Electrochemically Driven Diastereoselective Dearomative 2,3‐Diesterification of Indoles with Carboxylic Acids

An electrochemically driven radical cation‐mediated dearomative 2,3‐difunctionalization of indoles with carboxylic acids is described, which provides an efficient and straightforward route for the construction of a range of 2,3‐diesterified indolines with excellent trans ‐diastereoselectivity in moderate‐to‐good yields. This metal‐ and oxidant‐free electrochemical protocol proceeds in an undivided cell, exhibiting broad substrate scope and excellent functional group tolerance. Mechanistic studies reveal that the anodic single‐electron oxidation of indoles is the initial step and oxocarbenium ion formation is the key to controlling trans ‐diastereoselectivity.