Organophosphorus-Catalyzed "Dual-Substrate Deoxygenation" Strategy for C-S Bond Formation from Sulfonyl Chlorides and Alcohols/Acids
Gang Sun, Jing Li, Xin Liu, Yiting Liu, Xiaoan Wen, Hongbin Sun* and Qing-Long Xu*
*State Key Laboratory of Natural Medicines, China Pharmaceutical University, 24 Tongjia Xiang, Nanjing 210009, China,
Email: hongbinsun
cpu.edu.cn, qlxucpu.edu.cn
G. Sun, J. Li, X. Liu, Y. Liu, X. Wen, H. Sun, Q.-L. Xu, J. Org. Chem., 2023, 88, 8628-8635.
DOI: 10.1021/acs.joc.3c00532
Abstract
An organophosphorus-catalyzed umpolung reaction achieves the deoxygenation of sulfonyl chlorides and alcohols/acids to synthesize thioethers/thioesters driven by PIII/PV=O redox cycling. This operationally simple approach uses a stable phosphine oxide as a precatalyst and shows broad functional group tolerance.
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proposed mechanism
General Procedure
To an oven-dried 25 mL Schlenk tube equipped with a stir bar was successively added the sulfonyl chloride (1.0 equiv.), alcohol (1.5 equiv.) and catalyst I (10 mol%). The Schlenk tube was evacuated and refilled with dry argon (three times). 1,2-dimethoxyethane (DME) (5 mL) and phenylsilane (PhSiH3) (3.0 equiv.) dissolved in DME (1 mL) were then successively added by syringe. The mixture was warmed up to 85 °C and stirred for 45 min. N,N-Diisopropylethylamine (DIPEA) (1.5 equiv.) was added and stirring was continued for 1 h at 85 °C. The reaction was concentrated under reduced pressure. The residue was purified by column chromatography.
G. Sun, S.-P. Zhang, Y.-F. Zhao, Y. Du, M.-Y. Shi, J. Li, H. Yuan, X. Wen, H. Sun, Q.-L. Xu, J. Org. Chem., 2024, 89, 1083-1090.
Key Words
reduction of sulfonyl chlorides, benzylsulfides, thioesters, organocatalysis, phenylsilane
ID: J42-Y2023
