N-Alkylation of poor nucleophilic amines and derivatives with alcohols by a hydrogen autotransfer process catalyzed by copper(II) acetate: scope and mechanistic considerations
作者:Ana Martínez-Asencio、Diego J. Ramón、Miguel Yus
DOI:10.1016/j.tet.2011.02.075
日期:2011.4
simple catalyst for the selective N-monoalkylation of amino derivatives with poor nucleophilic character, such as aromatic and heteroaromatic amines as well as carboxamides, phosphinamides, sulfonamides, and phosphazenes, using in all cases primary alcohols as initial source of the electrophiles, through a hydrogen autotransfer process. In the case of sulfonamides, the monoalkylation process followed
乙酸铜(II)是一种通用,廉价且简单的催化剂,用于对亲核性较差的氨基衍生物(例如芳族和杂芳族胺以及羧酰胺,次膦酰胺,磺酰胺和磷腈)进行选择性N-单烷基化,在所有情况下均使用伯通过氢自动转移过程,将醇作为亲电试剂的初始来源。在磺酰胺的情况下,单烷基化过程随后是萘催化的还原性脱保护得到伯胺,这是氨直接单烷基化的间接替代方法。使用氘标记试剂对反应进行了研究,表明脱氢和氢化步骤不在同一铜原子配位球上进行,