通过C-H键活化实现α,β-不饱和亚胺的立体选择性烷基化反应。
Stereoselective alkylation of alpha,beta-unsaturated imines via C-H bond activation.
作者信息
Colby Denise A, Bergman Robert G, Ellman Jonathan A
机构信息
Department of Chemistry, University of California, and Division of Chemical Sciences, Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA.
出版信息
J Am Chem Soc. 2006 May 3;128(17):5604-5. doi: 10.1021/ja0584931.
Abstract
The stereoselective alkylation of alpha,beta-unsaturated imines via C-H activation followed by imine hydrolysis produces tri- and tetrasubstituted alpha,beta-unsaturated aldehydes. In the presence of a rhodium catalyst, alpha,beta-unsaturated N-benzyl imines derived from methacrolein, crotonaldehyde, and tiglic aldehyde undergo directed C-H activation at the beta-position and react with terminal alkenes and alkynes to form the tri- and tetrasubstituted alpha,beta-unsaturated imines with very high stereoselectivity. Hydrolysis to provide alpha,beta-unsaturated aldehydes can be performed under carefully controlled conditions that maintain the stereochemistry of the beta-alkylated imine products. Alternatively, for beta-alkylation products of the N-benzyl imine of methacrolein, hydrolysis can be performed under conditions that provide complete isomerization to the E isomer.
摘要
通过C-H活化然后进行亚胺水解实现α,β-不饱和亚胺的立体选择性烷基化反应可生成三取代和四取代的α,β-不饱和醛。在铑催化剂存在下，源自异丁烯醛、巴豆醛和惕各醛的α,β-不饱和N-苄基亚胺在β位发生定向C-H活化，并与末端烯烃和炔烃反应，以非常高的立体选择性形成三取代和四取代的α,β-不饱和亚胺。在精心控制的条件下进行水解以提供α,β-不饱和醛，这些条件能保持β-烷基化亚胺产物的立体化学。或者，对于异丁烯醛的N-苄基亚胺的β-烷基化产物，水解可在能使产物完全异构化为E异构体的条件下进行。
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