R

R''R'

R'R''CO

R = CN, CH=CH2, Ph

13 examples

high yields


Alkenyl Metathesis SynthonsRu

BAUGHMAN, T.W.; SWOREN, J.C.; WAGENER, K.B.

PL

Br( )9 Br

Br( )( )9

Br Br( )18

Br( )18

[RuCl2(PCy3)2=CHPh] [RuCl2(PPh3)2] KOtBu

toluene H29

Tetrahedron 10943 109482004 60 -, , 48 ,

Ruthenium(II) Bipyridyl-Transition Metal Dithiocarbamate MacrocyclesRu

Two other macrocycles have been synthesized. Luminescence spectroscopy has been used.

PRATT, M.D.; BEER, P.D.

PL

N

N N

N

N

N

Ru2+

O

N

O

N

N

SSM

N

SS

H

H

M = Ni, Cu, Zn56-95% yields

2PF6-

NiCuZn

Tetrahedron 11227 112382004 60 -, , 49 ,

Dinucleotides for Ring Closing MetathesisRu

BORSTING, P.; FREITAG, M.; NIELSEN, P.

PL

N

O

O

TBDMSO

NH

O

O

N

OTBDMS

O

O

NH

O

O

PCEO O

N

O

O

TBDMSO

HN

O

O

N

OTBDMS

O

O NH

O

O

PCEO O5 mol%, CH2Cl2, reflux23%

MesN NMes

Ru

PCy3

Cl

ClPh

CE = 2-cyanoethyl

Tetrahedron 10955 109662004 60 -, , 48 ,

33


New Polymers for Catalytic Carbene TransferRu

The polymer is able to catalyze cyclopropanations and 2,3-sigmatropic rearrangements with ethyl diazoacetate.

PAUL-ROTH, C.; RAULT-BERTHELOT, J.; SIMONNEAUX, G.

PL

N

N

N

N Ru

CO

Polymer

Anodic oxidationin CH2Cl2+ Bu4NPF6

Tetrahedron 12169 1121752004 60 -, , 52 ,

Asymmetric Reduction of Tetralones Derivatives by Ru-ComplexesRu

MOGI, M.; FUJI, K.; NODE, M.

PL

O

R

OH

R

[RuCl2(p-cymene)]21 or 2

KOH, 2-propanol50°C, 45 min

NH2

OH

NHTsPh

NH2Ph1

2

E.e. 73 to 96%Yields 71 to 85%R = H, 5-,6-,7- or 8-OMe


Macrocyclic Templates by Ring Enlargement of Ansa-SteroidsRu

BAURLE, S.; BLUME, T.; LEROY, E.; MENGEL, A.; PARCHMANN, C.; SCHMIDT, K.; SKUBALLA, W.

PL

TBSO

OTBS

OAc

H

OO

TBSO

OTBS

OAc

H

OO

[RuCl2(PCy3)2=CHPh]

CH2Cl2, rt, 6.5h36%


N-Heterocycles via Cross Metathesis-Reductive CyclizationRu

The synthesis of piperidine, pyrrolidine, indolizidine, pyrrolizidine derivatives has been realized.

GEBAUER, J.; DEWI, P.; BLECHERT, S.

PL

NHR1

CO2Bn

( )n OMe

ONHR1

CO2Bn

( )n OMe

O

N OH

R1

( )n

Ru

O

IHMes

ClCl

+

R1 = CO2Me, CH2OBn

71-76%

n = 0,1

H2, Pd/C

Pd


34


Hydrosilylation of Alkynes Catalyzed by Ru-Carbene ComplexesRu

MAIFELD, S.V.; TRAN, M.N.; LEE, D.

AF

R

R

SiR'3

R SiR'3 R

R'3Si

+ +HSiR'

E Z α[RuCl2(PCy3)2=CHPh]

R = Ph, (CH2)nOH, n-Bu E / Z / α up to19:0:1Yields up to 95%R' = Me2Ph, Ph2H, Et3, Ph3


Constrained Amino Acid Derivatives by Ring Closing MetathesisRu

KOTHA, S.; SINGH, K.

PL

NAc

EtO2C CO2Et

( )n

NAc

EtO2C CO2Et

( )n MesN NMes

Ru

PCy3

Ph

Cl

Cl

[Ru]

DCM, rt

83-92% for n = 1,3,4


Pauson-Khand Reaction with a Cyclobutadiene Equivalent Co

GIBSON, S.E.; MAINOLFI, N.; KALINDJIAN, S.B.; WRIGHT, P.T.

AF

R+ CO2Me

CO2Me1.5

7 mol % Co2(CO)8

CO (1 atm)DME, 75 ºC, 4 h

then 205 ºC, 6 torr, 1.5 h

RO

up to 10 mmol scale 90 %

Angew. Chem. Int. Ed. 5680 56822004 43 -, , 42 ,

Cobalamine-Colchicine ComplexCo

A novel tumor-targeted cytotoxin.

BAGNATO, J. D.; EILERS, A. L.; HORTON, R. A.; GRISSOM, C. B.

DCE

Co

O

NH

OO

NH

OOMe

MeO

MeO

MeO

NOH

Synthesis of Cobalamin Bioconjugate

J. Org. Chem. 8987 89962004 69 -, , 26 ,

35


Synthesis of Tricyclic Oxygen-Containing HeterocyclesCo

A tandem intramolecular Nicholas-Pauson-Khand reaction was used

QUINTAL, M.M.; CLOSSER, K.D.; SHEA, K.M.

AB

HO( )n

OMe

O

H

O( )n

HCo2(CO)8 Nicholas then

Pauson-Khand

n = 1-3 Y = 29-91%

O

H

O( )n

H+

1 21/2: from 37/63 to 72/28

Org. Lett. 4949 49522004 6 -, , 26 ,

N-Heterocyclic “Pincer” Dicarbene ComplexesCo

Co(I), Co(II), and Co(III) complexes have been characterized.

DANOPOULOS, A.A.; WRIGHT, J.A.; MOTHERWELL, W.B.; ELLWOOD, S.

AF

Co{N(SiMe3)2}2

(CH-N-CH)Br21 equiv.

THF

N N

Co

N N

NBr

Br

Ar

Ar

N N

Co

N N

N Br

Ar

Ar

Na(Hg)

Toluene

N N

Co

N N

N CH3

Ar

Ar

MeLi (1.5 equiv.)

Toluene

X-Ray90 % 86 % 68 %Ar: 2,6-Pr2C6H3


Preparation of Tetramethylcyclobutadiene ComplexesCo

Several examples of complexes are described along with their electrochemical, UV-visible and X-ray properties.

MUTSENECK, E.V.; LOGINOV, D.A.; PEREKALIN, D.S.; STARIKOVA, Z.A.; GOLOVANOV, D.G.; PETROVSKII, P.V.;ZANELLO, P.; CORSINI, M.; LASCHI, F.; KUDINOV, A.R.

AF

Rn

Rn PRn

P Rn

Co Co(MeCN)3

MeCNCo


Highly Enantioselective Hydrogenation of Itaconic Acids Bisphospholane-Rh(I)Rh

ALMENA, J.; MONSEES, A.; KADYROV, R.; RIERMEIER, T. H.; GOTOV, B.; HOLZ, J.; BÖRNER, A.

LF

MeO2CCO2Me

[Rh(COD)2]BF4

H2, 4 barMeO2C

CO2Me O

O

O

P

P

L

L =

TON up to 10,000TOF up to 40,000 / hee up to 99%

Adv. Synth. Catal. 1263 12662004 346 -, , 11 ,

36


Kinetic Study of Homogeneous Alkene Hydrogenation by Model DiscriminationRh

GREINER, L.; TERNBACH, M. B.

LF

Ph

CO2H

NHAc H2Ph

CO2H

NHAc

BzN

PPh2

PPh2

Rh BF4

Adv. Synth. Catal. 1392 13962004 346 -, , 11 ,

Phenoxaphosphino-Modified Xantphos-Type Ligands in HydroformylationRh

BRONGER, R. P. J.; BERMON, J. P.; HERWIG, J.; KAMER, P. C. J.; VAN LEEUWEN, P. W. N. M.

CFR

O

R1 R1

POP POP

POP =

O

P R2R2R1 aqnd R2 are either H or (branched) alkyl groups

Adv. Synth. Catal. 789 7992004 346 -, , 7 ,

Silyl Boryl Hydride Complexes: Formation and ReactivityRh

Borane more rapidly dissociated than silane.

COOK, K.S.; INCARVITO, C.D.; WEBSTER, C.E.; FAN, Y.; HALL, M.B.; HARTWIG, J.F.

AF

[Cp*Rh(H)2(SiEt3)2]excess HBpin

80 ºC or hν Rh

Bpin HSiEt3H

X-Ray

P(p-tol)3

∆ RhP

HSiEt3

Rh

Bpin HP(p-tol)3

13 %

(p-tol)3

68 %

+

BSi

Angew. Chem. Int. Ed. 5474 54772004 43 -, , 41 ,

Enantioselective Synthesis of DiarylmethylaminesRh

Other ligands investigated. Tuning of the aryl (Ar and Ar1) groups.

HAYASHI, T.; KAWAI, M.; TOKUNAGA, N.

AF

F3C

H

NSO2Ar

F3C

Ar1

HNSO2ArAr1Ti(OiPr)3

[{RhCl(C2H4)2}2]/L*(3 mol% Rh)

THF20 ºC, 1 h76 - 99 %

*

73 - 96 % ee

PPh2

PPh2

O

O

O

O(S)-segphos

L*:

Ti

Angew. Chem. Int. Ed. 6125 61282004 43 -, , 45 ,

37


Bicyclic Pyrrolidines SynthesisRh

Scope of the process explored.

YAN, M.; JACOBSEN, N.; HU, W.; GRONENBERG, L.S.; DOYLE, M.P.; COLYER, J.T.; BYKOWSKI, D.

AF

PhCO2Me

N2

+NAr

MeO

NAr

Ph

CO2MePh

MeOOC

MeO

Ar: p-NO2C6H4

Rh2(OAc)4cat

CH2Cl2reflux

69 %

Angew. Chem. Int. Ed. 6713 67162004 43 -, , 48 ,

Axially Chiral Phthalides Through Cross Alkyne CyclotrimerizationRh

Other examples given.

TANAKA, K.; NISHIDA, G.; WADA, A.; NOGUCHI, K.

AF

O

OAr

RO OR OROR

O

O Ar

+

[Rh{(S)-H8-binap}]BF45 mol %

CH2Cl2r. t., 3 h

*

Ar: 2-MeC6H4, 1-naphtyl, 2-F3CC6H4, 2-ClC6H4

R: Ac, H

86 - > 99 % ee45 - 73 %

Angew. Chem. Int. Ed. 6510 65122004 43 -, , 47 ,

Optically Active Intermediate in the Oxidative Addition ProcessRh

DOPPIU, A.; ENGLERT, U.; SALZER, A.

AF

PPh2

RhPh P

Ph2

RhPh

+I-

H3CCH3I

1 3 X-Ray

THFr. t.

93 % 7 %

PPh2

Rh

IPhH3C

2a

PPh2

Rh

H3CPh

I

2b

Chem. Commun. 2166 21672004 -, , 19 ,

Oxidative C-C Cleavage Producing Carbene ComplexesRh

Reactivity of the imidazolium salt examined in the presence of Ag2O.

CHIANESE, A.R.; ZEGLIS, B.M.; CRABTREE, R.H.

AF

NN

I 1. ion exchange2. Ag2O

3. [Rh(cod)Cl]2Rh

Cl

N

N

25 %

Ag

Chem. Commun. 2176 21772004 -, , 19 ,

38


Cyclocarbonylation with Rh Catalysts: Stereochemical AspectRh

NMR and kinetic investigations.

SCHMID T.M.; CONSIGLIO, G.

AF

E

E

E

EO

H

P

PRh

"Rh"

THFM.S. sat. CO

0 ºC, 4 h9 % conv.

33 %97 % ee

M.S. sat. CO: molecular sieve saturated with CO

Ph2

Ph2

"Rh":

E: COOEt

Chem. Commun. 2318 23192004 -, , 20 ,

Intermolecular Cyclopropanation: Enantio- and Diastereo-ControlRh

Catalyst has been optimized while varying the para substituent of the ortho metallated phosphine end of the auxiliary.

ESTEVAN, F.; LAHUERTA, P.; LLORET, J.; SANAU, M.; UBEDA, S.M.; VILA, J.

AF

+ N2CHCOOEt Ph COOEt + Ph COOEt90:1039 %

91 % ee 7 % ee

Rh2(II)

Rh2(II): Rh2(O2CR)2(PC)2

Chem. Commun. 2408 24092004 -, , 21 ,

Thiazolidine DerivativesRh

A mechanism explaining the role of Rh catalysis is proposed.

