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C-C Bond Formation viaCationic Alkyne Activation

Yiyun ChenOrganic Super Group Meeting,Department of Chemistry, Princeton UniversityWednesday, April 20th, 2005

Reactivity of 1,n-Enyne

Aubert, C.; Buisine, O.; Malacria, M. Chem. Rev. 2002, 102, 813-834.

Metallacycle Pathway

Skeletal Reorganization

E

E

E

E

E

H H

EE

E

E

E

E

E

E

E

H H

E

E

E

E

E/Z=100/0

E/Z=1/10

PdE

E

EE

68%

Trost, B. M.; Tanoury, G. J. J. Am. Chem. Soc. 1988, 110,1636-1638.


O

R1

PtCl4 R1=Ph, R2=H 20%R1,R2=Ph 97%

Blum, J.; Beer-Kraft, H.; Badrieh, Y. J. Org. Chem. 1995, 60, 5567-5569.

R2O

R1

R2

H

E

EE

E

EPtCl2E = COOMe80%, Z/E = 33/67

Chatani, N.; Furukawa, N.; Sakurai, H.; Murai, S. Organometallics 1996, 15, 901-903.

E


NE

Ts

E=COC3H7

N

E

Ts NTs

E

NTs

OOH

C3H7

N

E

Ts

79% 5% 2% 1%

PtCl2

BF3: 64%HBF4: 57%

Furstner, A.; Szillat, H.; Gabor, B.; Mynott, R. J. Am. Chem. Soc. 1998, 120, 8305-8314.

Nu

XX = SnR3, SiR3

R2

R1 = OR orR2 = OR

R1

M+Alkene Arene

Enol Allyl X

M = Ru(II), Ir (I), Pd(II), Pt(II), Pt(IV), Ag (I), Au(I), Au(III), Ga(III) et al

Cationic Alkyne Activation

Non-classical Carbocation

“In classical carbocations the positive charge is localized on one carbon atom or delocalized by resonance involving an unshared pair of electrons or a double or triple bond in the allylic position.”“In a non-classical carbocation, the positive charge is delocalized by a double or triple bond that is not in the allylic position or by a single bond.”

March, J. Advanced Organic Chemistry; 4th ed.; Wiley: New York, 1992, p312-326.


X X

M

X

M

X

MM+

X

M+

X X

M+M+

homoallyl cyclopropylmethyl cyclobutyl

norbornyl cation


Oi, S.; Tsukamoto, I.; Miyano, S.; Inoue, Y. Organometallics 2001, 20, 3704-3709.


O

R1

PtCl4 R1=Ph, R2=H 20%R1,R2=Ph 97%

Blum, J.; Beer-Kraft, H.; Badrieh, Y. J. Org. Chem. 1995, 60, 5567-5569.

R2O

R1

R2

H

E

EE

E

EPtCl2E = COOMe80%, Z/E = 33/66

Chatani, N.; Furukawa, N.; Sakurai, H.; Murai, S. Organometallics 1996, 15, 901-903.

E

O

R1

R2

H

M

E

E

EM


NE

Ts

E=COC3H7

N

E

Ts NTs

E

NTs

OOH

C3H7

N

E

Ts

79% 5% 2% 1%

PtCl2

Furstner, A.; Szillat, H.; Gabor, B.; Mynott, R. J. Am. Chem. Soc. 1998, 120, 8305-8314.

NCOC3H7

Ts

NTs

OM

C3H7

NTs

OM

C3H7

NTs

OM

C3H7

NTs

MOC3H7M+

M+

Carbenoid Character

E

E

E E

E

E

HH

H

H

E

E

HE

EE

E

Ru

HE

EE

E

Ru

[RuCl2(CO)3]2

Chatani, N.; Kataoka, K.; Murai, S.; Furukawa, N.; Seki, Y. J. Am. Chem. Soc. 1998, 120, 9104-9105.

Metallacycle Pathway

1,5-Enyne

Ph(PPh3)AuSbF6 Ph

Luzung, M.R.; Markham, J.P; Toste, F.D. J. Am. Chem. Soc. 2004, 126, 10858-10859.

HO(PPh3)AuSbF6

OR

R

or PtCl2

HR

HO

Cl2Pt

H

Ph

Au

Mamane, V.; Gress, T.; Krause, H.; Furstner, A. J. Am. Chem. Soc. 2004, 126, 8654-8655.Harrak, Y.; Malacria, M. et al. J. Am. Chem. Soc. 2004, 126, 8656-8657.

