Department of Chemistry, University of Alberta, Edmonton, Alberta, Canada T6G-2G2.
Org Biomol Chem. 2018 Jan 24;16(4):593-597. doi: 10.1039/c7ob02959d.
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 CO, to form an α-keto product. The mechanism of the rearrangement was elucidated using C 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.
发现了一种 Dess-Martin 过碘烷（DMP）介导的氧化重排反应。该反应通过β-羟基硫酯的氧化，形成β-酮硫酯，然后进行α-羟化，再进一步氧化形成偕二硫代三羰基。然后该产物重排，排出 CO，形成α-酮产物。通过 C 标记和中间体以及反应产物的分析，阐明了重排的机制。这种高效的过程允许轻松制备α-酮硫酯，它们是合成具有重要药用价值的杂环支架（如喹喔啉酮）的潜在中间体。
