Department of Chemistry, Princeton University, Princeton, New Jersey 08544, United States.
Department of Chemistry, Emory University, 1515 Dickey Drive, Atlanta, Georgia 30322, United States.
Org Lett. 2021 Dec 17;23(24):9393-9397. doi: 10.1021/acs.orglett.1c03502. Epub 2021 Dec 5.
An enantioselective formal synthesis of (-)-aflatoxin B from 4-methoxyphenylacetic acid has been achieved by an approach that produces a key carbon-carbon bond, a benzylic stereocenter, and two arene carbon-oxygen bonds in the course of three site-selective C-H functionalizations. The carbonyl-directed acetoxylation of two arene C-H bonds described herein is unprecedented in natural product synthesis and occurs under mild conditions that preserve the configuration of a sensitive benzylic stereocenter.
通过三种位点选择性 C-H 官能化反应，实现了从 4-甲氧基苯乙酸对映选择性地全合成 (-)-黄曲霉毒素 B，该方法生成了一个关键的碳-碳键、一个苄位手性中心和两个芳基碳-氧键。本文中描述的羰基导向的两个芳基 C-H 键的乙酰氧基化在天然产物合成中是前所未有的，并且在温和的条件下进行，这些条件保留了敏感的苄位手性中心的构型。
