电化学条件下磺酰肼与烯醇硅醚自由基偶联反应合成β-羰基砜化合物
Synthesis of β-Carbonyl Sulfone Compounds by the Free Radical Coupling Reaction of Sulfonyl Hydrazide and Enol Silyl Ether under Electrochemical Conditions
DOI: 10.12677/SSC.2021.91001, PDF,   
作者: 王杨丽, 周 烨, 曾东文, 何永辉*：云南民族大学，民族医药学院，云南 昆明
关键词: β-羰基砜；电催化；自由基偶联反应；β-Carbonyl Sulfone； Electrocatalysis； Radical Coupling Reaction
摘要: β-羰基砜是一类重要的有机合成砌块，合成该类化合物一直是研究热点。本文以四丁基碘化铵为媒介，在电化学条件下实现烯醇硅醚与各种取代的磺酰肼发生自由基磺酰化反应，经自由基加成和氧化，在最优条件下以55%~76%的收率合成了8种具有不同取代基的β-羰基砜类化合物。采用核磁共振和质谱等手段对产物结构进行表征，并提出了可能的反应机理。
Abstract: β-carbonyl sulfone is a kind of important organic synthesis block, and the synthesis of this kind of compounds has been a research hotspot. In this paper, β-carbonyl sulfones with different substi-tuents were synthesized by the free radical sulfonation of enol silyl ethers with various substituted sulfonyl hydrazides in the medium of tetrabutylammonium iodide under electrochemical conditions. Through radical addition and oxidation, eight β-carbonyl sulfones with different subs-tituents were synthesized in 55%~76% yield under the optimal conditions. The products were characterized by NMR and MS, and the possible reaction mechanism was proposed.
文章引用：王杨丽, 周烨, 曾东文, 何永辉. 电化学条件下磺酰肼与烯醇硅醚自由基偶联反应合成β-羰基砜化合物[J]. 合成化学研究, 2021, 9(1): 1-7. https://doi.org/10.12677/SSC.2021.91001

