Key Laboratory of Molecule Synthesis and Function Discovery, College of Chemistry, Fuzhou University, 2 Xueyuan Road, Fuzhou 350116, P. R. China.
Beijing National Laboratory for Molecular Sciences (BNLMS), Beijing 100190, P. R. China.
Org Lett. 2020 May 1;22(9):3692-3696. doi: 10.1021/acs.orglett.0c01180. Epub 2020 Apr 12.
Thioesters and related thiols are critically important to biological systems and also widely employed in the synthesis of pharmaceutically important molecules and polymeric materials. However, known synthetic methods often suffer from the disadvantage of being specific only to certain substrates. Herein, we describe a facile decarboxylative thioesterification of alkyl acid derived redox-active esters by merging photoredox catalysis and copper catalysis. This reaction is applicable to a wide range of carboxylic acids, as well as natural products and drugs, allowing for the synthesis of various thioesters with diverse structures, including tertiary ones that are not accessible via traditional nucleophilic substitution from tertiary halides. Moreover, product utilization is demonstrated with a direct transformation of thioesters to sulfonyl fluorides.
硫酯和相关硫醇对生物系统至关重要，也广泛应用于药物重要分子和聚合材料的合成。然而，已知的合成方法往往受到只能对某些特定底物起作用的缺点的影响。在此，我们描述了一种通过光氧化还原催化和铜催化合并来实现由烷基酸衍生的氧化还原活性酯的易脱羧硫酯化的方法。该反应适用于广泛的羧酸，以及天然产物和药物，允许合成各种具有不同结构的硫酯，包括传统亲核取代法无法从叔卤化物得到的叔硫酯。此外，通过硫酯直接转化为砜氟化物来证明产物的利用。
