Université de Montréal October 30 th 2007

Metal-Mediated Ring FormationThe contribution of Paul A. Wender

Guillaume Barbe

Charette’s Laboratories

Université de MontréalOctober 30th 2007

Paul Anthony Wender

Born: 1947, native of Wyoming Valley

Education

1969 B. S. Wilkes CollegeMentor: Dr. William Stine

1973 Ph.D. Yale UniversityAdvisor: Professor Frederick E. Ziegler

Career

1974 - 1981: Harvard University 1981 – now: Stanford University

Wender’s Ph.D. WorkThe Base-Induced Decomposition of Methyl Dialkylcyanodiazenecarboxylates.

The Transformation of Ketones into Nitriles, -carbomethoxynitriles, and -Methylnitriles

OMeO N

H

O

NH2N

NH

OMeO

HCN, MeOH

Br2, aq NaHCO3DCM

NC NH

HN

O

OMe

NC N

N

O

OMeNCOMe

O

NC Me

CN

NaOMeMeOH

LiOMeDME

MeO OMe

O

LiOMe, MeIDME

Ziegler, F. E.; Wender, P. A. J. Am. Chem. Soc. 1971, 93, 4318-4319.

Nickel(0)-Catalyzed Dimerization of 1,3-Butadiene

Ni(COD)2

NiNi NiII NiII

H

H

NiII

H

HNiIINi

Ni

NiIINi

Internal-allyls

External-allyl

Oxidative Addition

ReductiveElimination


-HydrideElimination

Graham, C. R.; Stephenson, L. M. J. Am. Chem. Soc. 1977, 99, 7098-7100.

Nickel-Mediated CycloadditionIntramolecular Version – Oxidative Addition

NiNi

Oxidative Addition

Ni Ni

NiII

H

H

NiIINiII H

H

( )n ( )n

( )n

( )n

Favored

NiII

Favoredn = 1

Favoredn = 2

Oxidative Addition

• Five-membered ring formation: cis-fused system favored• Six-membered ring formation: trans-fused system favored


Nickel-Mediated CycloadditionIntermolecular Version – Reductive Elimination


NiII NiIINiII



H


Nickel-Mediated CycloadditionIntramolecular Version – Reductive Elimination

NiII

H

H

NiIIH

H

( )n

( )n


H

H

( )n

NiII

H

H

( )n

H

H

( )n



NiII

H

H

( )n

H

H

( )n

H

H

( )n

H

H


H

H

H

H

H

H

Isomerisation

Favored

Favored

• 5-6 and 5-8 fused bicycles favored over 5-4 due to ring strain


Nickel-Mediated CycloadditionIntramolecular Version – -Hydride Elimination

NiII

H

H

NiIIH

H

( )n

( )n


H

H

( )n

NiII

HydrideElimination


Isomerisation

H

Favored

H

Favored

H

n = 1

Favoredn = 2

• Stereochemical outcome expected to be ring-size dependent


Nickel-Mediated CycloadditionIntramolecular Version

Ni(0)

H

H

H

H

Ni(0)

H

H

H

H

Wender, P. A.; Ihle, N. C. J. Am. Chem. Soc. 1986, 108, 4678-4679.

Nickel-Mediated Cycloaddition8-membered ring formation

EtO2C

EtO2C

Ni(COD)2 (11 mol%)PPh3 (33 mol%)

Toluene, 60 °C

EtO2C

EtO2C

EtO2C

EtO2C

EtO2C

EtO2C

EtO2C

EtO2C

H

H

H

H

2.6 %(37 %)

19 1:

70 %

O

POO

Me

MeMe

O

POO

Ph

PhPh

3:1 (P:Ni) 2:1 (P:Ni)

2.6 %(53 %)


Nickel-Mediated Cycloaddition8-membered ring formation


Toluene, 60 °C, 19 h

H

H

84 % (>95:5 trans:cis)

CO2Et EtO2C99:1



H

H

92 % (>95:5 trans:cis)

1.7:1

TBSO TBSO



H

H

82 % (>95:5 trans:cis)

2.2:1

AcO AcO

Me Me


Nickel-Mediated CycloadditionAsteriscanolide Total Synthesis

O H

H

H

H

MeMe

MeH

O

O

O

H

H

H

MeMe

O

Me

OH

MeMe

O

Me

Asteriscanolide

Wender, P. A.; Ihle, N. C.; Correia, C. R. D. J. Am. Chem. Soc. 1988, 110, 5904-5906

OH

MeMe

O

Me

Ni(COD)2PPh3

90 °C

O

H

H

H

MeMe

O

Me67 %

Synthesis: 13 steps, 2.7 overall yield

Nickel-Mediated CycloadditionApproach to Ophiobolin Natural Products

Ophiobolin F

Me

HOMe Me

H HMe

Me

HO

Me

TMSO

Wender, P. A.; Nuss, J. M.; Smith, D. B.; Suarez-Subrino, A.; Vagberg, J.; Decosta, D.; Bordner, J. J. Org. Chem. 1997, 62, 4908-4909.


60 °C

60 %

Me

HO

Me

TMSO

i)

ii) TBAF

Nickel-Mediated CycloadditionStudy on Type II Reaction

( )n

( )n

( )n

Type I

Type II

Type III

( )n

( )n

( )n

Wender, P. A.; Tebbe, M. J. Synthesis 1991, 110, 1089-1094.

O H

H

H

H

MeMe

MeH

O

O

Asteriscanolide

OMe

HO

OOH

O

Vulgarolide

Nickel-Mediated CycloadditionStudy on Type II Reaction

( )nType II

( )nMe

Me

Me

OTBSOTBS

Me

Me

OTBS

+

Ni(COD)2 (20 mol%)P(O-o-BiPh)3 (60 mol%)


74 %

7 : 1

Wender, P. A.; Tebbe, M. J. Synthesis 1991, 110, 1089-1094.

Nickel-Mediated CycloadditionSalsolene Oxide Total Synthesis

Wender, P. A.; Croatt, M. P.; Witulski, B. Tetrahedron 2006, 62, 7505-7511.

