English
往期目录
新闻公告
More
化学进展 2011, Vol. 23 Issue (01): 165-180 前一篇   后一篇

• 综述与评论 •

非对称环氧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:2010-06-01 修回日期:2010-09-01 出版日期:2011-01-20 发布日期:2011-09-02
  • 作者简介: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

下载PDF ( 105066 ) 引用
导出 被引次数 ( 35 | 9 )

Regioselective Nucleophilic Ring Opening Reactions of Unsymmetric Oxiranes

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:2010-06-01 Revised:2010-09-01 Online:2011-01-20 Published:2011-09-02

本文总结了常用亲核试剂对非对称环氧乙烷的亲核开环反应及其区域选择性。强亲核性的亲核试剂通常只受空间效应影响,进攻非对称环氧乙烷位阻小的碳原子,对于烯基取代环氧乙烷还可以进攻烯基的β-碳原子发生SN2'开环反应,其他亲核试剂同时受空间效应和电子效应的影响,对于烷基环氧乙烷通常进攻其取代少的碳原子, 空间效应起主导作用,而对芳基和烯基取代环氧乙烷开环反应通常发生在环氧乙烷芳甲位和烯丙位的碳原子上, 电子效应起主导作用。在质子酸或强Lewis酸存在下,虽然单烷基环氧乙烷的开环仍然发生在其取代少的碳原子上,但对于芳基、烯基和同碳双取代环氧乙烷,亲核开环反应将主要受电子效应控制,一般亲核试剂倾向于进攻环氧乙烷的芳甲位、烯丙位或多取代的碳原子。分子内的亲核开环反应主要受成环时环大小的控制, 成环时的倾向是五元环> 六元环> 七元环。环氧乙烷亲核开环的区域选择性是环氧乙烷和亲核试剂空间效应和电子效应平衡的结果。

关键词： 环氧乙烷, 亲核试剂, 亲核开环, 区域选择性

Nucleophilic ring opening reactions of unsymmetric oxiranes and their regioselectivity with widely used nucleophiles are reviewed. Strong nucleophiles attack the less substituted carbon atom of unsymmetric oxiranes, whatever alkyl, alkenyl, and aryloxiranes, controlled by the steric hindrance only. They can undergo an SN2' ring-opening reaction with alkenyloxiranes via the attack on the β-carbon atom of their alkenyl group. Other nucleophiles generally attack the less substituted carbon atom for alkyloxiranes, controlled by the steric hindrance, but attack the arylmethyl and allyl carbon atom for aryl and alkenyloxiranes, controlled by the electronic effect. In the presence of proton acids or strong Lewis acids, although monoalkyloxiranes are attacked on their less substituted carbon atom with nucleophiles (steric hindrance control), aryl, alkenyl, and geminal dialkyloxiranes are attacked on their more substituted carbon atom with weak nucleophiles (electronic effect control). The regioselectivity of intramolecular nucleophilic ring opening reaction of oxiranes is controlled by the ring size of products. The favorable order is five-membered ring > six-membered ring > seven-membered ring. Thus, the regioselectivity is controlled by a balance between the steric hindrance and electronic effect of oxiranes and nucleophiles.

Key words: oxirane, nucleophile, nucleophilic ring opening reaction, regioselectivity

中图分类号: 

()

