铑催化的非活化芳基仲烯丙基三氯乙酰胺的区域选择性胺化反应。

Rhodium-catalyzed regioselective amination of secondary allylic trichloroacetimidates with unactivated aromatic amines.

机构信息

Department of Chemistry, University of Iowa, Iowa City, Iowa 52242, USA.

出版信息

Org Lett. 2010 Oct 15;12(20):4580-3. doi: 10.1021/ol1019025.

DOI:10.1021/ol1019025

PMID:20843019

Abstract

The use of unactivated aromatic amines in the rhodium-catalyzed regioselective amination of secondary allylic trichloroacetimidates is explored. The desired N-arylamines are obtained in high yields and regioselectivity, favoring the branched amination products. The presence of the trichloroacetimidate leaving group was found to be critical for successful regioselective amination reactions with unactivated aromatic amines. Control studies show that rhodium is not simply acting as a Lewis acid to activate the trichloroacetimidate leaving group.

摘要

研究了在铑催化的仲烯丙基三氯乙酰亚胺酯的区域选择性胺化反应中使用未活化的芳胺。以高收率和区域选择性得到所需的 N-芳基胺，有利于支化的胺化产物。研究发现，三氯乙酰亚胺酯离去基团的存在对于未活化的芳胺的成功区域选择性胺化反应是至关重要的。控制研究表明，铑并不是简单地作为路易斯酸来活化三氯乙酰亚胺酯离去基团。