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Abstract：
Quaternary stereocenters are of great importance to the three-dimensionality and enhanced properties of new molecules, but the synthetic challenges in creating quaternary stereocenters greatly hinder their wide use in drug discovery, organic material design, and natural product synthesis. The asymmetric allylic alkylation (AAA) of allylic substrates has proven to be a powerful methodology for enantioselective formation of structure skeletons bearing single or more quaternary carbon centers in modern asymmetric organocatalysis. AAA has certain advantages in constructing the tetrasubstituted stereocenters, including but not limited to mild reactive conditions, effective reaction rates, new functional group introduction, and carbon chains length extension. This review outlines the key considerations in the application of AAA reactions and summarizes the recent progress of AAA reactions in the enantioselective synthesis of products containing quaternary stereocenters. Meanwhile, a detailed discussion of the AAA reactions such as ligands, scope of substrates, transformations and the general reaction mechanisms is also provided. We hope this review could stimulate further advances in much broader areas, including organic synthesis, asymmetric catalysis, C-H activation, and symmetrical pharmaceutical chemistry.
摘要：
四元立体中心对于新分子的三维性和增强性质具有重要意义,但是在创建四元立体中心方面的合成挑战极大地阻碍了它们在药物发现中的广泛应用，有机材料设计，和天然产物合成。烯丙基底物的不对称烯丙基烷基化（AAA）已被证明是现代不对称有机催化中具有单个或多个季碳中心的结构骨架的对映选择性形成的强大方法。AAA在构建四合立体中心方面具有一定的优势，包括但不限于轻度反应条件，有效反应速率,新功能组介绍，和碳链长度延长。本文概述了AAA反应应用中的关键考虑因素，并总结了AAA反应在含四元立体中心产物的对映选择性合成中的最新进展。同时,详细讨论了AAA反应，如配体，底物的范围，还提供了转化和一般反应机理。我们希望这次审查能够促进更广泛领域的进一步进展，包括有机合成，不对称催化，C-H活化,和对称药物化学。
