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Radical C(sp<sup>3</sup>)–S Coupling for the Synthesis of α-Amino Sulfides

Shengzu Duan, Yujin Zi, Ya Du, Jielun Cong, Xiaotong Sun, Jing Hong, Jingfeng Zhao, Wen Chen, Xiaodong Yang

2023Organic Letters18 citationsDOI

Abstract

A unique transition-metal-free radical thiolation of 2-azaallyl anions has been developed. Easily accessible thiosulfonates and 2-azaallyls undergo the tandem process of single-electron transfer and radical–radical coupling to construct C(sp 3 )–S bonds. This robust protocol enables a mild and chemoselective coupling between 2-azaallyl anions and thiosulfonates to access α-amino sulfides in 50–92% yields (25 examples). The scalability of this protocol was demonstrated by telescopic gram-scale experiments. Mechanistic studies provide significant evidence for this radical thiolation reaction.

Topics & Concepts

ChemistryTandemCombinatorial chemistryElectron transferCoupling (piping)Radical cyclizationRadical ionPhotochemistryMedicinal chemistryOrganic chemistryIonMaterials scienceEngineeringMechanical engineeringComposite materialSulfur-Based Synthesis TechniquesRadical Photochemical ReactionsCatalytic C–H Functionalization Methods