1,2-Acetate Migration

Mamane, V.; Gress, T.; Krause, H.; Furstner, A. J. Am. Chem. Soc. 2004, 126, 8654-8655.Harrak, Y.; Malacria, M. et al. J. Am. Chem. Soc. 2004, 126, 8656-8657.

AcO(PPh3)AuSbF6R

RAcO

OR

O

AuO

RO

Au O

RO

Au

or PtCl2

External Nucleophile TrapE

EE

EPtCl2

MeOH67%, 2/3

Mendez, M.; Munoz, M. P.; Echavarren, A. M. J. Am. Chem. Soc. 2000, 122, 11549-11550.

H OMe

EE

OMe

Nu

XX = SnR3, SiR3

R2

R1 = OR orR2 = OR

R1

M+Alkene Arene

Enol Allyl X



Enol Ether as NucleophileE

EOMe

E

EPtCl2

MeOH97%

Nevado, C.; Cardenas, D. J.; Echavarren, A. M. Chem. Eur. J. 2003, 9, 2627-2635.

OMe

MeOE

EPt

OMe

OMe

NTs NTsH

OMe

OMe

NTsH

OMe

Au+AuCl3

MeOH 43%

O

O

Ph O

O

Ph

PtCl2

TolueneO

O

Ph

Pt

84%

Nevado, C.; Ferrer, C..; Echavarren, A. M. Org. Lett. 2004, 6, 3191.

Furan as Nucleophile

O

TsNAuCl3

51%

Hashmi, A. S. K.; Frost, T. M.; Bats, J. W. J. Am. Chem. Soc. 2000, 122, 11553-11554.

TsN

OH

TsNOH

31%

TsN O TsNOAu

TsN

O

Furan as Nucleophile

O

OPtCl2

B: 4%

O

OH

A: 38%

H2O, AcetoneO

CHO

OC: 10%

O

CHO

O

Martin-Matute, B.; Nevado, C.; Cardenas, D. J., Echavarren, A. M. J. Am. Chem. Soc. 2003, 125, 5757-5766.

O

O

Pt

O O

PtO O

Pt

OPt

O O O

Pt

O O O

O

O O

PtCl

OHH2O

-HCl

HCl -PtCl2

O O O OH

O O

O-Pt(0)

-HCl

OH OH

A

B

C

β-Ketoester as Nucleophile

Kennedy-Smith, J. J.; Staben, S. T.; Toste, F.D. J. Am. Chem. Soc. 2004, 126, 4526-4527.Staben, S.T.; Kennedy-Smith, J. J.; Toste, F.D. Angew. Chem. Int. Ed. 2004, 43(40), 5350-5352.

MeOOCCOMe COMe

COOMe

COOMe

COMe

COMe

COOMe

(PPh3)AuOTf

(PPh3)AuOTf

COOMe

OHAu

COOMe

OAu

COOMe

OHAu

COOMe

OAu

β-Ketoester as Nucleophile

Staben, S.T.; Kennedy-Smith, J. J.; Toste, F.D. Angew. Chem. Int. Ed. 2004, 43(40), 5350-5352.

Nu

XX = SnR3, SiR3

R2

R1 = OR orR2 = OR

R1

M+Alkene Arene

Enol Allyl X



Allyl Silane/TinE

E E

EPtCl2

MeOHX = SiMe3, SnBu387%

Fernandez-Rivas, C.; Mendez, M.; Echavarren, A. M. J. Am. Chem. Soc. 2000, 122, 1221-1222.

X E

EPt

X

E

E

E

ED

NPtCl2

TolueneX = SiMe3, 76%

XTs N

X

Ts N

X

Ts

Pt

Furstner, A.; Szillat, H.; Stelzer, F. J. Am. Chem. Soc. 2000, 122, 6785-6786.

Nu

XX = SnR3, SiR3

R2

R1 = OR orR2 = OR

R1

M+Alkene Arene

Enol Allyl X



Arene as NucleophileE

E

OMe

[RuCl2(CO)3]2 E

E

OMe

E

E

OMe

81% (93:7)

E

E

OMe

[RuCl2(CO)3]2E

E

OMe

EE

OMe

19% (7:3)

or PtCl2

or PtCl2

E

E

OMe

Pt

EE

OMe

Pt

Chatani, N.; Inoue, H.; Ikeda, T.; Murai, S. J. Org. Chem. 2000, 65, 4913-4918.

E

E

[RuCl2(CO)3]2 E

E

E

E

58% (76:24)

OMe

OMe

OMe

or PtCl2E

E

OMe

Pt

XX = SnR3, SiR3

R2

R1 = OR orR2 = OR

R1

AlkeneArene

Enol Allyl X


homoallyl cyclopropylmethyl

cyclobutyl

M M

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