一锅串联法合成β-酮砜化合物及其衍生物
One-Pot Tandem Method Synthesis of β-Ketosulfone Compounds and Their Derivatives
摘要: 本文介绍了通过一锅串联法实现了从α-一溴甲基酮合成β-酮砜及其衍生类化合物的过程。在溶剂为乙醇和水(3:1/v:v)中，α-一溴甲基酮与对甲苯亚磺酸钠发生取代反应合成了β-酮砜化合物，后又分别加入硼氢化钠、盐酸羟胺、苯肼生成了β-酮砜类衍生化物，该方法溶剂绿色环保，后处理简单，产率损失较少，底物适应范围性广，所得已知化合物结构经1H NMR分析确证。
Abstract: This paper describes the synthesis of β-ketosulfones and their derivatives from α-bromomethyl ketones by a one-pot tandem method. In the solvent of ethanol and water (3:1/v:v), α-Monobro-momethyl ketone and sodium p-toluenesulfinate were substituted to synthesize β-ketosulfone compounds, and then sodium borohydride, hydroxylamine hydrochloride, and phenylhydrazine were added to form β-ketosulfone derivatives. The method has the advantages of green solvent, simple post-processing, less yield loss, wide substrate adaptability. The known compound structure was confirmed by 1H NMR analysis.
文章引用：张蕾, 古丽扎拜尔·阿不力皮孜, 阿布都热西提·阿布力克木. 一锅串联法合成β-酮砜化合物及其衍生物[J]. 化学工程与技术, 2022, 12(3): 226-233. https://doi.org/10.12677/HJCET.2022.123030

参考文献

[1] Meadows, D.C. and Gervay-Hague, J. (2006) Vinyl Sulfones: Synthetic Preparations and Medicinal Chemistry Applica-tions. Medicinal Research Reviews, 26, 793-814. [Google Scholar] [CrossRef] [PubMed]
[2] Nielsen, M., Jacobsen, C.B., Holub, N., et al. (2010) Asymmetric Organocatalysis with Sulfones. Angewandte Chemie International Edition, 49, 2668-2679. [Google Scholar] [CrossRef] [PubMed]
[3] Han, F., Su, B., Zou, F., et al. (2018) N-Bromosuccinimide Mediated Decarboxylative Sulfonylation of β-Keto Acids with Sodium Sulfinates toward β-Keto Sulfones: Evaluation of Human Carboxylesterase 1 Activity. Tetrahedron, 74, 5908-5913. [Google Scholar] [CrossRef] 
[4] Zheng, M., Li, G. and Lu, H. (2019) Photoredox- or Met-al-Catalyzed in Situ SO2-Capture Reactions: Synthesis of β-Ketosulfones and Allylsulfones. Organic Letters, 21, 1216-1220. [Google Scholar] [CrossRef] [PubMed]
[5] 谷旭晗, 彭延庆, 黄兮, 等. 微波-超声复合场辅助水介质砜类化合物合成[J]. 应用化学, 2019, 36(1): 16-23.
