四丁基碘化铵/过硫酸钾体系促进硝基烯烃与磺酰肼脱硝磺酰化反应合成(E)-β-烯基砜

doi:10.11944/j.issn.1000-0518.2019.06.180338

摘要/Abstract

摘要：

发展了一种硝基烯烃与磺酰肼脱硝磺酰化反应合成(E)-β-烯基砜。以四丁基碘化铵(TBAI)/过硫酸钾(K₂S₂O₈)为催化氧化体系,多种硝基苯乙烯衍生物与取代磺酰肼发生自由基加成/脱硝基反应,以中等到良好的收率获得各种(E)-β-烯基砜。反应具有底物适用范围广、反应操作简单、无金属催化及中性反应条件等优点,为含β-烯基砜类化合物的合成提供了一条高效、简单、环境友好的新途径。

关键词: (E)-β-烯基砜;, 硝基烯烃, 磺酰肼, 脱硝/磺酰化, 自由基反应

Abstract:

A novel and efficient protocol towards (E)-β-vinyl sulfone derivatives by tetrabutylammonium Iodide(TBAI)/K₂S₂O₈ mediated denitrative sulfonylation of readily prepared β-nitrostyrenes and economical sulfonylhydrazides was described. The corresponding (E)-β-vinyl sulfone compounds were obtained in moderate to good yields. Compared with reported methods, the present strategy features metal-free, acid and base-free.

Key words: (E)-β-vinyl sulfone;, β-nitrostyrenes;, sulfonylhydrazides, denitrative sulfonylation, radical reaction

唐裕才, 王萍, 冉书童, 陈飘. 四丁基碘化铵/过硫酸钾体系促进硝基烯烃与磺酰肼脱硝磺酰化反应合成(E)-β-烯基砜[J]. 应用化学, 2019, 36(6): 664-670.

TANG Yucai, WANG Ping, RAN Shutong, CHEN Piao. Synthesis of (E)-β-Vinyl Sulfones by Metal-Free Tetrabutylammonium Iodide/Potassium Persulfate Mediated Radical Denitrative Sulfonylation of β-Nitrostyrenes with Sulfonylhydrazides[J]. Chinese Journal of Applied Chemistry, 2019, 36(6): 664-670.

参考文献

[1]	Peter D V,Carlos M.Pharmacological Aspects of Experimental Headache Models in Relation to Acute Antimigraine Therapy[J]. Eur J Pharmacol,1999,375(1):61-74.
[2]	Cassani C,Bernardi L,Fini F,et al. Catalytic Asymmetric Mannich Reactions of Sulfonylacetates[J]. Angew Chem Int Ed,2009,48(31):5694-5697.
[3]	Sikervar V,Fleet J C,Fuchs P L.A General Approach to the Synthesis of Enantiopure 19-nor-Vitamin D3 and Its C-2 Phosphate Analogs Prepared from Cyclohexadienyl Sulfone[J]. Chem Commun,2012,48(72):9077-9079.
[4]	Doherty W,Adler N,Knox A,et al. Synthesis and Evaluation of 1,2,3-Triazole-Containing Vinyl and Allyl Sulfones as Anti-trypanosomal Agents[J]. Eur J Org Chem,2017,2017(1):175-185.
[5]	Liu S,Zhou B,Yang H,et al. Aryl Vinyl Sulfonates and Sulfones as Active Site-Directed and Mechanism-Based Probes for Protein Tyrosine Phosphatases[J]. J Am Chem Soc,2008,130(26):8251-8260.
[6]	Zhu Q,Lu Y.Enantioselective Conjugate Addition of Nitroalkanes to Vinyl Sulfone:An Organocatalytic Access to Chiral Amines[J]. Org Lett,2009,11(8):1721-1724.
[7]	Trost B M,Curran D P.Chemoselective Oxidation of Sulfides to Sulfones with Potassium Hydrogen Persulfate[J]. Tetrahedron Lett,1981,22(14):1287-1290.
[8]	Popoff I C,Dever J L,Leader G R.Alpha, beta.-Unsaturated Sulfones via Phosphonate Carbanions[J]. J Org Chem,1969,34(4):1128-1130.
[9]	Chodroff S,Whitmore W F.The Preparation of Unsaturated Sulfones by Condensation Reactions[J]. J Am Chem Soc,1950,72(3):1073-1076.
[10]	Gancarz R A,Kice J L.Photodecomposition of Selenosulfonates and Their Facile Photoaddition to Alkenes 1[J]. Tetrahedron Lett,1980,21(43):4155-4158.
[11]	Zhan Z,Ma H,Wei D,et al. Metal-Free Catalyzed Synthesis of the (E)-Vinyl Sulfones via Aromatic Olefins with Arylsulfonyl Hydrazides[J]. Tetrahedron Lett,2018,59(14):1446-1450.
[12]	Xue Q,Mao Z J,Shi Y,et al. Metal-Free, One-Pot Highly Selective Synthesis of (E)-Vinyl Sulfones and Sulfoxides via Addition Oxidation of Thiols with Alkynes[J]. Tetrahedron Lett,2012,53(14):1851-1854.
[13]	Xu Y,Tang X,Hu W,et al. Transition-Metal-Free Synthesis of Vinyl Sulfones via Tandem Cross-Decarboxylative/Coupling Reactions of Sodium Sulfinates and Cinnamic Acids[J]. Green Chem,2014,16(8):3720-3723.
[14]	Li X,Xu Y,Jiang C,et al. Copper-Catalyzed Aerobic Oxidative N-S Bond Functionalization for C-S Bond Formation:Regio- and Stereoselective Synthesis of Sulfones and Thioethers[J]. Chem Eur J,2014,20(26):7911-7915.
[15]	Tang S,Wu Y,Liao W,et al. Revealing the Metal-Like Behavior of Iodine:An Iodide-Catalysed Radical Oxidative Alkenylation[J]. Chem Commun,2014,50(34):4496-4499.
[16]	Gao J,Lai J,Yuan G.Iodine-Mediated Synthesis of (E)-Vinyl Sulfones from Sodium Sulfinates and Cinnamic Acids in Aqueous Medium[J]. RSC Adv,2015,5(82):66723-66726.
[17]	Twinkle K,Ritu K,Yadav L.Silver-Catalyzed Denitrative Sulfonylation of β-Nitrostyrenes:A Convenient Approach to (E)-Vinyl Sulfones[J]. Eur J Org Chem,2016,2016(15):2695-2699.
[18]	Xu X,Hu P,Yu W,et al. Bu4NI-Catalyzed Synthesis of Imidazo [1,2-a]pyridines via Oxidative Coupling of Aminopyridines with Nitroolefins[J]. Synlett,2014,25(5):718-720.
[19]	Yang X,Zhao L,Yuan B,et al. TBAI/K2S2O8 Initiated Radical Cyclization to Synthesize β-Arylsulfonyl Naphthalenes from Homopropargylic Alcohols and Sulfonyl Hydrazides[J]. Adv Synth Catal,2017,359(18):3248-3253.