参考文献

[1] Wolf, W.M. (1999) The Fungicidal Activity of β-Keto Sulfones. Molecular Conformation of α-Phenylhydrazono- β-Ketosulfones as Determined by an X-Ray Analysis. Journal of Molecular Structure, 474, 113-124. [Google Scholar] [CrossRef] 
[2] Ma, M., Cheng, Y., Xu, Z., Xu, P., Qu, H., Fang, Y., Xu, T. and Wen, L. (2007) Evaluation of Polyamidoamine (PAMAM) Dendrimers as Drug Carriers of Anti-Bacterial Drugs Using Sulfamethoxazole (SMZ) as a Model Drug. European Journal of Medicinal Chemistry, 42, 93-98. [Google Scholar] [CrossRef] [PubMed]
[3] Ihara, M., Suzuki, S., Taniguchi, T., Tokunaga, Y. and Fuku-moto, K. (1995) Preparation of Olefins and Acetylenes via Reductive Elimination with SmI2-HMPA. Tetrahedron, 51, 9873-9890. [Google Scholar] [CrossRef] 
[4] Marco, J.-L., Fernandez, I., Khiar, N., Fernandez, P. and Romero, A. (1995) Michael Additions of Alpha.-Sulfinyl and Alpha.-Sulfonyl Carbanions: The Unprecedented Reaction of Beta.-Keto Sulfoxides and Beta.-Keto Sulfones with Highly Stabilized Michael Acceptors. The Journal of Organic Chemistry, 60, 6678-6679. [Google Scholar] [CrossRef] 
[5] Sengupta, S., Sen Sarma, D. and Mondal, S. (1998) γ-Chiral β-Ketosulfones in Asymmetric Synthesis: A Unified Synthetic Strategy for Enantiopure γ-Amino and γ-Hydroxy Vinyl Sulfones. Tetrahedron: Asymmetry, 9, 2311-2316. [Google Scholar] [CrossRef] 
[6] Gotor, V., Rebolledo, F. and Liz, R. (2001) Enantioselective Bioreduction of β-Keto Sulfones with the Fungus Curvularia lunata. Tetrahedron: Asymmetry, 12, 513-515. [Google Scholar] [CrossRef] 
[7] Lu, Q., Zhang, J., Zhao, G., Qi, Y., Wang, H. and Lei, A. (2013) Dioxygen-Triggered Oxidative Radical Reaction: Direct Aerobic Difunctionalization of Terminal Alkynes toward β-Keto Sulfones. Journal of the American Chemical Society, 135, 11481-11484. [Google Scholar] [CrossRef] [PubMed]
[8] Singh, A.K., Chawla, R. and Yadav, L.D.S. (2014) Aerobic Oxysulfony-lation of Alkynes in Aqueous Media: Highly Selective Access to β-Keto Sulfones. Tetrahedron Letters, 55, 2845-2848. [Google Scholar] [CrossRef] 
[9] Tang, Y., Zhang, Y., Wang, K., Li, X., Xu, X. and Du, X. (2015) Tetrabutylammonium Iodide-Catalyzed Oxidative Coupling of Enamides with Sulfonylhydrazides: Synthesis of β-Keto-Sulfones. Organic & Biomolecular Chemistry, 13, 7084-7090. [Google Scholar] [CrossRef] 
[10] Cai, S., Chen, D., Xu, Y., Weng, W., Li, L., Zhang, R. and Huang, M. (2016) Visible-light-promoted syntheses of β-keto sulfones from alkynes and sulfonylhydrazides. Organic & Biomo-lecular Chemistry, 14, 4205-4209. [Google Scholar] [CrossRef] 
[11] Liu, C., Ding, L., Guo, G. and Liu, W. (2016) Oxysulfonylation of Alkenes with Sulfonyl Hydrazides under Transition-Metal-Free Conditions. European Journal of Organic Chemistry, 2016, 910-912. [Google Scholar] [CrossRef] 
[12] Chen, W., Liu, X., Chen, E., Chen, B., Shao, J. and Yu, Y. (2017) KI-Mediated Radical Multi-Functionalization of Vinyl Azides: A One-Pot and Efficient Approach to β-Keto Sulfones and α-Halo-β-Keto Sulfones. Organic Chemistry Frontiers, 4, 1162-1166. [Google Scholar] [CrossRef] 
[13] Wu, J., Zhang, Y., Gong, X., Meng, Y. and Zhu, C. (2019) Visi-ble-Light Promoted Aerobic Difunctionalization of alkenes with Sulfonyl Hydrazides for the Synthesis of β-Keto/Hydroxyl Sulfones. Organic & Biomolecular Chemistry, 17, 3507-3513. [Google Scholar] [CrossRef] 
[14] Chen, J., Allyson, Z.G., Xin, J.-R., Guan, Z. and He, Y.-H. (2020) Photo-Mediated Decarboxylative Ketonization of Atropic Acids with Sulfonyl Hydrazides: Direct Access to β-Ketosulfones. Advanced Synthesis & Catalysis, 362, 2045-2051. [Google Scholar] [CrossRef] 
[15] Li, G., Kong, X., Liang, Q., Lin, L., Yu, K., Xu, B. and Chen, Q. (2020) Metal-Free Electrochemical Coupling of Vinyl Azides: Synthesis of Phenanthridines and β-Ketosulfones. European Journal of Organic Chemistry, 2020, 6135-6145. [Google Scholar] [CrossRef] 
[16] 唐裕才, 屈煌, 张文熙, 王菲菲, 王钢. 无金属条件下I2 /TBHP体系促进磺酰肼与烯醇硅醚自由基偶联反应合成α-磺酰基酮[J]. 高等学校化学学报, 2020, 41(1): 118-124.
[17] Xiong, P. and Xu, H.-C. (2019) Chemistry with Electrochemically Generated N-Centered Radicals. Accounts of Chemical Research, 52, 3339-3350. [Google Scholar] [CrossRef] [PubMed]
[18] Yuan, Y. and Lei, A. (2019) Electrochemical Oxidative Cross-Coupling with Hydrogen Evolution Reactions. Accounts of Chemical Research, 52, 3309-3324. [Google Scholar] [CrossRef] [PubMed]

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