Salsolene Oxide

Me

O

Me Me

MeMe

Me Me


Toluene, 85 °C

67 %


Toluene, 85 °C

36 %


Toluene, 85 °C

0 %

1:1 E:Z

3:1 E:Z

1:0 E:Z

Me

Me

+

+

+

4:1

>10:1



Salsolene Oxide

Me

O

Me Me

Me350 nm h

Benzophenone

Benzene

80 %1:0 E:Z

Me

1:1.3 E:Z



Salsolene Oxide

Me

O

Me Me

MeMeNi(COD)2 (10 mol%)

P(O-o-BiPh)3 (30 mol%)

Toluene, 85 °C

35 %1.3:1 Z:E

Me

+



Toluene, 85 °C

80 %Z-isomer

Me

+



Toluene, 85 °C

0 %E-isomer

Me

+

7:3

7:3



Salsolene Oxide

Me

O

Me Me

Me350 nm h

Benzophenone

Benzene

80 %1:0 E:Z

Me

1:1.3 E:Z

Me350 nm h

BenzophenoneNi(COD)2 / P(O-o-BiPh)3 (1:3)

Benzene, 50-60 °C

34 %1:0 E:Z

Me Me

+

2.5:1

Nickel-Catalyzed Diels-Alder

Ni NiIIOxidative Addition

ReductiveEliminationNiII


Ni NiIIOxidative Addition

ReductiveEliminationNiII

Simple alkenes do not participate in oxidative addition

Alkynes reacts smoothly at room temperature

Nickel-Catalyzed Diels-AlderAlkynes

Wender, P. A.; Jenkins, T. E. J. Am. Chem. Soc. 1989, 111, 6432-6434.

TBSO

TBSO

TMS

CO2Me

OTMS

TBSO

TBSO

TMS

CO2Me

OTMS

TBSO

CO2Me

OTMS

>99 % (2:1)

25

Dienyne Products T °C Yield(d.r.)

Thermalt1/2 (h) / T °C

16.6 / 160

98 % (1.2:1)

25 11 / 140

88 % (2.2:1)

25 15 / 150

85 % (1.8:1)

55 76 / 200

98 % (>99:1)

25 22.5 / 80

OAc OAc

Dienyne Products


THF (0.01 M), 11h


Wender, P. A.; Smith, T. E. J. Org. Chem. 1995, 60, 2962-2963.

TMS

H

Ni(acac)2 (20 mol%)Et2AlOEt (40 mol%)

P(O-iC3HF6Ph)3 (60 mol%)

Cyclohexane (0.01 M)65 °C

TMS

TMS

H



Cyclohexane (0.01 M)50 °CTMS

50 %

53 %


Wender, P. A.; Smith, T. E. Tetrahedron 1998, 54, 1255-1275.

TMS

H


P(O-o-FPh)3 (60 mol%)


EtO2C

TMS

EtO2C

67 %

TMS

H




TMS

49 %57 %63 %

XX

X = HX = CO2EtX = Cl


Wender, P. A.; Jenkins, T. E. J. Am. Chem. Soc. 1989, 111, 6432-6434. Wender, P. A.; Smith, T. E. J. Org. Chem. 1995, 60, 2962-2963.

MeMe Me

TBSO TBSO TBSO

Me MeNi(COD)2 (10 mol%)


THF (0.01 M), 11h+

No Reaction

TMS

Me



Cyclohexane (0.01 M)80 °CTMS

54 %

R1

R1OR2

Me OR2

R1 = H, R2 = TBSR1 = OMe, R2 = TMS

R1 = H, R2 = TBSR1 = OMe, R2 = TMS

MeNi(COD)2 (20 mol%)P(O-iC3HF6Ph)3 (60 mol%)


90 %

MeOMeOOTMS

Me OTMS

MOMOMOMO



NTsTMS NTsTMS

25

Dienyne Products T °C YieldThermal

t1/2 (h) / T °C

4.8 / 100

25 17.6 / 100

25 26.3 / 100

25 12.9 / 150

60 2.6 / 150

TMS NTsTMS

NTs

NBocTMS NBocTMS

91 %

86 %

87 %

82 %

81 %

TMSNTs TMS NTs

TMSN TMS N

O O

10 % Ni(COD)2P(O-o-BiPh)3 (3:1)

THF

10 % Ni(COD)2P(O-o-BiPh)3 (3:1)

THF

20 % Ni(COD)2P(O-iC3HF6)3 (3:1)

Cyclohexane

20 % Ni(COD)2P(O-iC3HF6)3 (3:1)

Cyclohexane

20 % Ni(COD)2P(O-iC3HF6)3 (3:1)

Cyclohexane



20 % Ni(COD)2P(O-iC3HF6)3 (3:1)

THF, 0.01M, rt

NH

NH2

TMSBr

+

N

TMS

O

NBoc

N

TMS

O

NBoc

88 %

N

MeO2C O

H H

H

OMe

NH

MeO

O

OMe

OMe

OMeReserpine

Nickel-Catalyzed Diels-AlderAllenes

Wender, P. A.; Jenkins, T. E.; Suzuki, S. J. Am. Chem. Soc. 1995, 117, 1843-1844.

OTBS

Me

OTBSH10 % Ni(COD)2P(O-o-BiPh)3 (3:1)

THF, rt

97 % 2:1

Rhodium-Catalyzed Diels-AlderAllenes

OTBS

OTBS5 % [Rh(COD)Cl]248 % P(O-o-BiPh)3

THF, 45 °C

90 %

H

Me 1 diast.


Substrats Products Yield

O

98 %

94 %

77 %

87 %

87 %

Me

Me

Me

O

O

O

O

Me

CO2Me

CO2Me

Me

CO2Me

CO2Me

89 %Me

CO2Me

CO2Me

Me

Me

5 % [Rh(COD)Cl]240 % P(O-o-BiPh)3

THF, 45 °C

5 % [Rh(COD)Cl]220 % P(O-o-BiPh)3

THF, 45 °C

5 % Rh(H2C=CH2)2Cl10 % P(OCH(CF3)2)3

PhMe, 60 °C

5 % Rh(H2C=CH2)2ClP(OCH(CF3)(o-MeOPh))3

10 %PhMe, 60 °C


10 %PhMe, 80 °C

5 % Rh(H2C=CH2)2Cl10 % P(OCH(CF3)2)3

PhMe, 80 °C

d.r.

1 diast.

1 diast.

---

91:9

1 diast.

1 diast.

