Page 739 - Advanced Organic Chemistry Part B - Reactions & Synthesis

Scheme 8.8. Enantioselective Allylation of Diethyl Malonate 715
CH 3 S CH SECTION 8.2
1 a CH 3 3 CH 3
CCH P O P Reactions Involving
O 2 3 Ph Ph Organopalladium
CH 3 CH 3 Intermediates
PhCH CHCHPh + CH (CO C H )
2 2 2 5 2 [Pd(CH CH CH ) Cl] 2 CH(CO C H )
2
2 2
(CH ) SiN COSi(CH ) 2 2 5 2
3 3
3 3
97% e.e.
CH 3
2 b O N C(CH )
3 3
O CCH 3 N OCH 3
2
Ph Ph Ph
PhCH CHCHPh + CH (CO C H )
2
2 2 5 2
[Pd(CH CH CH ) Cl] 2
2 2
2
) SiN
2 2 5 2
(CH 3 3 COSi(CH ) CH(CO C H )
3 3
97% yield, >99% e.e.
3 c CH 3
)
CH(CH 3 2
O
PPh 2
C(CH )
O 2 3 3 PPh CH(CO 2 CH )
3 2
2
+ CH (CO C H ) O CH(CH )
2 2 5 2
2
3 2
64% yield, >99% e.e.
[Pd(CH CH CH ) Cl] 2
2
2 2
(CH ) SiN COSi(CH )
3 3
3 3
CH 3
a. P. Dierks, S. Ramdeehul, L. Barley, A. DeCian, J. Fischer, P. C. J. Kramer, P. W. N. M. van Leeuwen, and J. A. Osborne,
Angew. Chem. Int. Ed. Engl., 37, 3116 (1998).
b. K. Nordstrom, E. Macedo, and C. Moberg, J. Org. Chem., 62, 1604 (1997); U. Bremberg, F. Rahm, and C. Moberg,
Tetrahedron: Asymmetry, 9, 3437 (1998).
c. A Saitoh, M. Misawa, and T. Morimoto, Tetrahedron: Asymmetry, 10, 1025 (1999).
8.2.2. The Heck Reaction
Another important type of reactivity of palladium, namely oxidative addition to
Pd(0), is the foundation for several methods of forming carbon-carbon bonds. Aryl 126
and alkenyl 127 halides react with alkenes in the presence of catalytic amounts of
palladium to give net substitution of the halide by the alkenyl group. The reaction,
known as the Heck reaction, 128 is quite general and has been observed for simple
alkenes, aryl-substituted alkenes, and substituted alkenes such as acrylate esters, vinyl
ethers, and N-vinylamides. 129
126 H. A. Dieck and R. F. Heck, J. Am. Chem. Soc., 96, 1133 (1974); R. F. Heck, Acc. Chem. Res., 12, 146
(1979); R. F. Heck, Org. React., 27, 345 (1982).
127
B. A. Patel and R. F. Heck, J. Org. Chem., 43, 3898 (1978); B. A. Patel, J. I. Kim, D. D. Bender,
L. C. Kao, and R. F. Heck, J. Org. Chem., 46, 1061 (1981); J. I. Kim, B. A. Patel, and R. F. Heck,
J. Org. Chem., 46, 1067 (1981).
128 I. P. Beletskaya and A. V. Cheprakov, Chem. Rev., 100, 3009 (2000); B. C. G. Soderberg, Coord.
Chem. Rev., 224, 171 (2002); G. T. Crisp, Chem. Soc. Rev., 27, 427 (1998).
129
C. B. Ziegler, Jr., and R. F. Heck, J. Org. Chem., 43, 2941 (1978); W. C. Frank, Y. C. Kim, and
R. F. Heck, J. Org. Chem., 43, 2947 (1978); C. B. Ziegler, Jr., and R. F. Heck, J. Org. Chem., 43, 2949
(1978); H. A. Dieck and R. F. Heck, J. Am. Chem. Soc., 96, 1133 (1974); C. A. Busacca, R. E. Johnson,
and J. Swestock, J. Org. Chem., 58, 3299 (1993).