ZHOU, H.-B.; DONG, C.; ALPER, H.

GP

NS

O OEt

NAr N Ar NS

N

Ar

NHArO

+[Rh(cod)Cl)]2, 10%

dppf (30%), toluene130°C, 72h

14 examples42-81%

Chem. Eur. J. 6058 60652004 10 -, , 23 ,

C-H or C-F Activation and C-C Coupling Reactions of Fluorinated PyridinesRh

NOVESKI, D. ; BRAUN, T. ; NEUMANN, B. ; STAMMLER, A. ; STAMMLER, H.-G.

MVI

NF

FH

F

F N

FF

F

F

F

NF F

FF

Rh PEt3PEt3

Et3P

MeIN

FMe

F

F

F

N

FCOMe

F

F

F

or[RhH(PEt3)n]

n = 3 or 41) CO2) MeI

Dalton Trans 4106 41192004 -, , 24 ,

39


Regiospecific Functionalization of Methyl C-H Bonds of Alkyl GroupsRh

LAWRENCE, J. D.; TAKAHASHI, M.; BAE, C.; HARTWIG, J. F.

GVI

FGHn

Cp*Rh(η4-C6Me6) (5 mol%)B2pin2

FG = CH3C(OR)2, F, R2N, RO

FGBPinn

FGRn

R = Ar, OH, BF3Kneat, 150°C

J. Am. Chem. Soc. 15334 153352004 126 -, , 47 ,

Direct Access to Ketones from Aldehydes via Potassium Trifluoro(organo)boratesRh

PUCHEAULT, M.; DARSES, S.; GENET, J.-P.

GVI

O

Ar HAr'BF3K

[Rh(CH2CH2)2Cl]2 (1.5 mol%)

P(tBu)3 (3 mol%), 80°Csolvent/acetone

O

Ar Ar'+

J. Am. Chem. Soc. 15356 153572004 126 -, , 47 ,

Reductive and Catalytic Monoalkylation of Primary AminesRh

Nitriles were used as alkylating agents

SAJIKI, H.; IKAWA, T.; HIROTA, K.

AB

Alkyl-NH2 Alkyl-NHCH2R5% Rh/C, H2 (balloon)

RCN, MeOH, rt almost quant.

Org. Lett. 4977 49802004 6 -, , 26 ,

Ortho Alkylation of Aromatic Ketimine with Functionalized AlkenesRh

A variety of functional groups in the alkene were tolerated

LIM, S-G.; AHN, J-A.; JUN, C-H.

AB

NBn

+OMe

O

O

OMe

O1) (PPh3)3RhCl (5 mol%)toluene, 150°C, 2hr

2) H3O+

94% isolated yield

Org. Lett. 4687 46902004 6 -, , 25 ,

40


Rh(I) Perfluoroalkyl ComplexesRh

Other phosphines and perfluoroalkyl chains used. Other reactions described.

VICENTE, J.; GIL-RUBIO, J.; GUERRERO-LEAL, J.; BAUTISTA, D.

AF

Rh

F

PPh3

Rh

CF3

PPh3

XyCN

RhNCXy

CF3

Ph3P

XyCNRh

XyCN

CF3

PPh3

Me3Si-CF3 O

O

XyNCTHF O2

X-Ray X-Ray

THF10 min, r. t.

76 %

r. t., 1 h66 %

THF30 min.55 %

XyNC: 2,6-dimethylphenylisocyanide


N-Heterocyclic Carbene Complexes as RadiopharmaceuticalsRh

QUEZADA, C.A.; GARRISON, J.C.; PANZNER, M.J.; TESSIER, C.A.; YOUNGS, W.J.

AF

N

N N

NBu nBu

2 I -

1) 2.5 Ag2OH2O

n2) NH4PF6

93 %

N

N N

NBu nBun

N

NN

N nBuBun

Ag Ag+ +

2 PF6-

X-Ray

N

N N

NBu nBun

N

NN

N nBuBun Rh

Cl-1) RhCl3.3H2OH2O

2) DMSO 100 ºC, 1 h

Cl

Cl

+

Ag


Arene Chromium Phosphines in Enantioselective HydrogenationRh

Stereoselective synthesis of 3 ligands described. Dimethylitaconate hydrogenated with 87 % ee.

ENGLERT, U.; HU, C.; SALZER, A.

AF

PPh2 PCy2

(OC)3CrPh

COOMe

NHCOMe

[Rh(NBD)2]BF4(1 mol %)

L* (1.1 mol %)L*:+ H2

Ph

COOMe

NHCOMe1.5 bar THFr. t., 1 h 100%

H

88 % ee

Cr


ηηηη5-Semiquinone and ηηηη4-Benzoquinone Bearing ComplexesRh

Quinone complexes obtained by deprotonation of the polymer.

MOUSSA, J.; GUYARD-DUHAYON, C.; HERSON, P.; AMOURI, H.; RAGER, M.N.; JUTAND, A.

AF

[Cp*M(S)3][OTf] + HO OH

S: acetone M

M

OO HO O

OTf-

OTf-

X-Ray for Rh and Irn

Ir


41


Alkene Insertion into Rh-Acetyl BondRh

Catalytic activity for CO/alkene polymerization described. Norbornene and dicyclopentadiene also used.

HAYNES, A.; HASLAM, C.E.; BONNINGTON, K.J.; PARISH, L.; ADAMS, H.; SPEY, S.E.; MARDER, T.B.; COVENTRY, D.N.

AF

RhOC CO

1) MeI

2) AgBF4

Rh

OC COMe

+BF4-

Rh

OC

+BF4-

OMe

X-Ray


Synthesis of Dihydrofurans, Oxazoles, and DihydrooxepinesRh

35 examples; reaction of α , β -unsaturated esters and ketones, acrylonitriles, and 1,3-butadienes with various iodoniumLEE, Y.R.; YOON, S.H.; SEO, Y.; KIM, B.S.

AS

O

IPh

O O

N

O

O

O

CNCN

Rh2(OPiv)

4

++

+_

rt, 12h 49% 6%

0.5 mol%

Synthesis 2787 27982004 -, , 17 ,

Enantioselective Synthesis of Nitrogen Protected 3-Arylserine Esters Rh

BOURDON, L. H.; FAIRFAX, D. J.; MARTIN, G. S.; MATHISON, C. J.; ZHICHKIN, P.

CS

Ar

O

N2

O

OEtAr

O

HN

O

OEtOtBu

O

ArHN

O

OEtOtBu

O

OHtBuOC(O)NH2

Rh2Oct4, CH2Cl2

Et3N . HCO2H, i-PrOH

(RuCl2C6H6)2

(+)-Pseudoephedrine

Ru


Chiral Atropisomeric Diiodobiphenyls-Enantiodifferentiation by the Dirhodium MethodRh

MOELLER, S.; ALBERT, D.; DUDDECK, H.; SIMON, A.; TOTH, G.; DEMCHUK, O. M.; PIETRUSIEWICZ, K. M.

CS

I

I

H3C

H3C

X

R

R

X'

O

Rh

O

O

Rh

O

R*

OO

O*R

R*O

R*

OMe

PhCF3

1

23

4

56

1'

2'

3'4'5'

6'R* =

Rh*

R =H, CH3

X = H, Cl, OCH3, NH2, N(CH3)2, OH, SH


42


Stereoselective Synthesis with P,P* Rhodium(I) Complexes Rh

(SS,RR,RS,SR) Aminophosphonite-phosphinite was also tested and led also to good results.

CESAROTTI, E.; RIMOLDI, I.

CS

NR

OTBS

O

BPh3

Rh

NR

OTBS

O

CHONR

OTBS

O

CHONR

OTBS

O

CHO

N O

P

PO

O

P-P*, CO/H2

+ +

R = H, BOC, CH2COOCH2Ph

*

(SS,RR,RS,SR) Aminophosphine -phosphite

-

+

P-P* =


Intramolecular C-H InsertionRh

Conformational effects enhanced the regio- and stereoselectivities

FLANIGAN, D.L.; YOON, C.H.; JUNG, K.W.

GP

RN O

O

N2

N O

O

HEt

RRh3(OAc)4 (2%)

CH2Cl2, reflux, 12h

7 examples84-91%


Trimethylindolenine Enantioselective Hydrogenation in Ionic LiquidsIr

Media with comparable results to the conventional process with reduced reaction times identified.

GIERNOTH, R.; KRUMM, M.S.

AF

N NH

N NH3C C10H21

Ph2PPAr2

HCH3+ H2 *

[Ir(cod)Cl]2 / 3(0.4 mol % cat)TBAI, CF3CO2H

40 bar IL, 50 ºC, 15 h

IL: BF4-

Fe

Ar: 3,5-dimethylphenyl

3:

56 % 86 % eeTBAI: tetrabutylammonium iodide

Adv. Synth. Catal. 989 9922004 346 -, , 8 ,

Ir I/Ir III Based Cycle for a Gaz Phase Reaction of Olefin HydrogenationIr

Electrospray ionization tandem mass spectroscopy used to identify the catalytic intermediates.

DIETIKER, R.; CHEN, P.

AF

IrP N

+BArF-

IrP N

HH

Ph

+BArF-

two of the several species identified

P

N:

PPh2 N

O

B

Angew. Chem. Int. Ed. 5513 55162004 43 -, , 41 ,

43


Synthesis and Characterization of a Difluoroketene ComplexIr

CORDARO, J.G.; VAN HALBEEK, H.; BERGMAN, R.G.

AF

CF3

O

H CF3

O-

CF2

O

Cp*(PMe3)Ir

1.4 equiv. tBuLi[D8]THF- 80 ºC

NMR monitoringCp*(PMe3)Ir

Li+

Cp*(PMe3)Ir- LiF

X-Rayabove 0 ºC

Li

Angew. Chem. Int. Ed. 6366 63692004 43 -, , 46 ,

Regio- and Enantioselective Allylic Substitution using the Pybox LigandIr

MIYABE, H.; MATSUMARA, A.; MORIYAMA, K.; TAKEMOTO, Y.

AB

NO

N N

O

Ph Ph[IrCl(cod)2]2

Ar OP(O)(OEt)2 + NuHAr

Nu

ktkt =

up to 94% yieldup to 92% ee

Org. Lett. 4631 46342004 6 -, , 24 ,

Chiral (Allyl)Iridium(III) ComplexesIr

Characterization and reactivity (Lewis acid or iodine) of the complex studied.

GARCIA-YEBRA, C.; JANSSEN, J.P.; ROMINGER, F.; HELMCHEN, G.

AF

IrCl

ClPh

PHOX (1 equiv.)

THF, r. t., 1 h

O

N PPh2Ir

ClPh

exo

O

N PPh2Ir

OO

H3COOCH3

Ph

CH(COOCH3)X-Ray

X-Ray

2 NaCH(COOCH3)2

THF- 40 ºC to r. t., 2 h(quant. by NMR)


Unusual Reactivity of Ni-Carbene ComplexesNi

Other carbene complexes characterized as well, with participation of the tbutyl residue.

CADDICK, S.; CLOKE, F.G.N.; HITCHCOCK, P.B.; LEWIS, A.K. DE K.

AF

NC

NtBu

tBu

O

NiO

Ni

Si

Si

O

O

SiO

SiO

Ni(1,5-cod)2 +

Me2 Me2

Me2Me2

tBu

tBu

tBu

Ni

tBu

tBuBuTHF

14 days

geased Schlenk tube 25 ºC

t

X-Ray X-Ray

THF 5 days

greaseless ampoule25 ºC

sunlight

Angew. Chem. Int. Ed. 5824 58272004 42 -, , 43 ,

44


Cross-Coupling Reaction in the Presence of Tetraenes as AdditivesNi

Variation of both reactants. Optimization of the system.

TERAO, J.; TODO, H.; WATANABE, H.; IKUMI, A.; KAMBE, N.

AF

Alkyl-X + R'2Zn + MgBr2

1 mmol 1.3 mmol 3 mmol

NiCl2 (3 mol%)2a (9 mol%)

THF/NMP25 ºC, 1 h

Alkyl-R' 2a: CO2Me

CO2Me79 - 96 %

Pd

Angew. Chem. Int. Ed. 6180 61822004 43 -, , 45 ,

Directing Effects of Tethered Alkenes in Ni-Catalyzed Additions to Alkynes Ni

A complete inversed regioselectivity (A : B = 5 : >95) is observed when 20% Cyp3P are added

MILLER, K. M. ; JAMISON, T. F.

