Control of the regioselectivity in catalytic transformations involving amphiphilic bis-allylpalladium intermediates:: Mechanism and synthetic applications

被引:49
作者
Solin, N [1 ]
Narayan, S [1 ]
Szabó, KJ [1 ]
机构
[1] Univ Stockholm, Arrhenius Lab, Dept Organ Chem, S-10691 Stockholm, Sweden
关键词
D O I
10.1021/jo001374d
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
Various dialkyl-substituted allyl chloride derivatives (2d-i) undergo regioselective palladium-catalyzed coupling reactions with allylstannanes (1a,b) and benzylidenemalonitrile (4), providing functionalized 1,7-octadienes in good yield. The catalytic reaction proceeds through an unsymmetrical amphiphilic bis-allylpalladium intermediate. An:introductory electrophilic attack on the terminal position of the unsubstituted alkyl moiety is followed by a nucleophilic attack on the alkyl-substituted allyl ligand. A theoretical analysis was performed by applying density functional theory at the B3PW91/DZ+P level to study the substituent effects on the electrophilic attack. According to the theoretical results, the high regioselectivity can be ascribed to the electronic effects of the alkyl substituents: The terminal alkyl groups destabilize the eta (1),eta (3)-bis-allylpalladium intermediate of the reaction; in addition, the alkyl substitution increases the activation barrier for the electrophilic attack.
引用
收藏
页码:1686 / 1693
页数:8
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