Chongqing Key Laboratory of Natural Product Synthesis and Drug Research, School of Pharmaceutical Sciences, Chongqing University, Chongqing 401331, P. R. China.
Org Biomol Chem. 2019 Jan 31;17(5):1121-1129. doi: 10.1039/c8ob02967a.
A metal-free difunctionalization of alkynes to access tetrasubstituted olefins through spontaneous selenosulfonylation of vinylidene ortho-quinone methide (VQM) was described herein. The reaction was conducted under mild conditions without any catalysts or additives. Preliminary mechanism studies revealed that the formation of VQM was the key for this alkyne di-functionalization reaction. The reaction could be applied in the enantioselective asymmetric synthesis of axially chiral styrene. Furthermore, the selenosulfonylation adducts can be transformed into useful naphtho[2,1-b]furan and benzofuran scaffolds.
本文描述了一种通过乙烯基亚甲基邻醌甲亚胺（VQM）的自发硒磺酰化反应，实现炔烃的无金属双官能化，从而构建四取代烯烃的方法。该反应在温和条件下进行，无需任何催化剂或添加剂。初步的机理研究表明，VQM 的形成是实现该炔烃双官能化反应的关键。该反应可应用于轴手性苯乙烯的对映选择性不对称合成。此外，硒磺酰化加成物可以转化为有用的萘[2,1-b]呋喃和苯并呋喃骨架。