MVI

RCHO

n-hexn-hex

R

OH

A Bn-hex

HO R

3

+10% Ni(cod)2

Et3B, EtOAc 3+

3

10 examples

A : B = >95 : 5

60-69%

J. Am. Chem. Soc. 15342 153432004 126 -, , 47 ,

Cross-Coupling of Organozinc Reagents with Carboxylic Acid FluoridesNi

Acid chlorides, anhydrides and thioesters as also good coupling partners in this reaction

ZHANG, Y. ; ROVIS, T.

MVI

O

FR1

O

R2R1

N PPh2

0.55 equiv R22Zn, 10% Ni(COD)2

12% pyphos, 20% 4-fluorostyrene

THF, 23°C

pyphos

25 examples, 71-98%

Zn

J. Am. Chem. Soc. 15964 159652004 126 -, , 49 ,

Synthesis and Reactivity of a Mononuclear Parent Amido Ni Complex.Ni

Ni(PCP)(NH2) complex is structurally caracterized.

CAMPORA, J.; PALMA, P.; DEL RIO, D.; CONEJO, M. M.; ALVAREZ, E.

LD

[Ni]-Br [Ni]-NH2NaNH2

THF, sonication

[Ni]-NH2 + ROH [Ni]-OR + NH3

[Ni] =

P(iPr)2

Ni

P(iPr)2

R = H, Me

Organometallics 5653 56552004 23(24)

-, , 24 ,

45


Ni(II) N-Heterocyclic Carbene Complexes: Preparation, Structure and ReactivityNi

Polymerization activity

WANG, X.; LIU, S.; JIN, G.-X.

LD

Ni N

N

N

N

NNRR

MAO n

2+

2Cl-


-, , 25 ,

Diphosphine Complexes of Ni(II) : Polymerization and Oligomerization of EthyleneNi

Steric activation and ligand backbone effects

DENNETT, J. N. L.; GILLON, A. L.; HESLOP, K.; HYETT, D. J.; FLEMING, J. S.; LLOYD-JONES, C. E.; ORPEN, A. G.;PRINGLE, P. G.; WASS, D. F.; SCUTT, J. N.; WEATHERHEAD, R. H.

LD

NMe

Ar2P PAr2Ar2P PAr2 Ar2P PAr2

PAr2 PAr2Ar2P PAr2 PPh2 PPh2

OPPh2 PPh2


-, , 26 ,

Ni-Catalyzed Electrochemical Conjugate Addition ReactionsNi

Overview on additions of organic halides on electron-deficient olefins.

CONDON, S.; NEDELEC, J.Y.

GJ

N Br

Me

O NMe

O

+

NiBr2.3H2O (10 mol%)

9:1 DMF-pyridine, 60°C, 7 h

Fe anode, e- 30%(2.5 equiv)

Fe

Synthesis 3070 30782004 -, , 18 ,

Coupling Reactions of Aryl, Heteroaryl or Vinyl Halides with Activated Alkyl HalidesNi

Special topic on Ni-catalyzed electrochemical coupling reactions using a sacrificial Al rod anode.

DURANDETTI, M.; PERICHON, J.

GJ

H

Br

Ph Cl

Me Me

O

Bu4NBF

4, DMF

HPh

Me

OMe

+

(Z/E > 99:1)

64% (Z/E = 94:6)

Al anode, e-

NiBr2bipyAlB

Synthesis 3079 30832004 -, , 18 ,

46


An Iterative Route to Substituted [n]AcenesNi

Selective [2+2+2] cycloaddition of nickel-benzyne and an asymmetric 1,3-diyne

DEATON, K.R.; STROUSE, C.S.; GIN, M.S.

GJ

Br

Ni(PEt3)2 Me SiMe3

Et3P

SiMe3

SiMe3Me

Me

Me

Me

Br

Br

a) Na/Hg, THF, rt, 3 h

b)

a) NBS, AgNO3

acetone, rt, 9 h

b) 280°C, 2 h,1,4-cyclohexadiene,

sealed tube62% 48%

(2 equiv)

NaHgSiAg

Synthesis 3084 30882004 -, , 18 ,

Synthesis of 1,2-Disubstituted CycloalkanesNi

Ni-catalyzed three-component reactions.

KIMURA, M.; KOJIMA, K.; TAMARU, Y.

GJ

MeO2C

MeO2C

OMe

2Zn OH

MeO2C

MeO2C+ +

(2.4 equiv)

Ni(acac)2 (10 mol%)

THF, rt, 2.5 h84% (trans:cis 2:1)

Zn

Synthesis 3089 30912004 -, , 18 ,

Nickel in the Synthesis of Organic MoléculesNi

CARREIRA, E.M. (EDITOR)

PJP

"Nickel in Organic Synthesis" constitutes the special topic of this issue, with numerous articles

Synthesis 2943 31112004 -, , 18 ,

Improved Palladium and Nickel Catalysts Heterogenised on Oxidic Supports Pd

GONZALEZ-ARELLANO, C.; IGLESIAS, A. C. M.; SANCHEZ, F.

LF

EtO2C

CO2Et

N

H2

EtOH

EtO2C

CO2Et

HN

O

OSi

O

NHNH

O

N

OM

N

OAcR

Ni

Adv. Synth. Catal. 1316 13282004 346 -, , 11 ,

47


Recyclable Tridentate Stable Palladium(II) PCP-Type Catalysts Supported on SilicaPd

CHANTHATEYANONTH, R.; ALPER, H.

LF

O

OSi H

N

O

OHR

cat

48 h, dppb, CO/H2 OR O

O

R

O O

R

O

O O

NH

Ph2P

Pd

PPh2

TFAcat =

Adv. Synth. Catal. 1375 13842004 346 -, , 11 ,

Negishi Cross-Coupling of o-Nitroarylzinc ReagentsPd

SAPOUNTZIS, I.; DUBE, H.; KNOCHEL, P.

CFR

GF

NO2

I

MesMgBr, THF

-40°C, 20 min (-Mes-I)

GF

NO2

MgBr

ZnBr2, THF

-40°C, 10 minGF

NO2

ZnX

X= Br, Cl

Pd(dba)2 (5mol%)

tfp (10 mol%)-20°C to rt, 6h

GF

NO2

Ar

+ ArI

48-85%

Adv. Synth. Catal. 709 7122004 346 -, , 7 ,

Allylation of Carbon Pronucleophiles with Alkynes with Pd/Acetic Acid CatalystPd

PATIL, N. T.; KADOTA, I.; SHIBUYA, A.; GYOUNG, Y. S.; YAMAMOTO, Y.

CFR

R1

R2

Pd(0)/CH3COOH

H-Nu R1 R2

NuH-Nu active methynes and active methylenes

up to 99%

Adv. Synth. Catal. 800 8042004 346 -, , 7 ,

Hydroamination/Heck Reaction for the Synthesis of IndolesPd

SHIRAKAWA, E.; ISHII, K.; TSUCHIMOTO, T.

DH

1) TiCl4, tBuNH2, PhMe2) Pd(OAc)2, tBuOK

67-84%11 examples

+

Cl

NH2

RAr

N

Ar

R

H

NAr

H

+

a b

ratio a/b from 89/11 to 99/1

RTi

Chem. Commun. 2752 27532004 -, , 23 ,

48


Heck Reaction using a PhosphinophenolatePd

ACKERMANN, L.; KASPAR, L. T.; GSCHREI, C. J.

DH

Pd(OAc)2, Ligand, Bu4NBr, toluene, H2O

67-96%7 examples

+

Br

R

Ar

R

R'

HO

PPh2

ligand

Chem. Commun. 2824 28252005 -, , 24 ,

Bulky Monodentate Phosphoramidites in Tsuji-Trost ReactionsPd

ee up to 93% with 1,3-diphenyl-2-propenyl acetate and dimethylmalonate

BOELE, M. D. K.; KAMER, P. C. J.; LUTZ, M.; SPEK, A. L.; DE VRIES, J. G.; VAN LEEUWEN, P. W. N. M.; VANSTRIJDONCK, G. P. F.

CJM

O

O OP

OAr Ar

Ar Ar

NR2

R1 R1= Me, Et, iPrR2= Me, Et, iPr, (R)-CH(Me)PhAr= 3,5-(CH3)2C6H3, Ph, 2-Naphthyl

Chem. Eur. J. 6232 62462004 10 -, , 24 ,

Intramolecular Hydroalkylation of Alkenyl- ββββ-Keto Esters, αααα-Aryl and Alkyl KetonesPd

HAN, X.; WANG, X.; PEI, T.; WIDENHOEFER, R. A.

CJM

OR1

OR1

R1= Ester, aryl, alkyl

PdCl2(CH3CN)2 10%

CuCl2 30%TMSCl or HClR2 R2

> 45 examples

Chem. Eur. J. 6333 63422004 10 -, , 24 ,

Intramolecular Oxidative Alkylation of 4-Pentenyl ββββ-Dicarbonyl CompoundsPd

LIU, C.; WANG, X. PEI, T.; WIDENHOEFER, R. A.

CJM

OR1

OR1PdCl2(CH3CN)2 5%

CuCl2 2.5 Eq.dichloroethane rtR2 R2

27 examplesR1= Ester, ketone

Chem. Eur. J. 6343 63522004 10 -, , 24 ,

49


Electrophilic Alkene ActivationPd

HANH, C.

CJM

MNu - Nu

M-"Concept" article

62 refs

PtRh

Chem. Eur. J. 5888 58992004 10 -, , 23 ,

Polymer-Supported Bisphosphine Ligands with a Cyclobutane Backbone Pd

ZHAO, D.; SUN, J.; DING, K.

CJM

Ph Ph

OAc+ NuH Ph Ph

Nu

ee up to 95%

[(π-allyl)PdCl]2L*, BSA

RO O

P P

O

O

O

PEG-OMe

Ar Ar ArAr

L* =

Chem. Eur. J. 5952 59632004 10 -, , 23 ,

Stannylative Cycloaddition of EnynesPd

Two examples of stannylative cross-cycloadditions of enynes are also described

NAKAO, Y.; HIRATA, Y.; ISHIHARA, S.; ODA, S.; YUKAWA, T.; SHIRAKAWA, E.; HIYAMA, T.

CJM

R1R2

R3

+ (Bu3Sn)2O

R2

SnBu3R3

R1 R1

R2R3

[(π-allyl)PdCl]2 2.5%L 5%

THF, 50 °C

10 examples52-71% PPh2

N CyL=

Sn

J. Am. Chem. Soc. 15650 156512004 126 -, , 48 ,

Mechanistic Aspects of Amine OxidationPd

LU, C. C.; PETERS, J. C.

CJM

NR2R1

R3 PPd

PPh2B

Ph Ph

Ph Ph

R3

NR1

R2 NR2R1

R3

Pd(II)oxidation

J. Am. Chem. Soc. 15818 158322004 126 -, , 48 ,

50


Total Synthesis of Amphidinolide XPd

LEPAGE, O.; KATTNIG, E.; FURSTNER, A.

CJM

O O

O

OO

O

Pd-Alkyl-SuzukiPd-Allenylzinc

Fe cross-coupling

Fe

J. Am. Chem. Soc. 15970 159712004 126 -, , 49 ,

Enantioselective Diboration of Prochiral AllenesPd

PELZ, N. F.; WOODWARD, A. R.; BURKS, H. E.; SIEBER, J. D.; MORKEN, J. P.

CJM

R • + B BO

OO

O

Pd2dba3 2.5%L* 6%

toluene, rt R

BB

OO

O

OO

POO

ON

Ph Ph

Ph Ph

L*=8 examples57-75%87-91% ee

B

J. Am. Chem. Soc. 16328 163292004 126 -, , 50 ,

Proazaphosphatranes Ligands for Stille Cross-Coupling ReactionsPd

SU, W.; URGAONKAR, S.; MCLAUGHLIN, P. A.; VERKADE, J. G.

CJM

NP

NN

N

R2

PhR3

X+ Bu3SnR1

Pd2dba3 1.5%L 6%

CsF 2.2 eq.rt to 110 °C

R1 57 examplesX= Cl, Br, OTfR1= Ar, vinyl, allyl

R2, R3= i-Bu, Bn

Sn

J. Am. Chem. Soc. 16433 164392004 126 -, , 50 ,

Intermediates in Hydrogenation ReactionsPd

DUNNE, J. P.; AIKEN, S.; DUCKETT, S. B.; KONYA, D.; ALMEIDA LENERO, K. Q.; DRENT, E.