O

O

O

O

O

CO2Me

CO2Me

CO2Me

CO2Me

Me

Me

H

Me

Me

H

CO2Me

CO2Me

CO2MeCO2Me

Me

Me

Me

H

H

Me

CO2Me

CO2Me



87 %

Me

CO2Me

CO2Me


10 %PhMe, 60 °C

91 : 9

CO2Me

CO2MeMe

H

Me

CO2Me

CO2Me

5 % Rh(H2C=CH2)2Cl5 % AgO2CCF3

15 % P(OCH(CF3)-(2,6-Me2Ph))3

PhMe, 60 °C

CO2Me

CO2MeMe

H

CO2Me

CO2MeMe

H

CO2Me

CO2MeMe

H

+

+

5 : 9569 %


Rhodium-Catalyzed Homo-Diels-Alder

RhI RhIII

Oxidative Addition

ReductiveEliminationRhIII

Diene-Alkyne

RhI RhIII

Oxidative Addition


Vinylcyclopropane-Alkyne

Khusnutdinov, R. I.; Dzhemilev, U. M. J. Organomet. Chem. 1994, 471, 1-18.

Rhodium-Catalyzed Homo-Diels-AlderAlkynes

Substrats Products Time

1.5 h

Yield

83 %

88 %

MeO2C

MeO2C

MeMeO2C

MeO2C

20 min.

84 %2 d

Method

A

B

O

R

O

R = Me3.5 h 83 %

1.25 h 74 %1.5 h 80 %1.5 h 50 %

BBBBC

R = TMSR = CO2MeR = PhR = H

MeO2C

MeO2C

RMeO2C

MeO2C

R = MeR = MeR = HR = CO2MeR = TMS

2 d (3.5:1) 89 %2.5 h (1:2) 92 %2 d (1:0) 82 %16 h (1:0) 81 %7 d (0:1) 71 %

BDBBB

MeO2C

MeO2C

MeMeO2C

MeO2CMe

Me

R

R

Me

Me Me

30 min 82 %D

0.5 % RhCl(PPh3)30.5 % AgOTfPhMe, 110 °C

A

10 % RhCl(PPh3)3PhMe, 110 °C

B

10 % RhCl(PPh3)3THF, 100 °C

C

10 % RhCl(PPh3)310 % AgOTf

PhMe, 110 °C

D

Wender, P. A.; Takahashi, H.; Witulski, B. J. Am. Chem. Soc. 1995, 117, 4720-4721.


MeO2C

MeO2C

TMSMeO2C

MeO2C

TMS

Me Me

MeO2C

MeO2C

TMS

Me

10 % RhCl(PPh3)3

5 % [Rh(CO)2Cl]2PhMe, 110 °C, 7 d

CDCl3, 30 °C, 2 d

0 %

81 %

71 %

0 %

MeO2C

MeO2C

TMSMeO2C

MeO2C

TMS

Me Me

MeO2C

MeO2C

TMS

Me

10 % RhCl(PPh3)3

5 % [Rh(CO)2Cl]2PhMe, 110 °C, 2 d

PhMe, 2 M. 110 °C, 2 h

69 %

84 %

20 %

0 %

Wender, P. A.; Sperandio, D. J. Org. Chem. 1998, 63, 4164-4165.


O

Ph

O

Ph

10 % RhCl(PPh3)3/AgOTf

Me

O

Ph

Me

5 % [Rh(CO)2Cl]2

PhMe, 110 °C

PhMe, 110 °C, 20 min

0 %

80 %

0 %

0 %

O

Me

O

Me

10 % RhCl(PPh3)3/AgOTf

Me

O

Me

Me

5 % [Rh(CO)2Cl]2

THF, 100 °C, 17 h


65 %

78 %

13 %

0 %



O

Ph

O

Ph

10 % RhCl(PPh3)3

5 % [Rh(CO)2Cl]2

PhMe, 110 °C, 1.5 h

CDCl3, 30 °C, 14 h

80 %

80 %

5 % [Rh(CO)2Cl]2 CDCl3, 65 °C, 15 min 78 %

O

TMS

O

TMS

10 % RhCl(PPh3)3

5 % [Rh(CO)2Cl]2

PhMe, 110 °C, 3.5 h

CDCl3, 30 °C, 14 h

83 %

80 %

O O

10 % RhCl(PPh3)3

5 % [Rh(CO)2Cl]2

PhMe, 110 °C, 2 d

PhMe, 30 °C

50 % (volatile)

0 %




MeO2C

MeO2C

MeMeO2C

MeO2C

Me

0.5 % RhCl(PPh3)3/AgOTf

5 % [Rh(CO)2Cl]2

PhMe, 1 M, 110 °C, 20 min


83 %

82 %

MeO2C

MeO2C

0.1 % RhCl(PPh3)3/AgOTf

5 % [Rh(CO)2Cl]2

PhMe, 110 °C, 15 h

PhMe, 110 °C, 48 h

90 %

0 %

5 % [Rh(CO)2Cl]2 CDCl3, 30 °C, 16 h 79 %

1 % [Rh(CO)2Cl]2 PhMe, 2 M, 110 °C, 3 h 89 %

10 % RhCl(PPh3)3 CF3CF2OH, 65 °C, 19 h 90-95 %

10 % RhCl(PPh3)3 PhMe, 110 °C, 2 d 84 %

MeO2C

MeO2C

Rhodium-Catalyzed Homo-Diels-AlderAllenes

Substrats Products Time Yield

92 %MeO2C

MeO2C

MeO2C

MeO2C

1 h90 %0.75 h

Method

BD

0.2 % RhCl(PPh3)3PhMe, 1 M, 100 °C

A

5 % [RhCl(CO)2]2PhMe/DCE, 0.003-0.01 M

90 °C

C

10 % [RhCl(CO)2]2PhMe, 0.01 M, 110 °C

D


PhMe, 0.01 M, 100 °C

BR

R

RR

R = MeR = Me

90 %MeO2C

MeO2C

MeO2C

MeO2C20 min.A

t-Bu

t-Bu

68 %10 h83 %3.5 h

BC

R = HR = H

5 % [RhCl(CO)2]2PhMe, 0.01 M, 100 °C

E

88 %MeO2C MeO2C

1 hB

R1

R2

R1R2

R1=H, R2=t-Bu

93 %2 h91 %1 h

EE

R1=R2= MeR1=H, R2=t-Bu

TsN TsN85 %0.5 h90 %0.75 h

BE

70 %MeO2C

MeO2C

MeO2C

MeO2C16 hB

t-Bu

t-Bu

Wender, P. A.; Glorius, F.; Husfeld, C. O.; Langkopf, E.; Love, J. A. J. Am. Chem. Soc. 1999, 121, 5348-5349.