[1] Zhang W X, Ye K, Ruan S, Chen X, Xia Q H. Chin. J. Chem., 2007, 25: 1758—1761
[2] Mirkani V, Tangestaninejad S, Yadollahi B, Alipanah L. Tetrahedron, 2003, 59: 8213—8218
[3] Cristol S J, Douglouss J R, Meek J S. J. Am. Chem. Soc., 1951, 73: 816—818
[4] Parker R E, Isaacs N S. Chem. Rev., 1959, 59: 737—799
[5] Hodgson D M, Fleming M J, Stanway S J. J. Am. Chem. Soc., 2004, 126: 12250—12251
[6] Overman L E, Renhowe P A. J. Org. Chem., 1994, 59: 4138—4142
[7] Ouannes C, Dressaire G, Langlois Y. Tetrahedron Lett., 1977, 10: 815—818
[8] Ghribi A, Alexakis A, Normant J F. Tetrahedron Lett., 1984, 25: 3075—3078
[9] Mori S, Nakamura E, Morokuma K. J. Am. Chem. Soc., 2000, 122: 7294—7307
[10] Moser W H. Tetrahedron, 2001, 57: 2065—2084
[11] Smith A B, Pitram S M, Boldi A M, Gaunt M J, Moser W H. J. Am. Chem. Soc., 2003, 125: 14435—14445
[12] Brook A G. J. Am. Chem. Soc., 1958, 80: 1886—1889
[13] Takeda K, Sawada Y, Sumi K. Org. Lett., 2002, 4: 1031—1033
[14] Nicolaou K C, Prasad C V C, Somers P K, Hwang C K. J. Am. Chem. Soc., 1989, 111: 5330—5334
[15] Herr R W, Johnson C R. J. Am. Chem. Soc., 1970, 92: 4979—4981
[16] Fagnou K, Lautens M. Org. Lett., 2000, 2: 2319—2321
[17] Trost B M, Bunt R C, Lemoine R C, Calkins T L. J. Am.Chem. Soc., 2000, 122: 5968—5976
[18] Marshall J A. Chem. Rev., 1989, 89: 1503—1511
[19] Stork G, White W N. J. Am. Chem. Soc., 1953, 75: 4119—4120
[20] Magid R M. J. Org. Chem., 1971, 36: 2105—2110
[21] Stork G, Kreft A F. J. Am. Chem. Soc., 1977, 99: 3850—3851
[22] Magid R M. Tetrahedron, 1980, 36: 1901—1930
[23] Bordwell F G, Clemens A H, Cheng J P. J. Am. Chem. Soc., 1987, 109: 1773—1782
[24] Paquette L A, Stirling C J M. Tetrahedron, 1992, 48: 7383—7423
[25] Rona P, Tkes L, Tremble J, Crabbé P. J. Chem. Soc. Chem. Commun., 1969, 43—44
[26] Goering H L, Kantner S S, Seitz E P. J. Org. Chem., 1985, 50: 5495—5499
[27] Ibuka T, Nakao T, Nishii S, Yamamoto Y. J. Am. Chem. Soc., 1986, 108: 7420—7422
[28] Gao Y, Hanson R M, Klunder J M, Soo Y K, Masamune H, Sharpless K B. J. Am. Chem. Soc., 1987, 109: 5765—5780
[29] Marshall J A. Chem. Rev., 1989, 89: 1503—1511
[30] Ziegler F E, Cady M A. J. Org. Chem., 1981, 46: 122—128
[31] Suzuki T, Saimoto H, Tomioka H, Oshima K, Nozaki H. Tetrahedron Lett., 1982, 23: 3597—3600
[32] Yamaguchi M, Hirao I. Tetrahedron Lett., 1983, 24: 391—394
[33] Kim K, Okamoto S, Sato S. Org. Lett., 2001, 3: 67—69
[34] Kohler E P, Richtmyer N K, Hester W F. J. Am. Chem. Soc., 1931, 53: 205—221
[35] Ohno K, Hiramatsu K, Tanaka T. Tetrahedron Lett., 2004, 45: 75—78
[36] Tanaka T, Hiramatsu K, Kobayasha Y, Ohno K. Tetrahedron Lett. 2005, 61: 6726—6742
[37] Bonini C, Lelj F, Righi G. J. Org. Chem., 2003, 68: 3773—3780
[38] Gras J L. J. Org. Chem., 1981, 46: 3738—3741
[39] Bernard N, Chemla F, Normant J F. Tetrahedron Lett., 1998, 39: 6715—6718
[40] Myers A G, McKinstry L. J. Org. Chem., 1996, 61: 2428—2440
[41] Freitag D, Metz P. Tetrahedron, 2006, 62: 1799—1805
[42] Campbell J A, Hart D J. J. Org. Chem., 1993, 58: 2900—2903
[43] Pajkert R, Kolomeitsev A A, Milewska M, Koroniak H. Tetrahedron Lett., 2008, 49: 6046—6049
