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非对称环硫乙烷的区域选择性亲核开环反应

周婵, 许家喜*   

  1. 北京化工大学理学院有机化学系 化工资源有效利用国家重点实验室 北京 100029
  • 收稿日期:2011-07-01 修回日期:2011-09-01 出版日期:2012-03-24 发布日期:2011-11-25
  • 通讯作者: 许家喜 E-mail:jxxu@mail.buct.edu.cn
  • 基金资助:

    国家自然科学基金项目(No.20972013,20472005)资助

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导出 被引次数 ( 11 | 2 )

Regioselective Nucleophilic Ring Opening Reactions of Unsymmetric Thiiranes

Zhou Chan, Xu Jiaxi*   

  1. State Key Laboratory of Chemical Resource Engineering, Department of Organic Chemistry, Faculty of Science, Beijing University of Chemical Technology, Beijing 100029, China
  • Received:2011-07-01 Revised:2011-09-01 Online:2012-03-24 Published:2011-11-25
环硫乙烷与它的氧类似物环氧乙烷和氮类似物氮杂环丙烷一样,是一类重要的有机合成中间体,在医药和农用化学品工业领域也得到广泛应用。通过开环和异构化反应,还广泛用于制备硫醇和硫醚等含硫化合物。本文总结了常用亲核试剂对非对称环硫乙烷的亲核开环反应及其区域选择性。环硫乙烷的亲核开环反应通常只受空间效应影响,亲核试剂进攻非对称环硫乙烷位阻小的碳原子,对于烯基取代的环硫乙烷有时可以进攻烯基的β碳原子发生SN2'开环反应。强亲核性的亲核试剂容易致使环硫乙烷脱硫生成烯烃,而亲核性相对较弱的亲核试剂容易发生多聚反应生成多硫醚。在Lewis酸存在下,电子效应会对开环反应的区域选择性产生影响,甚至起主导作用。虽然烷基取代环硫乙烷在Lewis酸存在下的开环仍然主要发生在其取代基少的碳原子上(位阻控制),但受电子效应影响,芳基和烯基取代环硫乙烷的亲核开环,其亲核试剂一般倾向于进攻环硫乙烷的芳甲位和烯丙位碳原子(电子效应控制)。
关键词： 环硫乙烷, 亲核试剂, 开环, 区域选择性
Thiiranes are a class of important intermediates in organic synthesis, as well in pharmaceutical and agrochemical industries as their oxygen analogs oxiranes and nitrogen analogs aziridines. They have been widely applied in the preparation of sulfur-containing compounds, such as diverse thiols and thioethers and so on, via ring opening reaction and isomerization. Nucleophilic ring opening reactions of unsymmetric thiiranes and their regioselectivity with various widely used nucleophiles are reviewed. Generally, nucleophilic ring opening reactions of unsymmetric thiiranes occur on their less substituted carbon atom, controlled by the steric hindrance. 2-Alkenylthiiranes can undergo an SN2' ring opening reaction in some cases via the attack on the β-carbon atom of their alkenyl group. Strong nucleophiles easily lead to desulfurization of thiiranes to afford the corresponding olefins, while the relatively weak nucleophiles readily result in polymerization of thiiranes, affording polythioethers. In the presence of Lewis acid, the electronic effect affects the regioselectivity in ring opening reactions, even as the prominent effect in the reactions. Although aliphatic thiiranes are still attacked predominantly on their less substituted carbon atom with nucleophiles (the steric hindrance control), aromatic thiiranes and 2-alkenylthiiranes are attacked on their more substituted carbon atom with nucleophiles (the electronic effect control). The current review provides a general rule for the regioselectivity of the nucleophilic ring opening reaction of unsymmetric thiiranes. Contents
1 Introduction
2 Ring opening of thiiranes by carbon nucleophiles
2.1 Ring opening by organometallic reagents
2.2 Ring opening by benzyne
2.3 Ring opening by cyanide
3 Ring opening of thiiranes by nucleophiles in the nitrogen group
3.1 Ring opening by nitrogen-containing nucleophiles
3.2 Ring opening by phosphines
4 Ring opening of thiiranes by nucleophiles in the oxygen group
4.1 Ring opening by oxygen-containing nucleophiles
4.2 Ring opening by sulfur-containing nucleophiles
5 Ring opening of thiiranes by halogen nucleophiles
6 Ring opening of thiiranes by transition metal complexes
7 Ring opening of thiiranes by hydride anion
8 Conclusion and outlook
Key words: thiirane, nucleophile, nucleophilic ring opening reaction, regioselectivity

中图分类号: 