CJM

H

Ph

Ph

H

H2

P2PdPh

HH

Pd PhH

P

P H Ph

Ph

H

H

Ph

Ph H

H

PdP

P H

H

- H-H

- P2Pd

J. Am. Chem. Soc. 16708 167092004 126 -, , 51 ,

51


Enantioselective Synthesis of Palladacycles Containing ββββ-HydrogensPd

Reactivity, stability and acid-promoted epimerization of the palladacycles are described

BURKE, B. J.; OVERMAN, L. E.

CJM

BnN

OTfO ∗

R

NH

OO

OPd(OAc)2 1 eq.(S)-Binap 2 eq.pentamethylpiperidine

DMA, 80 °CR= Me, H 67-95%

NBn

Pd

NO

O

PPO

R

O

J. Am. Chem. Soc. 16820 168332004 126 -, , 51 ,

Threading-followed-by-shrinking Protocol for the Synthesis of a [2]-RotaxanesPd

YOON, I.; NARITA, M.; SHIMIZU, T.; ASAKAWA, M.

CJM

Pd(OAc)2

Threading Shrinking

J. Am. Chem. Soc. 16740 167412004 126 -, , 51 ,

Palladium-Catalyzed N-Vinylation of SulfoximinesPd

DEHLI, J.R.; BOLM, C.

MV

10 mol% Pd(OAc)315 mol% BINAP

NaOt-Bu, 110°Ctoluene> 98%

+

R1

R1N

R2

S NHO

RR2

R1

R1

Br SO

RR = Ph, Ar, Me, NaphtylR1 = H, MeR2 = Ph, Me

Na

J. Org. Chem. 8518 85202004 69 -, , 24 ,

Vinyldimethylphenylsilanes for Pd-Catalyzed Cross-Coupling ReactionsPd

vinyldimethylphenylsilanes as safety catch silanols in fluoride-free reactions.

ANDERSON, J.C.; MUNDAY , R.H.

MV

+R2SiMe2Ph

R3

R1

PhI5 mol% Pd2(dba)3

KOTMS, 18-C-6THF, rt or 67°C, 30 min or 2h

62-86%

R2Ph

R3

R1

R1 = H, Me, (CH2)3PhR2 = H, Ph, Me, (CH2)3PhR3 = H, Me

K

J. Org. Chem. 8971 89742004 69 -, , 25 ,

52


Pd-Mediated Arylation of 3-Aminopiperidines and 3-AminopyrrolidinesPd

JEAN, L.; ROUDEN, J.; MADDALUNO , J.; LASNE, M.-C.

MV

10 mol% Pd2(dba)315 mol% L

NaOt-Bu, 100 °C or 130°Ctoluene or xylene

> 85%

ZNR

NH2

+ Ar-XnZ

NR

NHAr

nR = H, Bn, BocZ = CH2, COX = Cl, Br, I

L =

PCy2

Me2N

Na

J. Org. Chem. 8893 89022004 69 -, , 25 ,

Allylation of Aromatic Amines and α-Aryl Aldehydes with AlkynesPd

PATIL, N.T.; WU, H.; KADOTA, I.; YAMAMOTO , Y.

MV

5 mol% Pd(PPh3)410 mol% PhCO2H

1,4-dioxane, 100 °C+

NH2

R'R

R = H, Me, Cl, CN, OMe, NO2, COMe, Ph, alkenylR' = Ph, p-Cl-C6H4, p-MeOC6H4, CO2Et

HN

R

R' CHO

R'

with α-arylaldehydes79-99%

R

86-98%

J. Org. Chem. 8745 87502004 69 -, , 25 ,

Pd-Catalyzed Oxidation of Alcohols and Hydrodechlorination of ChloroarenesPd

For hydrodechlorination : 2-propanol, K2CO3, Pd/L, 80°C

BEI, X.; HAGEMEYER, A.; VOLPE, A.; SAXTON, R.; TURNER, H.; GURAM, A.S.

MV

1 mol% Pd2(dba)32 mol% L

NaOt-Bu, or K2CO3 or K3PO4C6H5Cl, 95-105 °C

91-100%

R, R' = alkyl, aryl, benzyl, H

L =PCy2

PhR

OH

R'R

O

R' or PCy2

NaK

J. Org. Chem. 8626 86332004 69 -, , 25 ,

Oxydative Cross-Coupling of Acrylates Catalysed by a Pd(OAc)2/HPMoV/O 2 SystemPd

HATAMOTO, Y.; SAKAGUCHI, S.; ISHII, Y.

CS

OR

O

OAc

O

ORAcO+

cat. Pd(OAc)2

H4PMo11VO40.nH2O cat.

NaOAc, O2 (1atm) AcOH, 90°C

Org. Lett. 4623 46252004 6 -, , 24 ,

53


Pd-Catalysed Coupling of Aryl Bromides/Triflates and ThiolsPd

ITOH, T.; MASE, T.

CS

X

R

SH Alkyl or Aryl

2.5 mol% Pd2(dba)3 5 mol% Xantphos

2 eq. i-Pr2NEt1,4-dioxane, reflux

+ S

R

Alkyl or ArylO

PPh2PPh2

XantphosX = Br, OTf, Cl; R = functional group67-92% yields

Org. Lett. 4587 45902004 6 -, , 24 ,

Construction of Chiral Quaternary Carbon Centers Pd

HOU, X. -L.; SUN, N.

CS

OAc

Ar MeAr Me

E

E*

+

Me

ArE

E

[Pd(C3H5)Cl2] (2 mol.%) / L (4 mol.%)

CH2E2 / BSA KOAc / 25°C E = COOMe

Ar = phenyl, 1-naphtyl, 4-MeO-C6H4, 4-Me-C6H4, 4-Cl-C6H4, 4-CN-C6H4

PEt2N OR'

Fe N

O

R' = (R)-2-(2'-hydroxy-1,1'-binaphthyl)

L =

Org. Lett. 4399 44012004 6 -, , 24 ,

One-Pot Suzuki-Miyaura Biphenyl SynthesisPd

High yields were obtained in the case of electron-donor substituted aryl bromides.

BROUTIN, P. -E.; CERNA, I.; CAMPANIELLO, M.; LEROUX, F.; COLOBERT, F.

CS

Ar-Br BO

OH+

1) Pd(OAc)2, Et3N, DPEphos, dioxane, 100°C

2) Ar'-Br, CsF, Pd(OAc)2, dioxane, 100°C

Ar-Ar'

B

Org. Lett. 4419 44222004 6 -, , 24 ,

ηηηη2-dba Complexes of Pd(0)Pd

The electronic properties of substituents on the aryl groups of dba modulate the catalyst activity.

FAIRLAMB, I. J. S., KAPDI, A. R. LEE, A. F.

CS

ClMe Me

Pdy(dba-Rx)n (3 mol% Pd)N N ArAr

Cl (6 mol%)

Ar = bis-2,6-i-PrPh

B(OH)2toluene

R = 4,4'-OMe, 4,4'-t-Bu, 3,5,3',5'-OMe, 3,3'-NO2, 4,4'-CF3

n-Bu4NBr (10 mol%)

B

Org. Lett. 4435 44382004 6 -, , 24 ,

54


New synthesis of FulvenesPd

UEMURA, M.; TAKAYAMA, Y.; SATO, F.

CS

II

SiMe3

R1

R2

BrMgC CR3

Pd(PPh3)4

I

SiMe3

R1

R2

R3

I

H

R1

R2

R3

R1

R2R3

R1

R2

R3

or

(Z)-fulvene (E)-fulvene12 examples, 32-93 % yield

or

(or H)MgSi

Org. Lett. 5001 50042004 6 -, , 26 ,

One-pot Sequential Reduction and Arylation of Silyl Enol EthersPd

The use of nonpolar solvents for the reduction step is necessary to maintain high enantioselectivity.

CHAE, J.; YUN, J.; BUCHWALD, S. L.

CS

O

R

O

SiPhPh

O

R R

O

R

ArPt-Bu2

1mol. % CuCl

1 mol.% (S)-Tol-Binap

1 mol.% NaOt-Bu0.51 equiv. Ph2SiH2 toluene -78°C to 0°C

5 mol.% Pd(OAc)2 cat. (10 mol.%)

1.1 equiv. CsF1.5 equiv. ArBr THF, rt, 24h

cat. =

CuSi

Org. Lett. 4809 48122004 6 -, , 26 ,

Pd-Catalyzed Sequential Aryl-Aryl and N-Aryl CouplingPd

FERRACIOLI, R.; CARENZI, D.; ROMBOLA, O.; CATELLANI, M.

CFR

IR1

+ ArBr

O

NHR2Pd(OAc)2/Tri-2-furylphosphine

K2CO3, DMF or MeCN

NR1 R2

Ar

O

48-90%Ar: Aryl, heteroaryl

Org. Lett. 4759 47622004 6 -, , 25 ,

Pd-Catalyzed Intramolecular O-Arylation of EnolatesPd

WILLIS, M. C.; TAYLOR, D.; GILLMORE, A. T.

CFR

X

R2R1

OR3 Cs2CO3 or

NaHMDS orNaOtBu

X

R2R1

O-R3 Pd2(dba)3, DPEphos

toluene, 110°C

R1

R2

R3

68-95%

Org. Lett. 4755 47572004 6 -, , 25 ,

55


Allylic Substitution with OximesPd

Various examples.

MIYABE, H.; MATSUMURA, A.; YOSHIDA, K.; YAMAUCHI, M.; TAKEMOTO, Y.

MJ

Ph OAc

NOH Ph

+Ph

(1.5 eq.)

Pd(PPh3)4 (0.06 eq.)

K2CO3 (1 eq.)

CH2Cl2, 20°C

[IrCl(cod)]2 (0.04 eq.)

Et2Zn (0.5 eq.)

THF, 20°C 67%76% Ph

N

Ph

O Ph

Ph

N

Ph

O

Ph

IrZn

Synlett 2123 21262004 -, , 12 ,

Cross-Coupling ReactionsPd

BELLUR, E.; LANGER, P.

MJ

X OR

O

Br

Suzuki and Heck reactions from

X= O, NH

B

Synlett 2169 21712004 -, , 12 ,

Regiocontrolled Suzuki CouplingsPd

RYU, K.-M.; GUPTA, A. K.; HAN, J. W.; OH, C. H.; CHO, C.-G.

MJ

O

O

Br

Br

PhB(OH)2

O

O

Ph

Br

O

O

Br

Ph

O

O

Ph

Ph

Pd(PPh3)4 (0.1 eq.)

+ +

PhMe, K2CO3, 100°C: 81% trace traceDMF, Na2CO3, CuI (1 eq.), 50°C: trace 89% trace

4 h

BCu

Synlett 2197 21992004 -, , 12 ,

A New Ligand for Suzuki CouplingsPd

GUPTA, A. K.; RIM, C. Y.; OH, C. H.

MJ

Cl B(OH)2

OMe

+

Pd(OAc)2 (0.05 eq.)

(0.05 eq.)

t-BuOK (2 eq.) n-Bu4NBr (0.1 eq.)

DMF, 100°C, 12 h 88%

N

N N

NN

N

N NOMe

B

Synlett 2227 22292004 -, , 12 ,

56


Sonogashira ReactionPd

TUMKEVICIUS, S.; MASEVICIUS, V.

MJ

N

N NMe

NH2

O

OMe

Cl

MeS

Ar N

N NMe

NH2

O

OMeMeS

Ar

+

PdCl2(PPh3)2 (0.1 eq.)CuI (0.2 eq.)

NEt3 (2 eq.)(10 eq.)DMF, 60-70°C

56-62%

Cu

Synlett 2327 23302004 -, , 13 ,

Carbonylations under Air. Microwaves. Fluorous Ligand.Pd

Recycling of the fluorous catalytic phase (run 6: 70%).

HERRERO, M. A.; WANNBERG, J.; LARHED, M.

MJ

H2N

O

HN

IPh

Pd(OAc)2 (0.1 eq.)

Mo(CO)6 (1 eq.)

(3 eq.)

DBU (3 eq.)

P(PhCH2CH2C8F17)3 (0.3 eq.)

THF/FC-84 (1:1.5)microwaves,110°C, 5 min

79%

NH

O

HN Ph

O

+

Mo

Synlett 2335 23382004 -, , 13 ,

Homocoupling. Aqueous Solvents.Pd

PUNNA, S.; DIAZ, D. D.; FINN, M. G.

MJ

Ar-ArO

BO

PdCl2(PPh3)2 (0.1 eq.)

Bu4NF, H2O (1 eq.)

THF/H2O (4:1), air, rt67-85%

Ar-B(OR)2= Ar-B(OH)2,ArB(OR)2 Ar

B

Synlett 2351 23542004 -, , 13 ,

Sonogashira ReactionPd

Also with R2= Ar, SiMe3, alkyl.

