Dess–Martin periodinane oxidative rearrangement for preparation of α-keto thioesters

Abstract

A Dess–Martin Periodinane (DMP) mediated oxidative rearrangement reaction was uncovered. The reaction proceeds via oxidation of a β-hydroxy thioester to a β-keto thioester, followed by an α-hydroxylation and then further oxidation to form a vicinal thioester tricarbonyl. This product then rearranges, extruding CO₂, to form an α-keto product. The mechanism of the rearrangement was elucidated using ¹³C labelling and analysis of the intermediates as well as the products of the reaction. This efficient process allows for easy preparation of α-keto thioesters which are potential intermediates in the synthesis of pharmaceutically important heterocyclic scaffolds such as quinoxalinones.