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[1] Mauro P, Ferruccio B, Valeria D B, Paolo C. Curr. Org. Synth., 2009, 6: 290-324
[2] Christoph S. Synthesis, 2006, (23): 3919-3944
[3] Mauro P. Eur. J. Org. Chem., 2006, (22): 4979-4988
[4] Pastor I M, Yus M. Curr. Org. Chem., 2005, 9: 1-29
[5] Chemla F, Ferreira F. Curr. Org. Chem., 2002, 6: 539-570
[6] Krake S H, Bergmeier S C. Tetrahedron, 2010, 66: 7337-7360
[7] Lu P F. Tetrahedron, 2010, 66: 2549-2560
[8] Christoph S. Angew. Chem. Int. Ed., 2009, 48: 2082-2084
[9] Hu X E. Tetrahedron, 2004, 60: 2701-2743
[10] 马琳鸽(Ma L G), 许家喜(Xu J X). 化学进展(Progress in Chemistry), 2004, 16: 220-235
[11] 周婵(Zhou C), 许家喜(Xu J X). 化学进展(Progress in Chemistry), 2011, 23: 174-189
[12] Quirk R P, Ocampo M, Polce M J, Wesdemiotis C. Macromolecules, 2007, 40: 2352-2360
[13] Trost B M, Ziman S D. J. Org. Chem., 1973, 38: 932-936
[14] Ongoka P, Mauze B, Miginiac L. Synthesis, 1985, 1069-1070
[15] Briinalt J, Kvarnstram I, Svensson C T. J. Org. Chem., 1994, 59: 4430-4432
[16] Nakayama J, Takeue S, Hoshino M. Tetrohedron Lett., 1984, 25: 2679-2682
[17] Taddei M, Papini A, Piorenza M, Ricci A. Tetrohedron Lett., 1983, 24: 2311-2314
[18] Huang J X, Wang F, Du D M, Xu J X. Synthesis, 2005, (13): 2122-2128
[19] Howy R, Enechi F. J. Org. Chem., 1973, 38: 2405-2407
[20] Huang J X, Du D M, Xu J X. Synthesis, 2006, 2: 315-319
[21] Yu H, Cao S L, Zhang L L, Liu G, Xu J X. Synthesis, 2009, (13): 2205-2209
[22] Li X Y, Xu J X. Tetrahedron, 2011, 67: 1681-1688
[23] Sander M. Chem. Rev., 1965, 297-339
[24] Snyder H R, Stewart J M, Ziegler J B. J. Am. Chem. Soc., 1947, 69: 2672-2674
[25] Wright J B. J. Am. Chem. Soc., 1957, 79: 1694-1696
[26] Birk C, Voss J. Tetrahedron, 1996, 52: 12745-12760
[27] Turk S D, Louthanr R P, Cobb R L, Bresson C R. J. Org. Chem., 1964, 29: 974-975
[28] Guseinova A T, Magerramov A M, Allakhverdiev M A. Russ. J. Org. Chem., 2008, 44: 946-949
[29] Kakiuchi H, Iuima T, Horie H. Tetrahedron, 1979, 35: 303-308
[30] Dong Q, Fang X Q, Schroeder J D, Garvey D S. Synthesis, 1999, 7: 1106-1108
[31] Banks H D, White W E. J. Org. Chem., 2001, 66: 5981-5986
[32] Peng Q, Zhong Z L, Zhuo R X. Bioconjugate Chem., 2008, 19: 499-506
[33] Dwivedi A K, Sharma V L, Kumaria N, Kumar S T, Srivastava P K, Ansari A H, Maikhuri J P, Gupta G, Dhar J D, Roy R J, Joshi B S, Shukla P K, Kumar M, Singh S. Bioorg. Med. Chem., 2007, 15: 6642-6648
[34] Spogli R, Sabatini S, Manfroni G, Tabarrini O, Cecchetti V. Synthesis-Stuttgart, 2009, 9: 1513-1519
[35] Stewart J M. J. Org. Chem., 1963, 28: 596-598
[36] Guseinova A T, Aliev K I, Sadatova S S, Farzaliev V M, Allakhverdiev M A. Russ. J. Applied Chem., 2009, 82: 1251-1254
[37] Harfouche J, Herault D, Tommasino M L, Rostaing S P, Lemaire M. Tetrahedron: Asymmetry, 2004, 15: 3413-3418
[38] Vasilyeva S A, Kalimullina L K, Safarov M G. Chem. Heterocycl. Compounds, 2003, 39: 174-178
[39] Klen E E, Khaliullin F A. Russ. J. Org. Chem., 2009, 45: 468-469
[40] Denney D B, Boskin M J. J. Am. Chem. Soc., 1960, 82: 4376-4378