HUDSON, R. H. E.; DAMBENIEKS, A. K.; VIIRRE, R. D.

MJ

N

NHR1

I

CH2CO2Et

O

+ R2

+ Pd(PPh3)4 (cat.)

+ CuI (cat.)+ NEt3DMF

R1= H

rt

N

CH2CO2Et

ON

NH2

CH2CO2Et

O

R2NH

R2

R1= Bz

50°C

R2= CH2OMe

64%86%

Cu

Synlett 2400 24022004 -, , 13 ,

57


Sonogashira Reaction and Ag-catalyzed Cyclization.Pd

R= sugar.

AUCAGNE, V.; AMBLARD, F.; AGROFOGLIO, L. A.

MJ

R1+

PdCl2(PPh3)2(0.1 eq.)

CuI (0.2 eq.)

NEt3 (3 eq.)DMF, rtN

R

NH

O

I

O

(3 eq.)

NR

NH

O

O

R1

AgNO3 (0.2 eq.)

acetonert

overall: 95-98%NR

N

O

O

R1CuAg

Synlett 2406 24082004 -, , 13 ,

1,4-Benzodioxines, 1,4-Benzoazines and 2,3-Dihydro DerivativesPd

ACARI, B.; MANDAL, S. B.; DUTTA, P. K.; CHOWDHURY, C.

MJ

Review

> 77 references

Zn

Synlett 2449 24672004 -, , 14 ,

Synthesis of HeterocyclesPd

GABRIELE, B.; SALERNO, G.; COSTA, M.

MJ

Review> 44 references

Use of PdI2 as catalyst

Synlett 2468 24832004 -, , 14 ,

Sonogashira Reactions in Solid PhasePd

KASHIWAGI, Y.; CHIBA, S.; IKEZOE, H.; ANZAI, J.-I.

MJ

O

O

I

O

OSonogashira couplings from and

Cu

Synlett 2513 25162004 -, , 14 ,

58


Amination of Aryl ChloridesPd

NETTEKOVEN, U.; NAUD, F.; SCHNYDER, A.; BLASER, H-U.

MJ

Pd

N

HP

Cl

Fe

Pd

N

HP

ClArCl + HNR2

up to 97%

or22

ArNR2catalyst

catalyst

Synlett 2549 25522004 -, , 14 ,

Homoallylic IsonitrilesPd

KAZMAIER, U.; ACKERMANN, S.

MJ

OX

NC

CO2Et

NC

CO2Et+

[(η3-allyl)PdCl]2 (0.02 eq.)

Cs2CO3 (1 eq.)

THF, 50°C

dppe (0.04 eq.)

X= CO2Et (37%), COPh (6%), PO(OEt)2 (91%)

Synlett 2576 25782004 -, , 14 ,

Heck and Sonogashira Couplings.Pd

Known prrocedures have been used.

BRASHOLZ, M.; REISSIG, H.-U.

MJ

O

CO2Me

OOMe

BnO

I

O

CO2Me

OOMe

BnOO

CO2Me

OOMe

BnOHeckSonogashira

R

R

OR= Ph (84%), CH2OMe (91%) R= Ot-Bu (71%), Me (91%)

Cu

Synlett 2736 27382004 -, , 15 ,

Suzuki Couplings.Pd

A variety of substituted coumarins is described.

BELETSKAYA, I. P.; GANINA, O. G.; TSVETKOV, A. V.; FEDEROV, A. Y.; FINET, J.-P.

MJ

O O

OMe

MeO

OTfN

B(OH)2

n-Bu4NBr (0.1 eq.)

N

O O

O

MeO

Me+

PdCl2(dppf) (0.05 eq.)

K3PO4 (3 eq.)

MeCN, 80°C, 30 min96%

(1.3 equiv.)

B

Synlett 2797 27992004 -, , 15 ,

59


TetrathiafulvalenesPd

Various examples.

QVORTRUP, K.; ANDERSSON, A; S.; MAYER, J.-P.; JEPSEN, A. S.; NIELSEN, M. B.

MJ

I

I

SS

CO2Me

MeO2C

SS

CO2Me

MeO2C

SS

MeO2C

CO2Me

+PdCl2(PPh3)2 (cat.)

CuI (cat.)

NEt3, THF, rt, 2.5 h

78%

Cu

Synlett 2818 28202004 -, , 15 ,

Palladium-Catalyzed Synthesis of Pyrazine Derivatives.Pd

COELLO, A.; SOTELO, E.; NOVOA, H.; PEETERS, O. M.; BLATON, N.; RAVINA, E.

AM

NN

NN

R1R1

O O

I R2

R1 = H, Me, Bz ..R2 = Ar, CH=CH-X, COR,C CR

palladium-catalyzedreactions

Tetrahedron 12181 121932004 60 -, , 52 ,

New Catalyst for Heck Reaction.Pd

Triarylphosphine-functionlized N-heterocyclic carbene ligands for Heck reaction is reported.

WANG, AI-E.; XIE, J-H.; WANG, LI-X.; ZHOU, Q-L.

AM

XR1 R2

+

R1 R21 mol % Pd(dba)2 / L L = NN

Cl PPh2

Tetrahedron 259 2662005 61 -, , 1 ,

Palladium-Catalyzed Cross-Coupling Reaction.Pd

Synthesis of α, α’-disubstituted amino acids based on tandem reaction of dehydroamino acids derivatives is described.MIYABE, H.; ASADA, R.; TAKEMODO, Y.

AM

N CO2R'Ph

PhPh

OAc

Ph

OAcN

O

O

CO2R'

CO2R'N

R

Ph

+

+

RI, Et2Zn / Pd(PPh3)4

Bu3SnH / Pd(PPh3)4 (R = H)

ZnSn

Tetrahedron 385 3932005 61 -, , 2 ,

60


Stereoselective Intramolecular Heck Reaction.Pd

Synthesis of morhine fragments trans- and cis- octahydro-1H-benzo[4,5]-furo[3,2-e]isoquinolines is reported.

HSIN, LI-W.; CHANG, LI-TE.; HSU, C-H.; CHEN, H-W.

AM

N

O I

CO2EtN

O

CO2EtN

O

N

O

N

OPd(OAc)2

H3CO H3CO H3CO H3CO H3CO

H H

PtO2 orNaBH4 or

Pt

Tetrahedron 513 5202005 61 -, , 2 ,

Palladium-Dodecanethiolate Nanoparticules: Recyclable Catalysts for the Suzuki ReactionPd

The reaction yield remained quantitative so upon these six recycling reactions (resp. 100%, 100%, 98%, 94%, 92%,87%)LU, F.; RUIZ, J.; ASTRUC, D.

TJ

R X B(OH)2 R+

Biphasic THF/H2O (1/1)NaOH, rt

R = H, CH3, CH3OX = Cl, Br, I

Yield 27-100%

Pd-dodecanethiolatenanoparticule cat.

B


Pyrazole-Tethered Arylphosphine Ligands for Suzuki ReactionsPd

MUKHERJEE, A.; SARKAR, A.

TJ

X B(OH)2R R

N

PPh2

N

H3C

R+

R = CH3, CH3O, NO2, COCH3, CHOX = Cl, Br

Yield 31-99%

Pd2(dba)3 (1 mol%)CsF (3 equiv)

Toluene, 65-80 °C

Ligand (4 mol%)Ligand =

R = t-Bu, Ph

B


Pd-Catalyzed Cross-Coupling Reaction of (Z)- and (E)-BromoenynePd

Inversion product in cross-coupling reaction.

UENISHI, J.; MATSUI, K.; OHMI, M.

TJ

TBDPSO

Br

TMS

R SnBu3

TBDPSO

R

TMS TBDPSO TMS

Pd cat.

or

Sonogashira or Stillecoupling conditionsin DMF or CH2Cl2

or

yield 58-97%12 examples

SiSn


61


Regioselective Palladium-Catalyzed Allylic AlkylationsPd

Ligand = s-Binap, s,s-Trost; Nuc = 4-Methoxyphenol, Phenol, 4-t-Butylphenol, 4-Methoxyaniline

DONG, Y.; TEESDALE-SPITTLE, P.; HOBERG, J. O.

TJ

Ph OTBDPS

OCOEt

Ph OTBDPS

NucPd2dba3.CHCl3 3 mol%

Base, Ligand 8 mol%Nuc Yield 88-94%

ee = 87-98%Base = Cs2CO3, NaH, nBu4NCl


Palladium Catalyzed Allylation Reaction with Peptide-Derived Phosphine LigandsPd

AGARKOV, A.; GILBERTSON, S. R.

TJ

MeO OMe

O OMeO OMe

O ONH

HN N

H

OPPh2

NH O

O

PriO

N

HN

NH

O

O

O

Ph2P

Ph

OAc+

Pd-Ligand

MeCN, rtBSA, TBAF

Ligand =

Conversion > 95%ee = 73%


Convergent Synthesis of Organometallic DendrimersPt

ONITSUKA, K.; FUJIMOTO, M.; KITAJIMA, H.; OHSHIRO, N.; TAKEI, F.; TAKAHASHI, S.

CJMChem. Eur. J. 6433 64462004 10 -, , 24 ,

Coordination-Driven Self-Assembly of 2D MacrocyclesPt

CHI, K.; ADDICOTT, C.; ARIF, A. M.; STANG, P. J.

CJM

Pt

Pt

PEt3

PEt3

PEt3

PEt3

ONO2

ONO2

N X

CO2-M+

Pt

Pt

PEt3

PEt3

PEt3

PEt3

N

O

XO

O

XO

N Pt

Pt

PEt3

PEt3

PEt3

PEt3

2+

X=

J. Am. Chem. Soc. 16569 165742004 126 -, , 50 ,

62


The First Pentacoordinate d10 Pt(0) ComplexPt

CROSSLEY, I. R.; HILL, A. F.

LD

PtS

S

S

HPPh3

BNN

N+ Cl-

-HCl

PtS

SS

Ph3P

BNN

N


-, , 24 ,

Hetero-Diels-Alder Reactions Catalyzed by Lewis Acid Pt ComplexesPt

DOHERTY, S.; KNIGHT, J. G.; HARDACRE, C.; LOU, H.-K.; NEWMAN, C. R.; RATH, R. K.; CAMPBELL, S.;NIEUWENHUYZEN, M.

LD

+O

OH

X CH2Cl25h

X=OEt, Ph, p-tolyl

O

O

X

PPh2Ph2P Pt

OTfOTf

71-93%ee

[Pt]

[Pt] =


-, , 26 ,

Alkynylation of Aryl IodidesPt

OH, C. H.; REDDY, V. R.

MJ

B(Oi-Pr)3R Li ArR+ Ar I

Pt(PPh3)4 (0.025 eq.)CuI (0.05 eq.)

DMF, 120°C 23-86%

LiCuB

Synlett 2091 20942004 -, , 12 ,

Pt-Catalyzed Regio- and Stereoselective Pyridylthiolation of Terminal AlkynesPt

HIRAI, T.; KUNIYASU, H.; KAMBE, N.

TJ

N

IArSK R

N

R

SPhN

SPh+ +Pt(PPh3)4 5mol%

toluene, reflux, 24h+

9 examples : 50-77%


63


Platinum(II)/Europium(III)-Catalyzed Intramolecular Hydroalkylation Pt

The reaction proceeds with β-diketones and β-ketoesters. A mechanism is proposed.LIU, C.; WIDENHOEFER, R. A.

TJ

R3

O OR1

R2

O

R3

O

R2

R1

[PtCl2(H2C=CH2)]2 1mol%EuCl3 2 mol%HCl 1 equiv

dioxane90 °C, 18h

11 examples31-93%

R1; R2 = H, Me, -(CH2)5-R3 = Me, Et, i-Pr, t-Bu, Cy

Eu


Catalytic Diastereo- and Enantioselective Claisen Rearrangement Cu

ABRAHAM, L.; KÖRNER, M.; SCHWAB, P.; HIERSEMANN, M.

LF

O

O-i-Pr

TPSO

O

OBn

O-i-PrO

O

BnO

TPSON

O

N

O

Cu

H2O OH2

t-Bu t-Bu

2

2 SbF62.5 mol %

mol sieves, CH2Cl2, 1.5 h, rt

99%, 98% de, 99% ee

Adv. Synth. Catal. 1281 12942004 346 -, , 11 ,

Geminal Bis(sulfoximine)s: Synthesis and Applications in AsymmetricCatalysisCu

REGGELIN, M.; WEINBERGER, H.; SPOHR, V.