Rhodium-Catalyzed Homo-Diels-AlderAlkenes

0.1 % RhCl(PPh3)30.1 % AgOTfMeO2C

MeO2C

MeO2C

MeO2CH

H

PhMe, 110 °C, 15 h90 %


O O

H

H

THF, 65 °C, 10 h70 %

10 % RhCl(PPh3)310 % AgOTfMeO2C

MeO2C

MeO2C

MeO2CMe

H

PhMe, 110 °C, 1 h92 %


MeO2C

MeO2C

MeO2CH

Me

PhMe, 110 °C, 1 h94 %


MeO2C

MeO2C

MeO2C

H

PhMe, 110 °C, 15 h78 %

Me


MeO2C PhMe, 100 °C, 5 d77 % H

H

MeO2C

MeO2C

Wender, P. A.; Husfeld, C. O.; Langkopf, E.; Love, J. A. J. Am. Chem. Soc. 1998, 120, 1940-1941.

Limitation

MeO2C

MeO2C

MeO2C

MeO2CMe

Me

R2

R1

(-hydride elimination pathways)

Rhodium-Catalyzed Homo-Diels-AlderAllenes

Wender, P. A.; Glorius, F.; Husfeld, C. O.; Langkopf, E.; Love, J. A. J. Am. Chem. Soc. 1999, 121, 5348-5349.

1 % RhCl(PPh3)3

PhMe, 100 °C

MeO2C

MeO2C

MeO2C

MeO2C

t-Bu

t-BuH

91 % ee 92 % ee

Rhodium-Catalyzed Homo-Diels-AlderApproach to (+)-Allocyathin B2

(+)-Allocyathin B2

HO

MeMe

Me

MeOH

MeMe

Me

HO H

O

Me

MeMe

Me

HO

O

Me

Wender, P. A.; Bi, F. C.; Brodney, M. A.; Gosselin, F. Org. Lett. 2001, 3, 2105-2108.

5 % [RhCl(CO)2]2DCE, 0.02 M80 °C, 3.5 h

90 %

MeMe

Me

HO H

O

Me

MeMe

Me

HO

O

Me

Rhodium-Catalyzed Homo-Diels-AlderAsymmetric Total Synthesis of Dictamnol

Dictamnol

H

HHOMe

H

HHO HO

Wender, P. A.; Fuji, M.; Husfeld, C. O.; Love, J. A. Org. Lett. 1999, 1, 137-139.

2.5 % [RhCl(CO)2]2DCE, 0.025 M

80 °C, 7 h

76 %

H

HHOHO

Rhodium-Catalyzed Homo-Diels-AlderAlkynes – Substituted Cyclopropanes

Substrats Products Time YieldMethod

O

R

O 1 h 80 %2 h 77 %

6 h 83 %BB

AR = CO2MeR = Ph

R = H

MeO2C

MeO2C

RMeO2C

MeO2C

R

R0.5 % RhCl(PPh3)3

0.5 % AgOTfTHF, 65 °C

A

BMe Me

EtO2C

EtO2C

MeO2C

MeO2C10 h 90 %C

H

H MeMe

O

Me

O 1 h 90 %D

Me

OBn OBn

OEt O

30 h 73 %40 h 81 %

FE

R = MeR = H

0.5 % RhCl(PPh3)30.5 % AgOTfPhMe, 110 °C

C


PhMe, 110 °C

D


PhMe, 110 °C

E

5 % [Rh(CO)2Cl]2CDCl3, 30 °C

F

0.5 % [Rh(CO)2Cl]2DCM, rt

Wender, P. A.; Dyckman, A. J.; Husfeld, C. O.; Kadereit, D.; Love, J. A.; Rieck, H. J. Am. Chem. Soc. 1999, 121, 10442-10443.

Rhodium-Catalyzed Homo-Diels-AlderAsymmetric Total Synthesis of (+)-Aphanamol I

(+)-Aphanamol I

OMe

H OBn

Me

H OBn

Me

OBn

Me

Me

Wender, P. A.; Zhang, L. Org. Lett. 2000, 2, 2323-2326.

0.5 % [RhCl(CO)2]2Toluene, 0.1 M110 °C, 30 min

93 %

Me

H OBn

Me

OBn

Me

Me



MeO2C

MeO2C

Me

MeO2C

MeO2C

Me

Me

H

H

H

H

OR

H

R = TBSR = H

95 %96 %


PhMe, 110 °C, 1-1.5 h

MeO2C

MeO2C

Me

MeO2C

MeO2C

Me

Me

H

H

HH

H

81 %


PhMe, 110 °C, 2 hOTBS

OR

OTBS



O

R

O

R

Me

H

H

H

H

Me Me

H

R = MeR = H

80 %75 %


PhMe, 65 °C, 8.5 h

O

Me

O

Me

Me

H

H

H

H

SiMe2Ph SiMe2Ph

H

91 %


PhMe, 110 °C, 0.5 h

O

Me

O

Me

Me

H

H

H

OMeOMe

H

88 %

10 % [Rh(CO)2Cl]2

DCE, 80 °C, 0.5 h


Wender, P. A.; Dyckman, A. J. Org. Lett. 1999, 1, 2089-2092.

MeO2C

MeO2C

Me

MeO2C

MeO2C

Me

Me

H

H

H

H

R R

H

10 % Rh(I)

PhMe, 110 °C0.01 M

Entry CatalystR Time Yield A : B

1CH2OH

1.5 h 96 % 1 : 02 0.5 h 86 % 2.3 : 1

3 CH2OAc 2 h 92 % 1 : 04 1.5 h 85 % 2.5 : 1

5 CH2OTBS 1 h 95 % 1 : 06 1 h 86 % 3.5 : 1

7CHO

16 h decomp. ---8 0.5 h 68 % 0 : 19 8 h 98 % 0 : 1

10 CO2H 2 h 69 % 4 :111 2 h 73 % 1 : 22

12CO2Me

1 h 81 % 20 :113 1 h 93 % 1 : 11

Rh(PPh3)3OTf

Rh(PPh3)3OTf

Rh(PPh3)3OTf

Rh(PPh3)3OTf

Rh(PPh3)3OTf

Rh(PPh3)3OTf

[Rh(CO)2Cl]2

[Rh(CO)2Cl]2

[Rh(CO)2Cl]2

[Rh(CO)2Cl]2

[Rh(CO)2Cl]2 (55 °C)

[Rh(CO)2Cl]2

[Rh(CO)2Cl]2

MeO2C

MeO2C

Me

MeH

A B

R


Wender, P. A.; Dyckman, A. J. Org. Lett. 1999, 1, 2089-2092.

