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通过协同催化将 C1-氨烯醇盐与过渡金属亲电试剂联合起来:芳基乙酸酯的直接不对称 α-烯丙基化反应。

Uniting C1-Ammonium Enolates and Transition Metal Electrophiles via Cooperative Catalysis: The Direct Asymmetric α-Allylation of Aryl Acetic Acid Esters.

机构信息

Department of Chemistry, Indiana University , 800 E. Kirkwood Ave., Bloomington, Indiana 47405, United States.

出版信息

J Am Chem Soc. 2016 Apr 27;138(16):5214-7. doi: 10.1021/jacs.6b01694. Epub 2016 Apr 18.

DOI:10.1021/jacs.6b01694
PMID:27028057
Abstract

The direct, catalytic, asymmetric α-functionalization of acyclic esters constitutes a significant challenge in the area of asymmetric catalysis, particularly where the configurational integrity of the products is problematic. Through the unprecedented merger of two independent, yet complementary, catalysis events it has been possible to facilitate the direct asymmetric α-allylation of readily available aryl acetic acid esters. Since enantioselection is determined by the nucleophile, this conceptual approach to cooperative catalysis constitutes a potentially general solution to the direct catalytic asymmetric α-functionalization of acyclic esters.

摘要

在不对称催化领域,非环酯的直接、催化、不对称α-官能化是一个重大挑战,特别是在产物的构型完整性存在问题的情况下。通过将两个独立但互补的催化事件以前所未有的方式融合,我们已经能够促进易得的芳基乙酸酯的直接不对称α-烯丙基化。由于对映选择性取决于亲核试剂,这种协同催化的概念方法为非环酯的直接催化不对称α-官能化提供了一种潜在的通用解决方案。

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