Design of Modified Amine Transfer Reagents Allows the Synthesis of α-Chiral Secondary Amines via CuH-Catalyzed Hydroamination
作者:Dawen Niu、Stephen L. Buchwald
DOI:10.1021/jacs.5b05446
日期:2015.8.5
were used for the synthesis of chiral secondary amines, competitive, nonproductive consumption of these reagents by the CuH species resulted in poor yields. In this paper, we report the design of a modified type of amine transfer reagent that addresses this limitation. This effort has enabled us to develop a CuH-catalyzed synthesis of chiral secondary amines using a variety of amine coupling partners,
使用硅烷和胺转移试剂对烯烃和炔烃进行 CuH 催化的加氢胺化反应是一种获得手性胺产品的简单策略。我们最近报道了使用这种方法制备具有高效率和立体选择性的手性胺的方法。然而,目前的技术仅限于从二烷基胺转移试剂 (R2NOBz) 合成三烷基胺。当单烷基胺转移试剂 [RN(H)OBz] 用于合成手性仲胺时,CuH 物种对这些试剂的竞争性非生产性消耗导致收率不佳。在本文中,我们报告了一种解决此限制的改进型胺转移试剂的设计。这一努力使我们能够使用各种胺偶联伙伴(包括来自氨基酸酯、碳水化合物和类固醇的那些)开发 CuH 催化合成手性仲胺。机理研究表明,改性胺转移试剂不易与 CuH 直接反应。