Synthesis of 3-Acyloxyindolenines by TiCl3-Mediated Reductive Cyclization of 2-(ortho-Nitroaryl)-Substituted Enol Esters

Org Lett. 2022 Sep 30;24(38):7004-7008. doi: 10.1021/acs.orglett.2c02860. Epub 2022 Sep 19.

Abstract

In the presence of TiCl3, the reductive cyclization of tetrasubstituted enol esters bearing a 2-(ortho-nitroaryl) substituent affords 3-acyloxy-2,3-disubstituted indolenines in good yields. A domino process involving the partial reduction of nitro to a nitroso group followed by 5-center-6π-electrocyclization, 1,2-acyloxy migration, and the further reduction of the resulting nitrone intermediate accounts for the reaction outcome. The so-obtained indolenines are converted smoothly to 2,2-disubstituted oxindoles via a sequence of saponification and semipinacol rearrangement.