期刊

Chemical Science

标题

Anodic oxidation triggered divergent 1,2- and 1,4-group transfer reactions of β-hydroxycarboxylic acids enabled by electrochemical regulation

作者

Zhenxing Zhang, Lei Zhang, Xianhao Zhang, Jianxin Yang, Yunxing Yin, Yangye Jiang, Chengchu Zeng, Gang Lu, Yang Yang, Fanyang Mo

摘要

We report a set of electrochemically regulated protocols for the divergent synthesis of ketones and β-keto esters from the same β-hydroxycarboxylic acid starting materials. Enabled by electrochemical control, the anodic oxidation of carboxylic acids proceeded in either a one-electron or a two-electron pathway, leading to a 1,4-aryl transfer or a semipinacol-type 1,2-group transfer product with excellent chemoselectivity. The 1,4-aryl transfer represents an unprecedented example of carbon-to-oxygen group transfer proceeding via a radical mechanism. In contrast to previously reported radical group transfer reactions, this 1,4-group transfer process features the migration of electron-rich aryl substituents. Furthermore, with these chemoselective electrochemical oxidation protocols, a range of ketones and β-keto esters including those possessing a challenging-to-access medium-sized ring could be synthesized in excellent yields.

原文链接

https://pubs.rsc.org/en/content/articlelanding/2020/sc/d0sc02386h