Organophosphorus-Catalyzed Direct Dehydroxylative Thioetherification of Alcohols with Hypervalent Organosulfur Compounds (original) (raw)

Gang Sun, Shi-Ping Zhan, Yi-Feng Zhao, Xingyi Du, Mao-Ying Shi, Jing Li, Haoliang Yuan, Xiaoan Wen, Hongbin Sun*, Qing-Long Xu*

*State Key Laboratory of Natural Medicines, China Pharmaceutical University, 24 Tongjia Xiang, Nanjing 210009, China, Email: hongbinsuncpu.edu.cn, qlxucpu.edu.cn

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.

DOI: 10.1021/acs.joc.3c02175

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Abstract

PIII/PV=O redox cycling enables a one-step dehydroxylative thioetherification of alcohols with various hypervalent organosulfur compounds. This method offers excellent functional group tolerance, broad substrate scope, and scalability.

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proposed mechanism

Details

The article discusses a novel, metal-free, and thiol-free method for synthesizing thioethers using organophosphorus catalysis. This method leverages PIII/PV redox cycling to achieve one-step dehydroxylative thioetherification of alcohols with hypervalent organosulfur compounds. The approach is notable for its excellent functional group tolerance and broad substrate scope, including inactivated alcohols. The method also allows for scale-up reactions and further product transformations, making it a step-efficient and protecting-group-free strategy for synthesizing peroxisome proliferator-activated receptor (PPAR) agonists, which show potential for treating osteoporosis in mammals. Traditional methods for thioether synthesis often involve multiple steps, hazardous reagents, and generate side products, whereas this new method simplifies the process and improves efficiency. The study also explores the scope of sodium arenesulfinates and various alcohols, demonstrating good yields and functional group tolerance. Additionally, the method's utility is proven through the synthesis of biologically valuable targets, offering a shorter and higher-yielding route compared to previous methods. The article concludes that this protocol, characterized by mild reaction conditions and broad applicability, holds promise for diverse transformations in organic synthesis.

Organophosphorus-Catalyzed "Dual-Substrate Deoxygenation" Strategy for C-S Bond Formation from Sulfonyl Chlorides and Alcohols/Acids

G. Sun, J. Li, X. Liu, Y. Liu, X. Wen, H. Sun, Q.-L. Xu, J. Org. Chem., 2023, 88, 8628-8635.

Key Words

benzylsulfides,phenylsilane,organocatalysis

ID: J42-Y2024