[44] Ni C F, Li Y, Hu J B. J. Org. Chem., 2006, 71: 6829—6833
[45] Trost B M, Jiang C. J. Am. Chem. Soc., 2001, 123: 12907—12908
[46] Pineschi M. Eur. J. Org. Chem., 2006, (22): 4979—4988
[47] Sassaman M B, Prakash G K S, Olah G A. J. Org. Chem., 1990, 55: 2016—2018
[48] Onaka M, Ohta A, Sugita K, Izumi Y. Appl. Catal A, 1995, 125: 203—216
[49] Srinivas B, Kumar V P, Sridhar R, Surendra K, Nageswar Y V D, Rao K. J. Mol. Cat. A: Chem., 2007, 61: 1—5
[50] Bertolini F, Crotti P, Macchia F, Pineschi M. Tetrahedron Lett., 2006, 47: 61—64
[51] Bandini M, Cozzi P G, Melchiorre P, Umani-Ronchi A. J.Org.Chem., 2002, 67: 5386—5389
[52] Kotsuki H, Teraguchi M, Shimomoto N, Ochi M. Tetrahedron Lett., 1996, 37: 3727—3730
[53] Tabatabaeian K, Mamaghani M, Mahmoodi N O, Khorshidi A. Tetrahedron Lett., 2008, 49: 1450—1454
[54] Liu Y H, Liu Q S, Zhang Z H. Tetrahedron Lett., 2009, 50: 916—921
[55] Bandgar B P, Patil A V. Tetrahedron Lett., 2007, 48: 173—176
[56] Kotsuki H, Hayashida K, Shimanouchi T, Nishizawa H. J. Org. Chem., 1996, 61: 984—990
[57] Xu J X, Xu S. Synthesis, 2004, 276(2): 276—282
[58] Kamal A, Prasad B R, Reddy A M, Khan M N A. Catal. Commun., 2007, 8: 1876—1880
[59] Chakraborti A K, Rudrawar S, Kondaskar A. Eur. J. Org. Chem., 2004, (17): 3597—3600
[60] Kureshy R I, Singh S, Khan N H, Abdi S H R, Suresh E, Jasra R V. J. Mol. Cat. A: Chem., 2007, 264: 162—169
[61] Firouzabadi H, Iranpoor N, Khoshnood A. J. Mol. Cat. A: Chem., 2007, 274: 109—115
[62] Boa A N, Clark S, Hirst P R, Westwood R. Tetrahedron Lett., 2003, 44: 9299—9302
[63] Harris C, Fisher G B, Beardsley D, Lee L, Goralski C T, Nicholson L W, Singaram B. J. Org. Chem., 1994, 59: 7746—7751
[64] Singh S, Han H. Tetrahedron Lett., 2004, 45: 6349—6352
[65] Igarashi J J, Kobayashi Y. Tetrahedron Lett., 2005, 46: 6381—6384
[66] Ha J D, Shin E Y, Kang S K, Ahn J H, Choi J K. Tetrahedron Lett., 2004, 45: 4193—4195
[67] Yang S M, Murray W V. Tetrahedron Lett., 2008, 49: 835—839
[68] Glas H, Thiel W R. Tetrahedron Lett., 1998, 39: 5509—5510
[69] Torregrosa R, Pastor I M, Yus M. Tetrahedron, 2007, 63: 469—473
[70] Duprez V, Heumann A. Tetrahedron Lett., 2004, 45: 5697—5701
[71] Pathirana C, Shukla R, Castoro J, Weaver D, Byrne L, Thomas G P, Palaniswamy V. Tetrahedron Lett., 2009, 50: 1586—1587
[72] Leung W H, Chow E K F, Wu P W Y, Yeung L L. Tetrahedron Lett., 1995, 36: 107—108
[73] Das B, Reddy V S, Krishnaiah M, Rao Y K. J. Mol. Cat. A: Chem., 2007, 270: 89—92
[74] Sello G, Orsini F, Bernasconi S, Gennaro P D. Tetrahedron: Asymmetry, 2006, 17: 372—376
[75] Catasus M, Albert A, Aggarwal V K. Tetrahedron Lett., 2002, 43: 3475—3479
[76] Fox D L, Robinson A A, Frank J B, Salvatore R N.Tetrahedron Lett., 2003, 44: 7579—7582
[77] Krawiecka B, Jeziorna A. Tetrahedron Lett., 2005, 46: 4381—4384
[78] Sobhani S, Vafaee S A. Tetrahedron, 2009, 65: 7691—7695
[79] Moghadam M, Tangestaninejad S, Mirkhani V, Shaibani R. Tetrahedron, 2004, 60: 6105—6111
[80] Mirkhani V, Tangestaninejad S, Yadollahi B, Alipanah L. Tetrahedron, 2003, 59: 8213—8218
[81] Bukowska A, Bukowski W J. Chem. Technol. Biotechnol., 1998, 73: 341—344
[82] Meyer O, Ponaire S, Rohmer M, Billiard C G. Org. Lett., 2006, 8: 4347—4350