LF

OSp-Tol O

N

"one-pot"

MeLi

SN

O

S

O

N

OH HO

Adv. Synth. Catal. 1295 13062004 346 -, , 11 ,

Highly Selective Copper-Catalyzed Monoarylation of AnilineCu

Excellent results with bridged bisimidazolidenes and biphenyl-bisalkylphosphines as ligands

HAIDER, J.; KUNZ, K.; SCHOLZ, U.

CFR

NH2

+

Cl

NO2

K2CO3, 190°C, 4h

N

NO289%yld, 99% selectivity

PCu

BrH

BrHCu

P(tBu)2

(tBu)2

cat(2.5%)

Adv. Synth. Catal. 717 7222004 346 -, , 7 ,

64


Copper-Phosphine-Catalysed Process Induced by an Initial In Situ Phosphine OxidationCu

Initial phosphine oxidation leads to a more reactive and selective metal complex

CÔTÉ, A.; BOEZIO, A.; CHARETTE, A.B.

VE

P

P

Me

Me

Me

Me

P

P

Me

Me

Me

Me

O

H

NP

O

Ph

Ph

Et

HN

PO

PhPh

"Cu"1) Cu(OTf)2 (6 mol %),

Et2Zn (2 eq.)

2) ligand 1 or 2(3 mol%)

1 2

with 1: 38% yield, 0%ee ; with 2: 100% yield, 97% eein situ

oxidation

Angew. Chem. Int. Ed. 6525 65282004 43 -, , 47 ,

Copper-Binaphtylthiophosphoramide-Catalysed Asymmetric Conjugate AdditionCu

Several examples of cyclic and acyclic enones

SHI, M.; WANG, C.-J.; ZHANG, W.

VE

NHEt

NHPR2

O

n

O

Et (Ph)n

S*

1) CuI (3 mol%)

ligand (6mol%)

2) Et2Zn or Ph2Zn(1.5 eq.), rt

50-78% yield; up to 98% ee

ligand =

n = 0, 1, 2 R = Me, Ph

Zn

Chem. Eur. J. 5507 55162004 10 -, , 21 ,

Copper-catalysed N- and C- Arylation with Aryl Bromides and IodidesCu

An extensive study with mechanistic considerations

CRISTAU, H.-J.; CELLIER, P.P.; SPINDLER, J.-F.; TAILLEFER, M.

VE

H

X

R

Nu

RN

NH2

OH

N

OH

OH

Nu

azolesamides

Carbamatesmalonic derivatives X = I, Br R = H, EWG, EDG

+

CuI 0.1-10%, ligand 0.2-20%

Cs2O3 (1.4-2 eq.)

MeCN or DMF, 50-82°C

high yields

ligand =

or

Chem. Eur. J. 5607 56222004 10 -, , 22 ,

C2-Symmetric Fluorous Diamines and Diimines for Asymmetric CyclopropanationCu

SHEPPERSON, I.; QUICI, S.; POZZI, G.; NICOLETTI, M.; OHAGAN, D.

GVI

Ph

+N2CHCO2R

Cu(X)L*

C8F18/DCM

∗ ∗Ph CO2R ∗ ∗Ph

CO2Ree=10-62%

+NHHN

C8F17 C8F17

C8F17 C8F17

H H

L*

Eur. J. Org. Chem. 4545 45512004 -, , 22 ,

65


Preparation of Functionalized β,β β,β β,β β,β Di- and Trisubstituted Vinylic SulfoxidesCu

X = I, Br. Cu-cat. = CuI, CuCN, Cu(OTf)2.

MAEZAKI, N.; SAWAMOTO, H.; SUZUKI, T.; YOSHIGAMI, R.; TANAKA, T.

BS

n-Bu S

Tol

O

S

Tol

O

n-Bu

R

RZnX (1.1-10 eq.)Cu-cat. (2 eq.)

-78°C to RT

67-94%

R = Allyl, Bn, t-BuCO2CH2, TMSCH2, BocNH(CH2)3

J. Org. Chem. 8387 83932004 69 -, , 24 ,

Enantioselective Conjugate Reduction of NitroalkenesCu

R = aryl; R’ = Me, n-Pr, i-Pr, CH2OH.

CZEKELIUS, C.; CARREIRA, E.

AC

RNO2

R'

PhSiH3 (1.5 equiv), CuF2 (1 mol%)

(R)-(S)-JOSIPHOS (1.1 mol%)

CH3NO2 (10 mol%), H2O, PMHS (0.1 equiv)

toluene, rt

RNO2

R'

6 ex, 52-88%, er up to 98:2

Si

Org. Lett. 4575 45772004 6 -, , 24 ,

First Asymmetric Aminohalogenation of Alkenes in Ionic Liquid MediaCu

[Bmim][BF4] is the only effective media for success.

XU, X.; SAIBABU KOTTI, S.R.S.; LIU, J.; CANNON, J.F.; HEADLEY, A. D.; LI, G.

AC

Ar

N OO

O

1. 4 Å MS, CuOTf (8 mol%)

[Bmim][BF4], TsNCl2 (1.1 equiv)

2. Na2SO3 (aq)Ar

N OO

O

Cl

NHTs

H

8 ex, 60-72%, up to 75% de

Org. Lett. 4881 48842004 6 -, , 26 ,

Enantioselective Alkynylation of Prochiral sp3 C-H Bonds Adjacent to a Nitrogen AtomCu

Different ligands were tried, L* is the most efficient.

LI, Z.; LI, C.-J.

AC

N R1

+R2

10 mol% CuOTf15 mol% L*

1 equiv tBuOOH (5-6M in decane)

50 °C, 2 days

N R1

R2

NO

N N

O

Ph Ph

*

L*11 ex, 11-72%ee: 5-74%R1 = H, 4-MeO, 2-MeO ; R2 = Ph, 4-MeOPh, 4-BrPh, Hex, TMS, Py

Org. Lett. 4997 49992004 6 -, , 26 ,

66


Synthesis of Vinyl SulfidesCu

The reaction tolerates a wide variety of functional groups.

BATES, C. G.; SAEJUENG, P.; DOHERTY, M. Q.; VENKATARAMAN, D.

AC

R1 SH IR3

R2

+

5 mol% I1.5 equiv K3PO4

toluene, 110 °C

R1 SR3

R2

NNCu

Ph3P PPh3

NO3

I =

30 ex, 80-98%R1 = aryl, heteroaryl, alkyl ; R2, R3 = H, alkyl, aryl

Org. Lett. 5005 50082004 6 -, , 26 ,

Unusual Diaddition of Unsaturated Cyanocuprates onto αααα,ββββ-Unsaturated NitrilesCu

Diaddition giving 1 or monoaddition giving 2 depend on the electronic nature of the nitrile

BARBERO, A.; BLANCO, Y.; FERNANDEZ, H.;

VE

•+

tBuPh2SiCu(CN)Li

R2CN

R1

O

SiPh2tBu

SiPh2tBu

R1

R2

CN

SiPh2tBu

R1

R2or

1 250-78% yield

LiSi

Synlett 2833 28352004 -, , 15 ,

Copper Catalysed N-Arylation of Hydrazines with BismuthanesCu

LOOG, O.; MÄEORG, U.

VE

N N

Boc

R1 H

R2

N

N

Boc

R1

R2 O

O

O

O

BiCH2Cl2

+ 1.5Cu(OAc)2, Et3N

85-96% yieldR1 = Ph, Boc, Ac; R2 = Boc, Ac

Bi

Synlett 2537 25402004 -, , 14 ,

Preparation and Acylation of Highly Functionalised Cu Derivatives of 3-IodoindazolesCu

YANG, X.; KNOCHEL, P.

VE

N

N

I

BocO

Et

(Nphyl)2CuLi(1.2 eq.)

THF/Et2O = 3:1 N

N

Cu(Nphyl)Li

BocO

Et

cHexCOCl

NMP

N

N

BocO

Et

O

76%

Li

Synlett 2303 23062004 -, , 13 ,

67


Cu-Al-Catalysed Addition of Grignard Reagents onto Acyl ChlorideCu

No tertiary alcohols detected.

VICHA, R.; POTACEK, M.

VE

O

R ClCuCl (3 mol%)AlCl3 (3 mol%)

THF, 10°C, 10 min+ R'MgBr

O

R R'

R = adamantyl, Ph, Me, Et, tBuR' = Me, Et, Aryl

80-96% yield

Al

Tetrahedron 77 822005 61 -, , 1 ,

Asymmetric Allylic Oxidation of Bridged-bicyclic alkenesCu

CLARK, J. S.; CLARKE, M.-R.; CLOUGH, J.; BLAKE, A. J.; WILSON, C.

GVI

R R R R

O2CPh

H

Cu(MeCN)4PF6 (5 mol%)L* (6 mol%), t-BuO2COPh

MeCN, 40°CR = H, (CH2)2

60-70% ee

L* = box, pybox ligands


1,3-Dipolar Cycloaddition of Nitrones with 3-Alkenoyl-2-oxazolidinonesCu

On the preceding paper, the evaluation of the chiral bidentate ligand-metal complexes is presented.

SAITO, T.; YAMADA, T.; MIYAZAKI, S.; OTANI, T.

AC

HN

OR1

PhONR2

O O

+

N NR R

R1 = Ph, 4-MePh, 4-FPh, 4-ClPh, 4-BrPh, 4-CF3Ph, 4-CNPh, 4-NO2Ph, 2-naphthyl, 2-furyl

R2 = Me, H; R = Ph, 2,6-(MeO)2C6H4, 2,6-Cl2C6H4, C6F5

20 mol% [Cu(OTf)2-1]

CH2Cl2, rt, 4Å MS

ON R2Ph

R1 CO

N O

O

1endo26-99%; endo/exo up to >99/1


Propargyl Claisen RearrangementAu

Starting from enantiomerically pure starting materials, chirality tranfer is observed

SHERRY, B. D.; TOSTE, F. D.

CJM

R2

O

R3

R1

1) [(Ph3PAu)3O]BF4 1%CH2Cl2, rt

2) NaBH4, MeOH, rtR1 •

R2

R3R4

15 examples61-96%

R4 OH

J. Am. Chem. Soc. 15978 159792004 126 -, , 49 ,

68


Complexes with Vapochromic BahaviorAu

LEFEBVRE, J.; BATCHELOR, R. J.; LEZNOFF, D. B.

CJM

Cu[Au(CN)2]2(DMSO)2

solventCu[Au(CN)2]2(solvent)x

solvent= H2O, CH3CN,dioxane, DMF, pyridine, NH3

From green to dark-blue complexes

J. Am. Chem. Soc. 16117 161252004 126 -, , 49 ,

Zinc(II) Phtalocyanine DerivativesZn

Photodynamic activity of these compounds has been studied.

YSLAS, E.I.; RIVAROLA, V.; DURANTINI, E.N.

PL

CN

CNRO

DBU

Zn(CH3COO)21-pentanol N

N

N

N

N

N

N

N

OR

OR

RO

RO

Zn

R = CH3, 4-CF3C6H4CH2

38-41%

Bioorg. Med. Chem. 39 462005 13 -, , 1 ,

Stereoconservative Negishi Arylation and Alkynylation of 2,2’-Diodo-1,1’-binaphtylZn

An improved procedure for the preparation of the diiodo precursor is also described

KRASCENICSOVA, K. ; WALLA, P. ; KASAK, P. ; URAY, G. ; KAPPE, O. ; PUTALA, M.

MVI

II

ArZnCl orRC CZnCl

Ar

Ar Ar

Aror

5% Pd(PPh3)4

THF, Microwave120°C, 40s-20min

12 examples 75-99%

Pd

Chem. Commun. 2606 26072004 -, , 22 ,

Synthesis of a Fluorescent Sulfatide for the Study of CD1 Antigen Binding PropertiesZn

FRANCHINI, L.; COMPOSTELLA, F.; DONDA, A.; MORI, L.; COLOMBO, D.; DE LIBERO, G.; MATTO, P.; RONCHETTI, F.;PANZA, L.

OC

CHO

OO

O

O

C13H27

OH91% yield

syn/anti = 95:5

(−)-N-methylephedrinetoluene

pentadecyneZn(OTf)2, TEA

HO C13H27

N3

OBz

Eur. J. Org. Chem. 4755 47612004 -, , 23 ,

69


Chiral Sulfamide-Amine Alcohols as LigandsZn

Used for the enantioselective addition of diethylzinc to aldehydes with ee up to 99%.

MAO, J.; WAN, B.; WANG, R.; WU, F.; LU, S.

DCE

N

OH NHTs

Me

Ph Ph

N

NHTs

OH

Ph

Best ligands:

J. Org. Chem. 9123 91272004 69 -, , 26 ,

Lewis Acid Catalysis in Heterolysis Reactions Zn

MIRANDA, N.; XU, L.; NEWCOMB, M.

