cationic alkyne activation - princeton universityorggroup/supergroup_pdf/ychen042005.pdf ·...
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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.
Skeletal Reorganization
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
Skeletal Reorganization
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
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.
Non-classical Carbocation
X X
M
X
M
X
MM+
X
M+
X X
M+M+
homoallyl cyclopropylmethyl cyclobutyl
norbornyl cation
Non-classical Carbocation
Oi, S.; Tsukamoto, I.; Miyano, S.; Inoue, Y. Organometallics 2001, 20, 3704-3709.
Skeletal Reorganization
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
Skeletal Reorganization
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
M = Ru(II), Ir (I), Pd(II), Pt(II), Pt(IV), Ag (I), Au(I), Au(III), Ga(III) et al
Cationic Alkyne Activation
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
M = Ru(II), Ir (I), Pd(II), Pt(II), Pt(IV), Ag (I), Au(I), Au(III), Ga(III) et al
Cationic Alkyne Activation
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
M = Ru(II), Ir (I), Pd(II), Pt(II), Pt(IV), Ag (I), Au(I), Au(III), Ga(III) et al
Cationic Alkyne Activation
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
Cationic Alkyne Activation
homoallyl cyclopropylmethyl
cyclobutyl
M M