[41] Brugat N, Duran J, Polo A, Real J, Larena A A, Piniella J F. Tetrahedron: Asymmetry, 2002, 13: 569-577
[42] Dervisi A, Jenkins R L, Malik K M A, Hursthouse M B, Coles S. J. Chem. Soc. Dalton Trans., 2003, 1133-1142
[43] Iranpoor N, Shekarriz M, Shiriny F. Synth. Commun., 1998, 28: 347-366
[44] Iranpoor N, Owji J. Synth. Commun., 1990, 20: 1047-1053
[45] Iranpoor N, Firouzabadi H, Chitsazi M, Jafari A A. Tetrahedron, 2002, 58: 7037-7042
[46] Tamami B, Iranpoor N, Mahdavi H. Synth. Commun., 2002, 32: 1251-1258
[47] Hughes N A. Carbohydrate Res., 2000, 326: 323-325
[48] Uenishi J, Ohmiya H. Tetrahedron, 2003, 59: 7011-7022
[49] Zunszain P A, Varela O. Tetrahedron: Asymmetry, 2000, 11: 765-771
[50] Varela O, Zunszain P A. J. Org. Chem., 1993, 58: 7860-7864
[51] Tomashevskii A A, Sokolov V V, Potekhin A A. Russ. J. Org. Chem., 2003, 39: 226-234
[52] Vergizova T V, Rodin A A, V'yunov K A, Ginak A I, Leningr T I. Zhurnal Organicheskoi Khimii, 1984, 20: 2220-2224 (Chem Abst., 1984, 102: 95015)
[53] Vergizova T V, Rodin A A, Frolova G M, Zenkevich I G, V'yunov K A, Ginak A I, Leningr T I. Zhurnal Organicheskoi Khimii, 1985, 21: 1210-1214 (Chem. Abst., 1985, 104: 148416)
[54] Vergizova T V, Rodin A A, V'yunov K A, Ginak, A I, Leningr T I. Zhurnal Organicheskoi Khimii, 1986, 22: 1396-1399 (Chem. Abst.1986, 106: 119025)
[55] Funahashi K. Chem. Lett., 1978, 1043-1044
[56] Montigny F D, Bast R, Gomes A S P, Pilet G, Vanthuyne N, Roussel C, Guy L, Schwerdtfeger P, Saue T, Crassous J. Phys. Chem. Chem. Phys., 2010, 12: 8792-8803
[57] Helten H, Schirmeister T, Engels B. J. Phys. Chem. A, 2004, 108: 7691-7701
[58] Helten H, Schirmeister T, Engels B. J. Org. Chem., 2005, 70: 233-237
[59] Takeuchi H, Nakajima Y. J. Chem. Soc. Perkin Trans., 1998, 2: 2441-2446
[60] Reddy M S, Surendra K, Krishnaveni N S, Narender M, Rao K R. Helv. Chim. Acta, 2007, 90: 337-339
[61] Kameyama A, Kiyota M, Nishikubo T. Tetrahedron Lett., 1994, 35: 4571-4574
[62] Kudo H, Sato K, Nishikubo T. Macromolecules, 2010, 43: 9655-9659
[63] Kudo H, Makino S, Kameyama A, Nishikubo T. Macromolecules, 2005, 38: 5964-5969
[64] Adams R D, Perrin J L. J. Am. Chem. Soc., 1999, 121: 3984-3991
[65] Lupton D W, Taylor D K. Tetrahedron, 2002, 58: 4517-4527
[66] Li W S, Shen Z Q, Zhang Y F. Eur. Polymer J., 2001, 37: 1185-1190
[67] Ren X F, Konaklieva M I, Turos E, Krajkowski L M, Lake C H, Janik T S, Churchillt M R. J. Org. Chem., 1996, 60: 6484-6495
[68] Silvestri M G, Wong C H. J. Org. Chem., 2001, 66: 910-914
[69] Komiya S, Muroi S Y, Furuya M, Hirano M. J. Am. Chem. Soc., 2000, 122: 170-171
[70] Calet S, Alper H, Petrignani J F, Arzoumanian H. Organometallics, 1987, 6: 1625-1628
[71] Larksarp C, Sellier O, Alper H. J. Org. Chem., 2001, 66: 3502-3506
[72] Jacobs R L, Shuetz R D. J. Org. Chem., 1961, 26: 3472-3476
[73] Bordwell F G, Andersen H M, Pitt B M. J. Am. Chem. Soc., 1954, 76: 1082-1085
[74] Weckerle B, Schreier P, Humpf H U. J. Org. Chem., 2001, 66: 8160-8164
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