MeO2C

MeO2C

Me

MeO2C

MeO2C

Me

Me

H

H

H

R

H R

H

10 % Rh(I)

PhMe, 110 °C0.01 M

Entry CatalystR Time Yield A : B

1CH2OH

1 h 84 % 3.5 : 12 1 h 93 % 9 : 1

3 CH2OTBS 2 h 81 % 1 : 04 1 h 96 % 1 : 0

5 CHO 4 h decomp. ---6 15 h 92 % 0 : 1

7CO2Me

2 h 95 % 6.4 :18 2 h 98 % 1.5 : 1

Rh(PPh3)3OTf

Rh(PPh3)3OTf

Rh(PPh3)3OTf

Rh(PPh3)3OTf

[Rh(CO)2Cl]2

[Rh(CO)2Cl]2

[Rh(CO)2Cl]2 (55 °C)

[Rh(CO)2Cl]2

MeO2C

MeO2C

Me

MeH

A B

R

Rhodium-Catalyzed Homo-Diels-AlderAlkynes – Intermolecular Version

Wender, P. A.; Rieck, H., Fuji, M. J. Am. Chem. Soc. 1998, 120, 10976-10977.

5 % [Rh(CO)2Cl]2DCM, 0.1 M

Entry R2

1 H

2 Me

3 H

4 H

5 H

6 H

7 H

8 H

TBSO

R2

R1

+ OR1

R2

i)

HCl / EtOHii)

9 H

10 H

11 Et

12 H

R1

CO2Me

CO2Me

(CO)Me

CH2OMe

CH2OH

TMS

Ph

Cyhexene

Cypropane

iPr

Et

H

Temp Yield

40 93 %

40 92 %

40 88 %

40 88 %

40 74 %

40 77 %

30 81 %

40 75 %

40 88 %

40 84 %

40 65 %

40 79 %

Time

2 h

1.5 h

2.5 h

1.5 h

1.5 h

2 h

3 h

3 h

2 h

2.5 h

7 h

6 h

1 equiv 1.1-1.5 equiv


Wender, P. A.; Dyckman, A. J., Husfeld, C. O.; Scanio, M. J. C. Org. Lett. 2000, 2, 1609-1611.

EtO

TMSOCl OEt

ONa, TMSCl

Et2O, reflux69 %

EtO

HOMeOH, rt

84 %

HO

Et2O, 0 °C - rt

64 %

MgBr

2,6-lutidineDCM, rt

87 %

TBSClTBSO

2-methoxyethanol-78 °C - rt

NBS

rt - 90 °C

KOH

O

Br

O

45 - 57 % (2 steps)O

O

Zn(Cu), AcClEt2O

1.3 equiv CH2I2

53 %

O

O


0.5 % [Rh(CO)2Cl]2DCE, 0.5 M, 80 °C

Entry R2

1 H

2 CO2Et

3 Me

4 H

5 H

6 H

7 H

8 H

R2

R1

+ OR1

R2

i)

HCl / MeOHii)

9 H

10 H

11 Et

R1

CO2Me

CO2Et

CO2Me

H

CH2OMe

CH(OH)Me

CH2NHTs

CH2OH

(CH2)3CO2H

Cycyclohexene

CH2-Phtalimide

Yield

84 %

96 %

81 %

75 %

92 %

89 %

87 %

82 %

87 %

85 %

97 %

Time

10 min

1 h

2 h

2 h

15 min

12 min

15 min

25 min

1.5 h

7 h

11 min

1 equiv 1.2-1.3 equiv

O

O


Rhodium-Catalyzed Homo-Diels-AlderAlkynes – Intermolecular Version – Scale Up

0.5 % [Rh(CO)2Cl]2DCE, 0.5 M, 80 °C

Entry

1

2

3

+ O

i)

HCl / MeOHii)

Scale

1 mmol

10 mmol

100 mmol

Yield

92 %

88 %

94 %

Time

15 min

25 min

30 min

O

O

(14.2 g)

OMeOMe


Rhodium-Catalyzed Homo-Diels-AlderNon-Activated Alkynes – Intermolecular Version

5 % [Rh(CO)2Cl]2

Entry DCE

1 2 h, 93 %

2 4 h, 92 %

3 22 h, 49 %

4 6 h, 73 %

5 48 h, 79 %

6 72 h, 77 %

R+

R

R

CO2Me

Ph

CH2OMe

CH2OH

C3H7

TMS

5 % TFE / DCE

1 h, 95 %

2 h, 81 %

5 h, 90 %

5 h, 90 %

23 h, 81 %

23 h, 90 %

OTBS

Solvent, 80 °C

TBSO

Wender, P. A.; Barzilay, C. M.; Dyckman, A. J. J. Am. Chem. Soc. 2001, 123, 179-180.

Rhodium-Catalyzed Homo-Diels-AlderNon-Activated Alkynes – Intermolecular Version

5 % [Rh(CO)2Cl]2

Entry DCE

1 2 h, 82 %

2 1.5 h, 76 %

3 8 h, 81 %

4 30 h, 23 %

5 72 h, 38 %

6 72 h, 64 %

CO2Me+

CO2Me

R1

iPr

iPr

Me

H

H

H

5 % TFE / DCE

---

---

---

2 h, dec.

6 h, dec.

45 min, 69 %

R3

R1 Solvent, 80 °C

R2

R1

R3

CH2OH

H

CH2OTBS

CH2OH

CH2OH

CH2OTBS

7 3 h, 53 %

8 2 h, 82 %

9 20 h, 75 %

10 15 h, 63 % (2:1 dr)

11 >24 h, no Rx

TMS

CH2OTBS

CH2OTBS

CH(OTBS)Me

CH(OH)Me

---

---

3 h, 76 %

---

21 h, 62 % (1:1 dr)

CH2OTBS

CH2OH

CH2OMe

CH2OMe

CH2OMe

R2

H

H

H

H

Me

Me

H

H

H

H

H

R2 R2

Wender, P. A.; Barzilay, C. M.; Dyckman, A. J. J. Am. Chem. Soc. 2001, 123, 179-180.


