Shandong Lunan Coal Chemical Research Institute of Engineering and Technology, Zaozhuang University, 1 Bei'an Road, Zaozhuang, Shandong 277160, China.
Org Biomol Chem. 2021 Apr 7;19(13):2991-2996. doi: 10.1039/d1ob00187f. Epub 2021 Mar 18.
We report conversion of esters to thioesters via selective C-O bond cleavage/weak C-S bond formation under transition-metal-free conditions. The method is notable for a general and practical transition-metal-free system, broad substrate scope and excellent functional group tolerance. The strategy was successfully deployed in late-stage thioesterification, site-selective cross-coupling/thioesterification/decarbonylation and easy-to-handle gram scale thioesterification. Selectivity and computational studies were performed to gain insight into the formation of weak C-S bonds by C-O bond cleavage, which contrasts with the traditional trend of nucleophilic additions to carboxylic acid derivatives.
我们报告了在无过渡金属条件下通过选择性 C-O 键断裂/弱 C-S 键形成将酯转化为硫酯。该方法的特点是具有通用和实用的无过渡金属体系、广泛的底物范围和优异的官能团耐受性。该策略已成功应用于晚期硫酯化、位点选择性交叉偶联/硫酯化/脱羰以及易于处理的克级硫酯化。进行了选择性和计算研究，以深入了解 C-O 键断裂形成弱 C-S 键的情况，这与羧酸衍生物的传统亲核加成趋势形成对比。