CS

Ph

Ph

OMeOX

R

ZnBr2 Ph

Ph

MeOOX

R

Zn2+

Ph

Ph

OX

R

OXPh

Ph RKbind

kcat fast

Org. Lett. 4511 45142004 6 -, , 24 ,

Stereoselective Synthesis of Tetra-Substituted Olefins Zn

NAKAMURA, M.; FUJIMOTO, T.; ENDO, K., NAKAMURA, E.

CS

HN O

NR22

H R3+

O O

NR22

H3C R3

1) (C2H5)2Zn(1.0-0.05 equiv)

2) HCl aq.

R1 = allyl, butyl, 2-methoxyethyl, ; NR22 = dialkylamino, morpholinyl; R3 = aryl, alkyl

R1

Org. Lett. 4837 48402004 6 -, , 26 ,

Facile CyclopropanationZn

Simple and friendly environmentally preparation of cyclopropane via substituted olefins.

SAKUMA, D.; TOGO, H.

OS

IR'

CO2R

R'''

R''CO2R

R''

R'

R'''

Zn (3 equiv.)

t-BuOH-H2O (2:1)

Reflux (5-99%)

R', R'', R''' = Me, n-Pr, c-hex

R = Bn, Et

Synlett 2501 25042004 -, , 14 ,

70


Reductive Cyclization to Nine-Membered Lactone by Zinc-Acetic AcidZn

Access to the core of ent-Griseoviridin.

CHAUME, G.; KULIGOWSKI, C.; BEZZENINE-LAFFOLEE, S.; RICARD, L.; PANCRAZI, A; ARDISSON, J.

GJ

O

S)2

O

H

BocNHS

OH

O

BocNHS

O

O

BocNH

H

b) AgNO3

a) Zn, AcOH, AcOEt

+

31% 4.5%(ent-series)

Ag

Synthesis 3029 30362004 -, , 18 ,

Enantioselective Addition of Diethylzinc to Benzaldehydes.Zn

C2 symetrical bipyridyldiol ligands used as chiral ligands.

CHEN, Y.-J.; LIN, R.-X.; CHEN, C.

CB

CHOR

R

OH

up to 99% ee

+ Et2Zn

1.5% Ti(O-iPr)4 5% L* / rt / 30h

L* =*

N N

Ph2C CPh2HOOH


Enantioselective Addition of Diethylzinc Induced by Chiral Epoxides.Zn

Asymmetric autocatalysis using chiral epoxides.

KAWASAKI, T.; SHIMIZU, M.; SUZUKI, K.; SATO, I.; SOAI, K.

CB

N

N

CHO

tBu

N

N

tBu

OHO

R H

R = Me or Ph

2% ee

Toluene / rt / 2h

iPr2Zn+

H

70-94% ee


Enantioselective Alkynylation of Aromatic Ketones.Zn

LIU, L.; KANG, Y.-F.; WANG, R.; ZHOU, Y.-F.; CHEN, C.; NI, M.; GONG, M.-Z.

CB

Ar CH3

O

ArCH3

HOPh

Ph

(2 eq.)

+

ee = 60-80%

Hexane / 0°C / 30-48h10% mol L*

L* =

Bn

OH

PhPh

H2NH

*Et2Zn

(2 eq.)

+


71


Asymmetric Addition of Diethylzinc to Aldehydes.Zn

Synthesis of new chiral ferrocenyl aziridino alcohols.

WANG, M.-C.; LIU, L.-T.; ZHANG, J.-S.; SHI, Y.-Y.; WHANG, D.-K.

CB

Et2Zn

(2 eq.)R H

O+

R = Ar, CH=CH-Ph

CH2-CH2-Ph

3% mol L* =

Toluene / rt / 48h

R Et

OH

up to 98.8% ee

*

Fe

N

R'R'

OH

H


Asymmetric Alkylation of Aldehydes.Zn

HARADA, T.; KANDA, K.; HIRAOKA, Y.; MARUTANI, Y.; NAKATSUGAWA, M.

CB

Et2Zn R Et

OH

(3 eq.)

R CHOTi(O-iPR)4 (0.2-1 eq.)

+CH2Cl2 - Hexane / 19h

ee up to 91%L* = Dinuclear bis-BINOLate Titanium(IV)


Alkynylation of TosyliminesZn

9 examples.

LEE, K.Y.; LEE, C.G.; NA, J.E.; KIM, J.N.

GP

NTs

R R'R'

NHTs

R

+

DIEA (1.2 eq.)ZnBr2 (1.2 eq.)

CH3CN, 50-60°C6-8h

67-81%


A Mercury Bis(tricarbido) ComplexHg

This complex was structurally characterised as a DMSO hexasolvate

DEWHURST, R. D. ; HILL, A. F. ; WILLIS, A. C.

MVI

W C C C SiMe3

OCOC

Tp TBAF

HgCl2W C C C

OCOC

TpHg WCCC

COCO

Tp BHN N

N NN

N

Tp = hydrotrispyrazolylborate

Chem. Commun. 2826 28272004 -, , 24 ,

72


Highly Enantioselective Synthesis of Secondary Alcohols using TriphenylboraneB

RUDOLPH, J.; SCHMIDT, F.; BOLM, C.

CFR

RH

O First BPh3 (1equiv.), ZnEt2(3 equiv.),

chiral ferrocene (10 mol%) R Ph

OH

up to 98% ee

Fe N

O

PhPhOH

Zn

Adv. Synth. Catal. 867 8722004 346 -, , 7 ,

Synthesis of 1-Amino-3-[(dihydroxyboryl)methyl]-cyclobutanecarboxylic AcidB

Synthesis of a novel boronated aminoacid is descibed.

KABALKA, G. W.; YAO, M.-L.

FV

(HO)2B

CO2H

NH2

This new agent is currently evaluated as a Boron Neutron Capture Therapy (BNCT).

J. Org. Chem. 8280 82862004 69 -, , 24 ,

Synthesis of 1-Acyldipyrromethanes Containing a Dialkylboron Mask.B

The dialkylboron complex provides an effective mask of both the R-acyl and pyrrolic nitrogen entities.

ZAIDI, S. H.; MUTHUKUMARAN, K.; TAMARU, S.-I.; LINDSEY J. S.

FV

N HN

R1 H

OR2

B

N HN

R1 H

OR2

BO

R3

MgBr(2 mol eq.)

1.

2.R3

O

S N R3

O

Clor

J. Org. Chem. 8356 83652004 69 -, , 24 ,

Highly Enantioselective Conjugate Additions of RBF3K to Enones.B

DUURSMA, A.; BOITEAU, J.-G.; LEFORT, L.; BOOGERS, J. A.; DE VRIES, A.; DE VRIES, J.; MINNAARD, A. J.; FERINGA,B. L.

FV

O

+ RBF3K

2% Rh(acac)(eth)24% Ligand

Ethanol, ∆

O

R

PO

ON = Ligand

R = alkenyl e.e. : up to 88%R = aryl, e.e. : up to 99%

Rh

J. Org. Chem. 8045 80522004 69 -, , 23 ,

73


Preparation of 5-Hydroxy-1-Alkenyboronates from 1-Alkynylboronates and Aldehydes.B

Reasonable yields could be obtained with only 2 equiv. of aldehydes.

AL AZIZ QUNTAR, A.; SREBNIK, M.

FV

+ Cp2ZrCl2 / 2 EtMgBrR1 B

O

O

HO

R2

1. R2CHO

2. H3O+

Yields = 43 - 58%

R1 BO

O

ZrMg

Org. Lett. 4243 42442004 6 -, , 23 ,

Convenient, Eficient, and Regioselective Synthesis of 1,3_Diaryl-1,3-dihalopropanesB

KABALKA, G.X.; WU, Z.; JU, Y.

MMA

H

O XXBX3

X Y

+

R

RCH2Cl2

X = Cl, BrR = H, Me

Yield= 95-99%

Synthesis 2927 29292004 -, , 17 ,

Palladium-Catalyzed C-C Bond-Forming 1,2-Ligand Migration of OrganoalanesAl

FILLION, E.; CARSON, R. J.; TREPANIER, V. E.; GOLL, J. M; REMOROVA, A. A.

OC

R

X

( )n

R MeMe1) Me3Al, Cp2ZrCl2, DCE

2) Pd[P(p-MeOPh)3]2Cl2

P(p-MeOPh)3 (20 mol%), Et3NDABCO, CH3CN, 100-120 °C ( )n

6 - 67% yieldX = OTf, I

ZrPd

J. Am. Chem. Soc. 15354 153552004 126 -, , 47 ,

The First Bicyclobutane Dianion of Heavier Group 14 ElementSi

LEE, V.YA.; TAKANASHI, K.; ICHINOHE, M.; SEKIGUCHI, A.

EJ

RGe

Si(Cl)R

GeR

R(Cl)Si

(R = SiMetBu2)

M/THF

M = Mg, Ca Si SiR

GeRM

RGe

R

RGe

Si SiR

GeR

R

SrX2/THF2-

rt/2d M = Mg, 73%

2h/rt

M = Sr, 74%

(THF)n

2K+(THF)2

GeKMgCaSr

Angew. Chem. Int. Ed. 6703 67052004 43 -, , 48 ,

74


Recent Developments in the Synthesis and Structure of OrganosilanolsSi

CHANDRASEKAR, V.; BOOMISHANKAR, R.; NAGENDRAN, S.

EJ


Chem. Rev. 5847 59102004 104 -, , 12 ,

Recent Developments in the Chemistry of Stable SilylenesSi

HILL, N.J.; WEST, R.

EJ


J. Organomet. Chem. 4165 41832004 689 -, , 24 ,

Isolable Silylenes, Disilenes, Trisilaallene and Related CompoundsSi

KIRA, M.

EJ


J. Organomet. Chem. 4475 44882004 689 -, , 24 ,

A New and Practical Acrolein ββββ-Anion Equivalent : γγγγ-p-Toluene-α,βα,βα,βα,β-epoxysilaneSi

SASAKI, M.; TAKEDA, K.

PJP

Me3Si SO2Tol

O O R

OR

OH

1/ NHMDS (1.0 eq), THF 2/ n-BuNF (1.0 eq) EtOH (3.0 eq)

68-85%

+R-X

RCHO

(1.0 eq)

71-80%

Org. Lett. 4849 48512004 6 -, , 26 ,

75


Condensation of Allenylsilanes with Acceptor-Substituted CyclopropylmethylsilanesSi

These formal [3+2] nd [3+3] additions give high regio- and stereocontroled adducts

YADAV, V.K.; SRIRAMURTHY, V.

PJP

SiR3

R2

R1

O TBDPS

R2

R3Si

R1

O

TBDPS

SiR3

R2

R1

TBDPS

+ Lewis acid

or

Org. Lett. 4495 44982004 6 -, , 24 ,

Free Radical Reactions of Stable Silylenes and GermylenesSi

1 is formed by reaction between the intermediates R2Si(ONR’2)2 and R2Si=O (R2 = tBuNCH=CHNtBu)

NAKA, A.; HILL, N.J.; WEST, R

EJ

N

M

N

tBu

tBu

O

N

Si

N

tBu

tBu

N

Si

N

tBu

tBuONR'2

hexaneN

Ge

N

tBu

tBu

ONR'2

ONR'2R'2NO

1

2 TEMPO

hexane

30 min

2 TEMPO

15 min/0°C87%

55%

Ge


1,2-Addition Reactions of Disilenes: an Ab Initio StudySi

The first step in the addition of ROH is the formation of a weak complex between O and Si.

TAKAHASHI, M.; VESZPREMI, T.; KIRA, M.

EJ

H2Si=SiHF H2Si=SiH(C CH) H2Si=SiH(NH2)H2Si=SiHMe


Electrochemistry and Computations of Stable Silylenes and GermylenesSi

1 and 3 are more easily oxidized than 2 and 4. Oxidation is easier for silylenes than germylenes.

DHIMAN, A.; MÜLLER, T.; WEST, R.; BECKER, J.Y.

EJ

N

Si N

tBu

tBu

N

Si N

tBu

tBu

N

Ge N

tBu

tBu

N

Ge N

tBu

tBu

1 2 3 4

Ge


76


Thermal Equilibrium between a Disilene and a SilyleneSi

The equilibrium between disilene and silylene was investigated by DFT calculations.

TSUTSUI, S.; TANAKA, H.; KWON, E.; MATSUMOTO, S.; SAKAMOTO, K.