5 % [Rh(CO)2Cl]2+

CyN

CO2Me

N-CyCO2Me

CO2Me

CO2Me

DCE, 0.1 M, 60 °C1.5 h

CyN CO2Me

CO2Me

CO2Me

MeO2C+

MNCy

M

MNCy

MNCy

MeO2C

MeO2C

CO2Me

CO2MeMeO2C

MeO2C

MeO2C

MeO2C

MeO2C CO2Me

[M]A

B D

C21

2 1

3 4

1 2 3 4

39 %22 %

Wender, P. A.; Pedersen, T. M., Scanio, M. J. C. J. Am. Chem. Soc. 2002, 124, 15154-15155.


Entry

1

R1 R2

H

5 % [Rh(CO)2Cl]2+

NR1

CO2Me

N-R1 CO2Me

CO2Me

CO2Me

PhMe, 0.1 M, 60 °C12.5 h

(CH2)5-CH32 H

3 H

4 H

5 H

R2R2

Yield

83 %

91 %

83 %

79 %

61 %

6 85 %

7 88 %Ph(CH2)3-CH3

(CH2)3-CH3



Entry

1

R1 R2

H

1) H2N-R1, Dean-Stark2) 5 % [Rh(CO)2Cl]2

+

NR1

CO2Me

OCO2Me

CO2Me

CO2Me

PhMe, 0.1 M, 60 °C12.5 h

Bn

Bn

2 H

3 H

4 H

5 iPr

R2

Temp.

60 °C

60 °C

60 °C

60 °C

100 °C

6(3.4 % cat.)

60 °CBn

Yield

91 %

84 %

95 %

82 %

74 %

89 %

R2

R3

R3

H

H

H

Me

H(CH2)5-CH3

H H

R3

(4.07 g)



Entry

1

R1 R2

H

A : B

1 : 1.8

R3

Me

1 % [Rh(CO)2Cl]2DCE, 0.2 M, 80 °C

+

Oi)

ii)O

O

H+

R3 R3

R2

R1

R2

R3

R3 O

R3

R3+

Yield

95 %

A B

TMS

2 H 1 : 1.6Me 83 %Ph

3 CH2CO2Et 1 : 2Me 92 %Ph

4 C4H9 2 : 3Me 80 %Ph

5 C4H9 2 : 5Me 80 %TMS

6 C4H9 1 : 1.2Me 65 %

7 H 1 : 1.3Me 45 %CH2OMe

8 C4H9 1 : 2.2Me 22 %CH2NBn2

9 CH2CO2Et ---Me no Rx

10 C4H9 ---Me no Rx

11 H ---H no RxPh

CH2CH2OH

H

H

R1

R1

R2

Wegner, H. A.; de Meijer, A.; Wender, P. A. J. Am. Chem. Soc. 2005, 127, 6530-6531.


Entry

1

R1 R2

H

A : B

2 : 1

R3

Me

1 % [Rh(CO)2Cl]2DCE, 0.2 M, 80 °C

+ O

i)

ii)O

O

H+

R3 R3

R1 R2

R2

R1

R3

R3

OR1

R2

R3

R3

+

Yield

69 %

A B

2 Me ---Me no RxCO2Et

3 H 2 : 3Me 99 %

4 H ---H no Rx

5 H 5 : 299 %

6 H 1 : 2H/Me 52 %CN

Ph

Time

1 h

36 h

1 h

36 h

1 h

1 h

CN

CN

CN



1 % [Rh(CO)2Cl]2DCE, 0.2 M, 80 °C

+ O

i)

ii)O

O

HCl / EtOH

H Me

H (CH2)nCN (CH2)nCN

O(CH2)nCN

+

A B

Me

n = 1n = 3

56 %58 %

71

21


Rhodium-Catalyzed CyclisationDiene + Alkene + Alkyne

RhI RhIII

Oxidative Addition


Alkyne insertion

RhIII


Rhodium-Catalyzed [4+2+2]

5 % [Rh(CO)2Cl]210 % AgSbF6

Entry Time

1 3 h

2 3.5 h

3 2 h

4 1.5 h

5 0.5 h

6 5 h

R

R

CH2OMe

CH2OTBS

CO2Me

(CO)Me

H

Yield

85 %

76 %

88 %

72 %

81 %

75 %

DCE, 0.1 M, 40 °C

H

HiPr

MeO2C

MeO2C

H

HiPr

MeO2C

MeO2C+

R

R

1.2 equiviPr

MeO2C

MeO2C+

A : B

4.2 : 1

2.4 : 1

11.7 : 1

6.4 : 1

1 : 1.9

---

A B

Wender, P. A.; Christy, J. P. J. Am. Chem. Soc. 2006, 128, 5354-5355.


5 % [Rh(CO)2Cl]210 % AgSbF6

Entry Time

1 3 h

2 3 h

3 24 h

4 4 h

5 2 h

6 27 h

R1

H

H

H

H

Me

Yield

85 %

76 %

70 %

79 %

74 %

68 %

DCE, 0.1 M, 40-60 °C

R1

HR2

X

R1

HR2

X+

R2

X +

A : B

4.2 : 1

3.4 : 1

2.8 : 1

4.0 : 1

5.1 : 1

1.5 : 1

A B

OMe

OMe OMe

R1

R3

R2

iPr

Me

iPr

iPr

iPr

R3

H

H

H

H

H

7 20 hH 37 % 1 : 0H Me

H H H

X

C(CO2Me)2

C(CO2Me)2

O

NTs

C(CO2Me)2

C(CO2Me)2

C(CO2Me)2

R3 R3

1.2-2.0 equiv

Wender, P. A.; Christy, J. P. J. Am. Chem. Soc. 2006, 128, 5354-5355.

Rhodium-Catalyzed CyclisationDiene + Alkene + CO

RhI RhIII

Oxidative Addition


Rhodium-Catalyzed CyclisationDiene + Alkene + CO

RhI RhIII

Oxidative Addition


RhIII

RhIII

CO insertionO


CO insertion

RhIII

O ReductiveElimination O

O

Rhodium-Catalyzed Pauson-KhandDiene + alkene : Intramolecular Version

Wender, P. A.; Croatt, M. P., Deschamps, N. M. J. Am. Chem. Soc. 2004, 126, 5948-5949.

