α-氨基烷基铜酸盐与α,β-烯基、α,β-炔基、α,β-β,γ-联烯基和α,β-γ,δ-二烯基羧酸衍生物、腈类及亚砜的共轭加成反应。

Conjugate addition reactions of alpha-aminoalkylcuprates with alpha, beta-alkenyl-, alpha,beta-alkynyl-, alpha,beta-beta,gamma-allenyl-, and alpha,beta-gamma,delta-dienyl carboxylic acid derivatives, nitriles, and sulfoxides.

作者信息

Dieter R K, Lu K, Velu S E

机构信息

Hunter Laboratory, Department of Chemistry, Clemson University, Clemson, South Carolina 29634-0973, USA.

出版信息

J Org Chem. 2000 Dec 15;65(25):8715-24. doi: 10.1021/jo0056038.

DOI:10.1021/jo0056038

PMID:11112594

Abstract

alpha-Aminoalkylcuprates prepared from alpha-lithio carbamates and CuCN.2LiCl participate in 1,4-addition reactions with alpha, beta-unsaturated esters, thiol esters, imides, and nitriles in poor to excellent yields depending upon the electron-withdrawing substituent and the substitution pattern of the unsaturated substrate. These reagents also undergo conjugate addition reactions with alpha,beta-alkynyl esters, sulfoxides, and nitriles and with alpha,beta-beta,gamma-unsaturated allenyl esters. Excellent stereocontrol is achieved in the conjugate additions of alpha-aminoalkylcuprates to the allenyl esters, while poor stereoselectivity results in the conjugate additions to the alkynyl derivatives. Deprotection and cyclization of the alkynyl adducts affords pyrrolin-2-ones, while similar treatment of the allenyl adducts affords 4-alkylidine- pyrrolidin-2-ones and pyrrolizidinones.

摘要

由α-锂代氨基甲酸酯和CuCN·2LiCl制备的α-氨基烷基铜酸盐，可与α,β-不饱和酯、硫醇酯、酰亚胺和腈发生1,4-加成反应，产率从低到高不等，这取决于吸电子取代基和不饱和底物的取代模式。这些试剂还可与α,β-炔基酯、亚砜和腈以及α,β-β,γ-不饱和联烯酯发生共轭加成反应。在α-氨基烷基铜酸盐与联烯酯的共轭加成反应中可实现出色的立体控制，而在与炔基衍生物的共轭加成反应中立体选择性较差。炔基加合物的脱保护和环化反应可得到吡咯啉-2-酮，而对联烯基加合物进行类似处理则可得到4-亚烷基-吡咯烷-2-酮和吡咯里西啶酮。