轉自：康龍化成

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 (反應類型), S-N, S=O(成鍵類型), thioethers, amine hydrochloride salts (原料), sulfilimines, sulfoximines, isopeptides (產物), 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.

康奈爾大學林松課題組開發了一種利用易得原料硫醚與胺鹽酸鹽的電化學偶聯合成硫亞胺和亞磺酰亞胺的方法。研究團隊創新性地利用電化學氧化實現硫醚與一級烷基胺的直接S?N偶聯，通過調節反應物和產物的質子化狀態，實現了化學選擇性氧化。值得注意的是，該方法還可用于合成具有磺氧化亞胺鍵的異肽，為肽化學提供了新途徑，有望在藥物研發中得到廣泛應用。此外，通過進一步氧化硫亞胺產物，可方便地制備相應的磺氧化亞胺化合物，為合成更多含硫-氮功能團的復雜分子提供了可能。

（轉自：康龍化成）

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