5 % [Rh(CO)2Cl]2CO (1 atm)

Entry Time

1 3.8 h

2 3 h

3 22 h

4 23 h

5 3.5 h

6 3 h

R1

H

H

Me

H

H

Yield (A)

84 %

94 %

0 %

92 %

93 %

84 %

DCE, 0.1 M, 80 °C

R3

X

Yield (B)

---

5 %

71 %

---

---

---

A B

R1

R2

H

H

H

H

H

R3

iPr

Me

iPr

Me

iPr

7a 48 hH 28 % ---Me H

H H H

X

C(CO2Me)2

C(CO2Me)2

C(CO2Me)2

NTs

O

C(CO2Me)2

C(CO2Me)2

R2

X

R1

HR2

R3

O X

R1

HR3

O+

a) 5 % [Rh(CO)2Cl]2, 10 % AgSbF6, 60 °C

48 h

H

HiPr

OMeO2C

MeO2C

MeO2C

MeO2C iPr

89 %

Rhodium-Catalyzed Pauson-KhandDiene + allene : Intramolecular Version

Wender, P. A.; Croatt, M. P., Deschamps, N. M. Angew. Chem. Int. Ed. 2006, 45, 2459-2462.

[Rh(CO)2Cl]2CO

Entry t (h)

1 8

2 1.5

3 0.3

4 1.5

5 16

6 24

R1

Me

Me

Me

H, Me

H, Me

97 %

97 %

92 %

81 %

39 % (4.6:1)

81 % (1.2:1)

Solvent, rt

R2

X

A : B

---

2.9:1

71 %

---

---

---

R2

Me

H

iPr

iPr

iPr

7 24H, tBu 94 % (1:0 7.5:1H

Me iPr

X

NTs

O

C(CO2Me)2

NTs

NTs

O

C(CO2Me)2

X

H

HR2

O

R1

R1

R1

R1

X

H

HR2

O

R1

R1

+

0.1

2.5

5

2.5

1

2.5

1

8 1.5H 62 % 2.3:1 (DA)

iPrNTs 5

cat.(mol %)

1

1

1

1

1

1

1

4

CO (atm) Solvent[M]

TFE (0.5)

TFE (0.1)

DCE (0.1)

TFE (0.5)

DCE (0.05)

TFE (0.1)

TFE (0.1)

DCE (0.01)

Yield (A)(E:Z)

A B

Rhodium-Catalyzed CyclisationDiene + Alkyne + CO

RhI RhIII

Oxidative Addition


RhIII

RhIII

CO insertionO


CO insertion

RhIII

O ReductiveElimination O

O

Rhodium-Catalyzed Pauson-KhandDiene + alkyne : Intramolecular Version

Wender, P. A.; Deschamps, N. M.; Gamber, G. G. Angew. Chem. Int. Ed. 2003, 42, 1853-1857.

5 % RhCl(CO)(PPh3)25 % AgSbF6CO (1 atm)

THF, 0.1 M23 h, 40 °C

iPr HiPr

O

+

MeMeO2C

MeO2C

Me

H

Me

iPr

H

Me

iPr

MeO2C

MeO2C

MeO2C

MeO2C

MeO2C

MeO2C

+

45 %

25 %

18 %

O


Entry T (°C)

1 rt

2 rt

3 rt

4 rt

5 rt

6 rt

R1

Me

TMS

Me

H

H

CO (atm)

1

2

1

1

1

1

R2

H

H

-(CH2)3-

-(CH2)3-

H

R3

iPr

iPr

Me

7 40Me 1H Me

H H iPr

RhCl(CO)(PPh3)2AgSbF6

CO (1 atm)

DCE, 0.1 M

R3 HR3

O

R1MeO2C

MeO2C

R1

MeO2C

MeO2C

1

2

1

1

5

1

2.5

t (h)

14

12

40

24

32

30

Yield

89 %

85 %

43 %

96 %

45 %

46 %

12 86 %

8 40Me 2H H

9 40Me 1Me H

2.5

2.5

12 90 %

10 96 %

R2R2

cat. (Rh+Ag) (mol %)




DCE, 0.1 M3 days, 80 °C H

O

MeMeO2C

MeO2C

Me

MeO2C

MeO2C


DCE, 0.1 M4 days, 80 °C

PhH Ph

O

MeMeO2C

MeO2C

Me

MeO2C

MeO2C

71 %

33 %


Rhodium-Catalyzed CyclisationAlkynes – Intermolecular Version – CO insertion

2.5 % [Rh(CO)2Cl]2 / CODioxane, 0.5 M, 60 °C

Entry R2

1 Et

2 TMS

3 Ph

4 Ph

5 Ph

6 Ph

7 TMS

8 Me

R2

R1

+

i)

ii)

9 CO2Me

R1

C(O)Me

C(O)Me

C(O)Me

C(O)NH2

CHO

CO2Et

CO2Et

CO2Et

CO2Me

Yield

97 %

54 %

88 %

96 %

69 %

79 %

67 %

85 % (6:1 regio)

48 %

Time [h]

20

42

26

40

26

24

26

20

30

O

O

H3O+

H

OH

O

R2

R1

CO [atm]

2

1

1

1

2

1

1

1

1

Wender, P. A.; Gamber, G. G., Hubbard, R. D.; Zhang, L. J. Am. Chem. Soc. 2002, 124, 2876-2877.

Rhodium-Catalyzed CyclisationVCP + Alkyne + CO

RhIII

CO insertion

O

CO insertion


RhI RhIII

Oxidative Addition RhIII

RhIII

O

O

OMe

OMeO

O

OMe

OMeO

OMeO

O

OMeO

H+

H

OH

O

Rhodium-Catalyzed CyclisationVCP + Alkene + CO

RhIII

CO insertion

O


CO insertion

ReductiveElimination O

O

RhI RhIII

Oxidative Addition


RhIII

O

Rhodium-Catalyzed Homo-Diels-AlderAlkenes + CO

Wang, Y.; Wang, J.; Su, J.; Huang, F.; Jiao, L.; Liang, Y.; Yang, D.; Zhang, S.; Wender, P. A.; Yu, Z. J. Am. Chem. Soc. 2007, 129, 10060-10061.

Entry

1

R1 R2

H

R3

H

5 % [Rh(CO)2Cl]2CO (0.2 atm), N2 (0.8 atm)

Yield

70 %

2 H H 81 %

3 H H 90 %

4 H H 29 %Me

5 H H 71 %Me

6 H Ph 78 %

7 H Ph 92 %

8 H Ph 73 %

9 Me Ph 83 %

Me

H

X

R1

R2

R3

X

C(CO2Me)2

NTs

C(CO2Me)2

NTs

NTs

O

O

O

O

H

H

H

H

H

X

R1

R2

R3

O

Dioxane, 0.01 M, 80 °C

H

HPh

O

TsN

Ph

TsN

90 %, 5:1 trans:cis

Rhodium-Catalyzed Homo-Diels-AlderAlkenes + CO

Wang, Y.; Wang, J.; Su, J.; Huang, F.; Jiao, L.; Liang, Y.; Yang, D.; Zhang, S.; Wender, P. A.; Yu, Z. J. Am. Chem. Soc. 2007, 129, 10060-10061.

