转自：康龙化成

Chemoselective Electrochemical Coupling of Thioethers and Primary Amines for Accessing Sulfilimines and Sulfoximines

Sukwoo Lee, Jonas Rein, Evan A. Weingarten, and Song Lin* 

Department of Chemistry and Chemical Biology, Cornell University, Ithaca, New York 14853, United States

—J. Am. Chem. Soc. 2025, 10.1021/jacs.5c04012

Recommended by Rui Jin_MC5

KEY WORDS:electro chemistry, oxidation,chemoselective (反应类型), S-N, S=O(成键类型), thioethers, amine hydrochloride salts (原料), sulfilimines, sulfoximines, isopeptides (产物), cyclic voltammetry, protonation state, convergent paired electrolysis, high-throughput electrosynthesis, small photoelectronic electrochemical synthesizers (SPECS) (其他) 

ABSTRACT: The authors report the electrooxidative coupling of thioethers with primary alkylamines, furnishing structurally diverse sulfilimines and sulfoximines including unconventional isopeptides. Cyclic voltammetry and control experiments revealed that modulating the protonation states of reactants and products is key to achieving chemoselective oxidation.

Background and this work

Condition Screening

Substrate scope

Proposed mechanism and stereochemical integrity of pre-existing stereocenters

In summary, Prof. Song Lin et al.report the electrosynthesis of sulfilimines and sulfoximines from readily available thioethers and amine hydrochloride salts. This selective transformation is achieved by controlling the oxidation potentials of substrates and products through varying their protonation states in a convergent paired electrolysis.

康奈尔大学林松课题组开发了一种利用易得原料硫醚与胺盐酸盐的电化学偶联合成硫亚胺和亚磺酰亚胺的方法。研究团队创新性地利用电化学氧化实现硫醚与一级烷基胺的直接S−N偶联，通过调节反应物和产物的质子化状态，实现了化学选择性氧化。值得注意的是，该方法还可用于合成具有磺氧化亚胺键的异肽，为肽化学提供了新途径，有望在药物研发中得到广泛应用。此外，通过进一步氧化硫亚胺产物，可方便地制备相应的磺氧化亚胺化合物，为合成更多含硫-氮功能团的复杂分子提供了可能。

（转自：康龙化成）