EJ

SiSi

tBu

tBu

tBu

tBu

Si Si

tBu

tBu

tBu

tBu

tBu

tBu

MeOH

rttoluene

SiSi

tBu

tBu

tBu

tBu

tBu

tBuSiSi

tBu

tBu

tBu

tBu

H

OMe

tBu

tButBu

tBu

94%

K


Spiro-oxindoles from Isatins via a Silicon RouteSi

NAIR, V.; MATHAI, S.; AUGUSTINE, A.; VIJI, S.; RADHAKRISHNAN

PJP

Me

Si NMeMe

OMe

Ph

N

Ph

+- N

R2

R1

O

NO

Ph

N

R2

R1O

OTFAcat.

86-96%

Synthesis 2617 26192004 -, , 16 ,

Ketones, Imines and Electrophilic Double Bonds: Their Asymmetric HydrosilylationSi

Only Ru and Ti catalysts are concerned

RIANT, O.; MOSTEFAÏ, N.; COURMARCEL, J.

PJP

Recent Advances : a Review with > 81 references

RuTi

Synthesis 2943 29582004 -, , 18 ,

Enantioselective Allylation of Aldehydes with AllyltrichlorosilanesSi

NAKAJIMA, M.; KOTANI, S.; ISHIZUKA, T.; HASHIMOTO, S.

PJP

OH R3

R2R1Ph

P

P

O

OPh

PhPh

Ph

cat. =

(S)-BINAPO

Ph CHO

R2

R1

R3

SiCl3

+ cat. (10% mol), i-Pr2NEt (5 equiv.) Bu4N+I- (1.2 equiv.) CH2Cl2, rt


77


Organosilicon Polymers via Lewis-acid Catalyzed trans-Allylation of AlkynesSi

ASAO, N.; TOMEBA, H.; YAMAMOTO, Y.

PJP

Sim

*

Si*m

n

m = 1, 2

cat. HfCl4


Chemical Routes to GeS2 and GeSe2 NanowiresGe

GeSe2 nanowires were obtained by a rather similar route.

NATH, M.; CHOUDHURY, A.; RAO, C.N.R.

EJ

(TMA)4Ge4S10controlled acid

hydrolysisNa dodecyl sulfate

GeS2 nanowires

80%TMA = Me4N

+

Chem. Commun. 2698 26992004 -, , 23 ,

Characterization of Transient Germylenes and Digermenes in SolutionGe

1 gives 2. 1 and 2 have been characterized in solution by UV.

LEIGH, W.J.; HARRINGTON, C.R.; VARGAS-BACA, I.

EJ

GeR2R2Ge: R2Ge=GeR2

R2Ge(H)OMe R2Ge(H)Ge(OMe)R2

MeOH

hexane(R = Me, Ph, Mes)1 2

+248 nm

+

J. Am. Chem. Soc. 16105 161162004 126 -, , 49 ,

Stille Coupling of StereoChemically Defined αααα-SulfonamidoorganostannanesSn

Ligands used : PPh3, (o-tol)3P, dppe, TTMPP, (Fu)3P, Ph3As.

KELLS, K. W.; CHONG, J. M.

SFR

H

NSO

tBu

X

SnBu3

NHBus

X

NHBus

XO

Ph

(yields : 86-94%; dr >99:1)

1) Bu3SnM THF, -78°C

X = H, Me, OMe, NMe2, Cl, Br, CF3

M = Li, ZnEt2Li

2) mCPBA

Bus = t-Butanesulfonyl

PhCOCl, Pd2.dba3, CuCN

toluene, ligand, 70°C

(best yields : 63-98%)

PdCuZn

J. Am. Chem. Soc. 15666 156672004 126 -, , 48 ,

78


Stannylative Cycloaddition of Enynes Catalyzed by Palladium-IminophosphineSn

T h e r e g i o s e l e c t i v e c y c l o a d d i t i o n o f e n y n e s 1 c a t a l y z e d b y a P d - c o m p l e x h a v i n g 2NAKAO, Y.; HIRATA, Y.; ISHIHARA, S.; ODA, S.; YUKAWA, T.; SHIRAKAWA, E.; HIYAMA, T.

TT

H

Me

Me

SnBu3

Me

Me

Me

NCy

PPh2

+ (Bu3Sn)2O

3 equiv 0.5 equiv

+

Cp(allyl)Pd (5.0 mol%)

maleic anhydride (7.5 mol%)

81% 14%3 (5 mol%)

2

1

Pd

J. Am. Chem. Soc. 15650 156512004 126 -, , 48 ,

New Tin Templates for the Synthesis of Macrocyclic Polythiaether-Polythiaester LigandsSn

VUJASINOVIC, I.; VELJKOVIC, J.; MLINARIC-MAJERSKI, K.

BI

SHS

SHn

O SnBu

Bu

toluene, reflux24h

BuSn

Bu

S

SS

n

n=1 - 1 (83%)

n=2 APTS cat. 2+1 (50%, 2/1)

n=3 APTS cat. 3+2+1 (60%, 6/2/1)

ClCl

O

O

CHCl3reflux, 12h

S

SS

n

O

O

S

S

O

O

SS

SS

O

O

n

n

+

7-62%

J. Org. Chem. 8550 85532004 69 -, , 24 ,

Silylstannylation/Cyclization of Allene-Aldehydes for Synthesis of IndolizidinesSn

The structures of diastereomers were unambiguously assigned by spectroscopic and X-ray methods.

KUMARESWARAN, R.; GALLUCCI, J.; RAJANBABU, T.V.

BI

N

O

O

4 diastereomers (1/0.7/0.5/0.6)

Me3SiSnBu3

Pd(II), THFrt, 10 min.

N

O

HHO

Me3Si

4 diastereomers : 32% / 24% / 12% / 14%

82% yield

SiPd

J. Org. Chem. 9151 91582004 69 -, , 26 ,

Lewis Acid-Promoted Annulation of o-Quinonediimines by AllylstannaneSn

A mechanism is proposed to explain the rule of the protective group.

NAIR, V.; DHANYA, R.; RAJESH, C.; BHADBHADE, M.; MANOJ, K.

BI

R1 NR

NR

+

SnBu3

R2

ZnCl2

N

NR1

R2

SO2Ph

SO2Ph

SnBu3

R= SO2Ph

CH2Cl20°C, 30 min

R1=Cl, Br, Me R2=H, Cl, Me

44-98%ZnCl2

R= COPh

CH2Cl20°C, 30 min

NHCOPh

NHCOPh

R4

R1

R3

If R2=H then R3= allyl and R4=H

If R2=Cl or Me then R3=R2 and R4=allyl

61-77%

Org. Lett. 4743 47452004 6 -, , 25 ,

79


Oligomethylene-Bridged Dinuclear Triorganotin triflates and DiphenylphosphinatesSn

The X-ray structure of 1 a shows two symmetry related six-membered rings weakly associated with two bidentate triflateanions.BECKMANN, J.; DAKTERNIEKS, D.; DUTHIE, A.; MITCHELL, C.

TT

O

Sn Sn

OP

PhPh

Ph

Ph

PhPh ( )n

+

- H2O

HO2PPh2[Ph2Sn(CH2)nSnPh2(OH)](O3SCF3)

-(O3SCF3)

1a-c

a : n = 1b : n = 2c: n = 3


Synthesis of Propargyl C-Glycosides Using AllenyltributylstannaneSn

Propargyl C-glucose and C-galactose have been prepared.

CHAN, K. L.; COUMBARIDES, G. S.; ISLAM, S.; WYATT, P. B.

SFR

O X

OBn

OBn

OBn

BnO

OOBn

OBn

OBn

BnO

SnBu3

TMSOTf or BF3.Et2O (1eq)-15°C to 20°C

X = OAc, OC(=NH)CCl3 or F

, CH2Cl2

yields = 39-73%


One-pot Procedure for the Synthesis of Stable Dioxadiazastannepines and DioxadiazasilepanesSn

SINGH, M. S.; SINGH, A. K.

SFR

NAr

Ar N

OHOH

OM

O

N

N

Ar

Ar

R

R'

(60-77%)

1) 2 NaH, THF

2) RR'MCl2

Ar = Ph, p-ClC6H4, p-MeC6H4, p-MeOC6H4

M=Sn and R=R'=Me, Bu, Ph M=Si and R=R'=Me, Ph or R=Me, R'=Cl

Si


SnCl4-Promoted Rearrangement of 2,3-Epoxy Alcohol DerivativesSn

KITA, Y.; MATSUDA, S.; INOGUCHI, R.; GANESH, J. K.; FUJIOKA, H.

SFR

OR'R3O

R4 R1

R2R2R1

OH O

R4R3

R2O

OR'

R1R4R3

(34-98%)

R' = SiR''3

SnCl4

R' = Me, Bn, H

SnCl4

β-hydroxyketone α-Alkoxy (or α-hydroxy)ketone

(39-100%)

R1,R2,R3,R4 = H, alkyl, cycloalkyl, aryl

Si


80


A Stannylene Strategy for Regioselective Fonctionnalisation of myo-InositolSn

WATANABE, Y.; KIYOSAWA, Y.; HYODO, S.; HAYASHI, M.

SFR

OHO

O

OHOH OH

OHO

O

OHOH OH

OHO

O

OHOHOH

OPO(OR)2

OO

OHOH OH

+

1) Bu2Sn=O2) (S)-O-acetylmandeloyl chloride

3) resolution

4) NH2NH2

L (40%) D (25%)

1) Bu2Sn=O2) [(RO)2P(O)]2O

(for DL)(for DL or L)(86-94%)


Diastereoselective Access to TetrahydrooxazinonesSn

R = Ph, p-MeO-Ph, p-CF3-Ph, Bn, t-Bu. Exo-b > 90%.Yields (exo-b) 18-70%

GIZECKI, P.; YOUCEF, R. A.; POULARD, C.; DHAL, R.; DUJARDIN, G.

TJ

N

t-Bu-O O

OMeH

R

OO

O

N

O OO

HR

O

O

+SnCl4 (1.1 equiv)

CH2Cl2-40 or -78 °C

R = Ph, p-MeO-Ph, p-CF3-Ph, Bn, t-Bu exo-β > 90% yield (exo-β) 18-70%


Three Component Coupling ReactionBi

Mannich-type reaction catalysed by bismuth triflate.

OLLEVIER, T.; NADEAU, E.

DCE

CHO OSiMe3

Ph

NH O

Ph

Ph

Ph

Bi(OTf)3

+ PhNH2 +MeCN, 25 °C

.4H2O (1 mol%)

82%

Si

J. Org. Chem. 9292 92952004 69 -, , 26 ,

Fries Rearrangement of Aryl AcetatesBi

The reaction appears to be more general for naphtyl acetates as compared to phenyl acetates.

OLLEVIER, T.; DESYROY, V.; ASIM, M.; BROCHU, M. -C.

OS

R R'

O

O

R R'

OH O

Bi(OTf)3 10 mol%

Solvent, 110 °CR = H, OMe

R' = H, OMe, O2CMe(64-82%)

Synlett 2794 27962004 -, , 15 ,

81


Bismuth Triflate Catalyzed Synthesis of Substituted 3,4-Dihydro-2H-1-benzopyransBi

An extension to synthesis of pyrano[2,3,b]benzopyran has also been achieved.

NGUYEN, M. P. ; ARNOLD, J. N. ; PETERSON, K. E. ; MOHAN, R. S.

MVI

R

OH

CHO

MeO OMe

Me MeR

O

OMe

MeOMe

R

O

OMe

OMeMe

+Bi(OTf)3.xH2O

CH3CN, 0°C+

7 examples56-72% Major

ds = 9:1


Synthesis of Peracylated αααα-Aldopyranosyl Chlorides Catalyzed by BiCl3Bi

BiCl3 is generated in situ from BiOCl and SOCl2

GHOSH, R. ; CHAKRABORTY, A. ; MAITI, S.

MVI

OR'

ROOR''

OR''

OR'' OR'

RO

OR''

OR''

Cl2 equiv SOCl2, 10-20% BiOCl

CH2Cl2 or neat, r.t.

α only9 examples, 82-97%


Application of Cyclopropanation of Esters with Dialkoxytitanacyclopropane ReagentsRv

Review (77 references)

KULINKOVICH, O.

OC

R CO2R'

Ti(OiPr)2 OHR

R

ER

O

R Hal

Reagent Natural products

TiMg

Eur. J. Org. Chem. 4517 45292004 -, , 22 ,

Asymmetric Fluorous Catalysis.Rv

The review focuses on the particular case of nitrogen-containing chiral auxiliaries.

FACHE, F.

CB

Review (48 References)

New J. Chem. 1277 12832004 28 -, , 11 ,

82


Enantioselective Protonations: Fundamental Insights and New ConceptsRv

DUHAMEL, L.; DUHAMEL, P.; PLAQUEVENT, J.-C.

PJL

Review51 references


83

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