均相金催化在过去十几年经历了飞速的发展,展现出了非常高的催化效率和非常强的官能团兼容性.另一方面。催化去芳构化反应能够直接高效地将芳香化合物转化为高度官能团化的具有丰富三维立体结构的分子.因此,金催化去芳构化反应将会为天然产物和复杂分子的合成提供新颖直接高效的路径.本文总结了近几年金催化去芳构化反应的例子,主要可分为金催化的重排反应和炔烃/联烯的氢一官能团化反应两方面,同时还介绍了这两类反应的特点与可能的反应机理.
Homogeneous gold catalysis has experienced rapid development since 2004 and generally exhibited high effi- ciency and good functional group tolerance. On the other hand, catalytic dearomatization reactions provide a unique and straight approach to the construction of highly functionalized molecules with diverse three-dimensional structures from sim- ple aromatic compounds. In this perspective, recent examples on gold-catalyzed dearomatization reactions are summarized in two main categories: gold-catalyzed rearrangements and gold-catalyzed hydrofunctionalizations of alkynes and allenes. In the first category, intra- and inter- molecular dearomatization reactions were achieved via gold-catalyzed rearrangements of pro- pargylic ester and its derivatives. Although this area is still at its early stage, several outstanding asymmetric examples have been reported by Shi and Toste. In the second category, an array of dearomatization reactions via gold-catalyzed hydrofunc- tionalizations of alkynes and allenes were presented. All these cases have shown great potentials for convenient and straight- forward construction of spiro and/or bridged polycyclic molecules, and some of them have exhibited excellent enantioselec- tivity. In addition, salient features and proposed mechanisms for these two types of reactions are also described.