5 % [Rh(CO)2Cl]2CO (0.2 atm), N2 (0.8 atm)X

X

H

H

O

Dioxane, 0.05 M, 80 °C

MeMe

X

H

H

O

Me

+

X = C(CO2Me)2 E/Z : 3:1

E/Z : 1:3

16 %

52 %

50 %

16 %

X = NTs E/Z : 3:1

E/Z : 1:3

15 %

31 %

44 %

10 %

Rhodium-Catalyzed CyclisationVinylcyclobutanone + Alkene/allene

RhIII

CO insertion

O

CO insertion

ReductiveElimination O

RhI RhIII

Oxidative Addition


RhIII

O

RhI RhIII

Oxidative Addition RhIII

O O O

Rhodium-Catalyzed CyclisationVinylcyclobutanone + Alkene/allene

Wender, P. A.; Correa, A. G., Sato, Y.; Sun, R. J. Am. Chem. Soc. 2000, 122, 7815-7816.

Substrats Products Time YieldMethod

20 h 78 %26 h 71 %

3 h 95 %BC

AR1=H, R2=MeR1=Me, R2=H

R1=R2=H 10 % RhCl(PPh3)310 % AgOTf

PhMe (0.014 M), 110 °C

A

B

TsN TsN

14 h 80 %C

R1

R2

10 % RhCl(CO)(PPh3)310 % AgOTf

PhMe (0.014 M), 110 °C

C

5 % [Rh(CO)2Cl]210 % PBu3, 10 % AgOTfPhMe (0.014 M), 110 °C

D

5 % [Rh(CO)2Cl]210 % PBu3, 10 % AgOTfPhMe (0.010 M), 110 °C

E

5 % [Rh(CO)2Cl]2PhMe (0.010 M), 110 °C

OO

R1

R2

O O

H

H

OO

20 h 77 %26 h 78 %

17 h 80 %DC

CR1=H, R2=MeR1=Me, R2=H

R1=R2=HR1

R2

OO

R1

R2MeO2C

MeO2C

MeO2C

MeO2C

0.75 h 91 %ETsN TsN

H

H

OO


Entry

1

2

3

4

5

6

R2

Catalyst

1 %

1 %

1 %

1 %

1 %

2 %

PhMe, 0.3 M+

7 5 %

R2

Me

CH2OMe

Cl

C(O)NH2

CH(OH)Me

CN

C(O)Me

8 1 %CHO

9 10 %

10 1 %Ph

Ph

O

Ph R1

Ph

1.0-1.5 equiv

Conditions

2 h, 80 °C

4 h, 110 °C

18 h, 110 °C

6 h, 110 °C

12 h, 80 °C

23 h, 110 °C

Yield

94 %

97 %

91 %

71 %

99 %

64 %

11 h, 110 °C 37 %

3 h, 110 °C 42 %

21 h, 60 °C 35 %

65 h, 80 °C 17 %

[Rh(CO)2Cl]2 Ph

R1 R2

Ph

O

11 1 %Ph

12 1 %

13 5 %C(O)Me

17.5 h, 110 °C 57 %

7.5 h, 110 °C 44 %

5 h, 110 °C 61 %

Me

R1

Ph

Ph

Ph

Ph

Ph

Ph

Ph

Ph

Ph

Me

Me

Me

Ph

Wender, P. A.; Paxton, T. J.; Williams, T. J. J. Am. Chem. Soc. 2006, 128, 14814-14815.


Entry

1

2

3

4

5

6

R2

Catalyst

1 %

1 %

1 %

1 %

1 %

1 %

PhMe, 0.3 M+

7 1 %

R2

Me

CH2OMe

Me

Me

Me

CH2OMe

Me

8 1 %CH2OMe

9 1 %

10 3 %

O

Ph Ph

R1

1.5 equiv

Conditions

2.5 h, 80 °C

5 h, 110 °C

6.5 h, 110 °C

20 h, 80 °C

5 h, 110 °C

3 h, 80 °C

Yield

94 %

78 %

91 %

77 %

98 %

88 %

17.5 h, 110 °C 52 %

20 h, 80 °C 52 %

7.5 h, 80 °C 65 %

3.5 h, 120 °C 69 %

[Rh(CO)2Cl]2 Ph

Ph R2

R1

O

R1

p-MeOPh

p-MeC(O)Ph

o-F

o-Me

p-CF3

Benzyne

n-Pr

O

N

n-Pr

---

Wender, P. A.; Paxton, T. J.; Williams, T. J. J. Am. Chem. Soc. 2006, 128, 14814-14815.

Rhodium-Catalyzed CyclisationNew Catalysts

N

NBn

O

Bn

RhBr

Gomez, F. J.; Kamber, N. E.; Deschamps, N. M.; Cole, A. P.; Wender, P. A.; Waymouth, R. M. Organometallics 2007, 26, 4541-4545.

10 % RhCl(PPh3)3MeO2C

MeO2C

MeO2C

MeO2CH

TFE, 65 °C, 19 h90-95 %

Me

2 % Cat.2 % AgSbF6

DCE, rt, 15 min93 %

1 % [Rh(CO)2Cl]2

PhMe, 110 °C, 3 h90 %


N

NBn

O

Bn

RhBr

Gomez, F. J.; Kamber, N. E.; Deschamps, N. M.; Cole, A. P.; Wender, P. A.; Waymouth, R. M. Organometallics 2007, 26, 4541-4545.

O O

H

1 % Cat.1 % AgSbF6

DCE, rt, 15 min99 %

Me


Rh+SbF6

-

Wender, P. A.; Williams, T. J. Angew. Chem. Int. Ed. 2002, 41, 4550-4553.

10 % RhCl(PPh3)3MeO2C

MeO2C

MeO2C

MeO2CH

TFE, 55 °C, 19 h90-95 %

Me

2 % Cat.

DCE, rt, 15 min>99 %

1 % [Rh(CO)2Cl]2

PhMe, 110 °C, 3 h89 %

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Université de Montréal October 30 th 2007

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