[6] Tao, L., Yin, C.C. and Dong, X.Q. (2019) Efficient Synthesis of Chiral β-Hydroxy Sulfones via Iridium-Catalyzed Hydro-Genation. Organic & Biomolecular Chemistry, 17, 785-788. [Google Scholar] [CrossRef] 
[7] Curti, C., Laget, M.A., Vanelle, P., et al. (2007) Rapid Syn-thesis of Sulfone Derivatives as Potential Anti-Infectious Agents. European Journal of Medicinal Chemistry, 42, 880-884. [Google Scholar] [CrossRef] [PubMed]
[8] Xiang, J., Ipek, M., Suri, V., et al. (2007) β-Keto Sulfones as Inhibitors of 11β-Hydroxysteroid Dehydrogenase Type I and the Mechanism of Action. Bioorganic & Me-dicinal Chemistry, 15, 4396-4405. [Google Scholar] [CrossRef] [PubMed]
[9] Chan, C.K., Lo, N.C., Chen, P.Y. and Chang, M.Y. (2017) An Ef-ficient Organic Electrosynthesis of β-Hydroxysulfones. Synthesis, 49, 4469-4477. [Google Scholar] [CrossRef] 
[10] Trost, B.M. and Curran, D.P. (1981) Chemoselective Oxidation of Sulfides to Sulfones with Potassium Hydrogen Per-Sulfate. Tetrahedron Letters, 22, 1287-1290. [Google Scholar] [CrossRef] 
[11] Xie, Y.Y. and Chen, Z.C. (2001) Hypervalent Iodine in Synthesis. Part 80. One-Pot Preparation of Se-(β-Oxoalkyl) O,O-Dialkyl Selenophosphates by Reaction of Ketones, [Hydroxy(tosyloxy)iodo]benzene, and Potassium O,O-Dialkyl Selenophosphates. Synthetic Communications, 31, 3145-3149. [Google Scholar] [CrossRef] 
[12] Wei, W., Liu, C.L., Yang, D.S., et al. (2013) An Exper-imentally Observed Trimetallofullerene Sm3@Ih-C80: En-Capsulation of Three Metal Atoms in a Cage without a Non-metallic Mediator. Chemical Communications, 49, 10239-10241.
[13] Chan, C.K., Wang, H.S. and Chang, M.Y. (2017) Copper Triflate Mediated α-Monohalogenation of α-Diazo β-Ketosulfones with Ammonium Halides. Synthesis, 49, 2045-2056. [Google Scholar] [CrossRef] 
[14] Chen, Y., Xu, L., Wang, B., et al. (2021), Cop-per-Catalyzed Aerobic Oxidative Cross-Coupling Reactions of Vinylarenes with Sulfinate Salts: A Direct Approach to β-Ketosulfones. Tetrahedron Letters, 65, Article ID: 152794. [Google Scholar] [CrossRef] 
[15] Grondal, C., Jeanty, M. and Enders, D. (2010) Organocatalytic Cascade Reactions as a New Tool in Total Synthesis. Nature Chemistry, 2, 167-178. [Google Scholar] [CrossRef] [PubMed]
[16] Enders, D., Grondal, C. and Huttl, M.R.M. (2007) Asymmetric Organo-catalytic Domino Reactions. Angewandte Chemie International Edition, 46, 1570-1581. [Google Scholar] [CrossRef] [PubMed]
[17] Nicolaou, K.C., Edmonds, D.J. and Bulger, P.G. (2006) Cascade Reactions in Total Synthesis. Angewandte Chemie International Edition, 45, 7134-7186. [Google Scholar] [CrossRef] [PubMed]
[18] Qiu, L., Guo, X., Ma, C., Qiu, H., Liu, S., Yang, L. and Hu, W. (2014) Efficient Synthesis of Chiral Cyclic Acetals by Metal and Brønsted Acid Co-Catalyzed Enantioselective Four-Component Cascade Reactions. Chemical Communications, 50, 2196-2198. [Google Scholar] [CrossRef] 
[19] 杨莹, 哈斯木江•巴拉提, 阿布都热西提•阿布力克木. 苯硫酚还原α,α,α-三溴甲基酮类化合物的研究[J]. 有机化学, 2019, 39(3): 727-733.
[20] 郑梦霞, 曾竟, 买里克扎提•买合木提, 阿布都热西提•阿布力克木. HBr催化α-溴代甲基酮类化合物的全脱溴反应研究[J]. 有机化学, 2021, 41(5): 2121-2126.
[21] Wang, H., Zheng, M.X., Rexit, A.A., et al. (2020) Selective Debromination of α,α,α-Tribromomethylketones with HBr-H2O Reductive Catalytic System. European Journal of Organic Chemistry, 41, 6455-6458. [Google Scholar] [CrossRef] 
[22] Gulizhabaier, A., Balati, H. and Rexit, A.A. (2021) Synthesis of α-Bromomethyl Ketones in CuBr-bpy System. Heterocycles, 102, 318-324. [Google Scholar] [CrossRef]