[83] Das B, Krishnaiah M, Venkateswarlu K. Tetrahedron Lett., 2006, 47: 6027—6029
[84] Das B, Reddy V S, Tehseen F. Tetrahedron Lett., 2006, 47: 6865—6868
[85] Stamatov S D, Stawinski J. Tetrahedron, 2005, 61: 3659—3669
[86] Fan R H, Hou X L. Tetrahedron Lett., 2003, 44: 4411—4413
[87] Barluenga J, Zquez-Villa H V, Ballesteros A, Gonzalez J M. Org. Lett., 2002, 4: 2817—2819
[88] Crkva V C, Gaboyard1 M, Paleta O. J. Fluorine Chem., 2000, 102: 349—361
[89] Fagnou K, Lautens M. Org. Lett., 2000, 2: 2319—2321
[90] Benfatti F, Cardillo G, Gentilucci L, Tolomelli A. Eur. J. Org. Chem., 2007, 3199—3205
[91] Benfatti F, Cardillo G, Gentilucci L, Tolomelli A. Bioorg. Med. Chem. Lett., 2007, 17: 1946—1950
[92] Das B, Krishnaiah M, Thirupathi P, Laxminarayana K. Tetrahedron Lett. 2007, 48: 4263—4265
[93] Shepperson I, Cavazzini M, Pozzi G, Quici S. J. Fluorine Chem., 2004, 125: 175—180
[94] Narina S V, Sudalai A. Tetrahedron, 2007, 63: 3026—3030
[95] Langlois N, Moro A. Eur. J. Org. Chem., 1999, (12): 3483—3488
[96] Polshettiwar V, Kaushik M P. Catal. Commun., 2004, 5: 515—518
[97] Azizi N, Saidi M R. Catal. Commun., 2006, 7: 224—227
[98] Murthy S N, Madhav B, Reddy V P, Rao K R, Nageswar Y V D. Tetrahedron Lett., 2009, 50: 5009—5011
[99] Chumachenko N, Sampson P. Tetrahedron, 2006, 62: 4540—4548
[100] Kiasat A R, Mehrjardi M F. Catal. Commun., 2008, 9: 1497—1500
[101] Kiasat A R, Mirzajani R, Shalbaf H, Tabatabaei T. Chin. Chem. Lett., 2009, 20: 1025—1029
[102] Zhou Z H, Li Z M, Wang Q Y, Liu B, Li K Y, Zhao G F, Zhou Q L, Tang C C. J. Organometal. Chem., 2006, 691: 5790—5797
[103] Li Z M, Zhou Z H, Li K Y, Wang L X, Zhou Q L, Tang C C. Tetrahedron Lett., 2002, 43: 7609—7611
[104] Guo W X, Chen J X, Wu D Z, Ding J C, Chen F, Wu H Y. Tetrahedron, 2009, 65: 5240—5243
[105] Das B, Reddy V S, Ramu R. J. Mol. Cat. A: Chem., 2007, 263: 276—278
[106] Zhang W X, Ye K, Ruan S, Chen Z X, Xia Q H. Chin. J. Chem., 2007, 25: 1758—1761
[107] Haufe G, Bruns S, Runge M. J. Fluorine Chem., 2001, 112: 55—61
[108] Yoshino H, Nomura K, Matsubara S, Oshima K, Matsumoto K, Hagiwara R, Ito Y. J. Fluorine Chem., 2004, 125: 1127—1129
[109] Righi G, Pescatore G, Bonadies F, Bonini C. Tetrahedron, 2002, 57: 5649—5656
[110] Ha J D, Kim S Y, Lee S J, Kang S K, Ahn J H, Kim S S, Choi J K. Tetrahedron Lett., 2004, 45: 5969—5972
[111] Nishitani T, Shiraishi H, Sakaguchi S, Ishii Y. Tetrahedron Lett., 2000, 41: 3389—3393
[112] 马琳鸽(Ma L G), 许家喜(Xu J X). 化学进展(Progress in Chemistry), 2004, 16: 220—235
[1] 郭文迪, 刘晔. 过渡金属配合物催化炔烃和亲核试剂的羰化反应[J]. 化学进展, 2021, 33(4): 512-523.
[2] 孔令斌, 严胜骄*, 林军*. 杂环烯酮缩胺:构筑分子多样性稠杂环化合物的合成先导分子[J]. 化学进展, 2018, 30(5): 639-657.
[3] 陈兴鹏, 许家喜*. 非对称氮杂环丁烷的区域选择性开环反应[J]. 化学进展, 2017, 29(2/3): 181-197.
[4] 李思琦, 许家喜*. 非对称氧杂环丁烷的选择性开环[J]. 化学进展, 2016, 28(12): 1798-1810.
[5] 周婵, 许家喜. 非对称环硫乙烷的区域选择性亲核开环反应[J]. 化学进展, 2012, 24(0203): 338-347.
[6] 石玉刚, 蔡燕, 励建荣, 朱延和. 离子液体中酶促区域选择性合成CFAE[J]. 化学进展, 2011, 23(11): 2247-2257.
[7] 冯汝明,刘仲能,顾荣,曹勇,谢在库. 环氧乙烷胺化制乙醇胺* [J]. 化学进展, 2009, 21(0708): 1636-1643.
[8] 孔峰峰,宋钦华. Paternò-Büchi反应的区域选择性*[J]. 化学进展, 2007, 19(06): 911-919.
[9] 许家喜. 微波与有机化学反应的选择性*[J]. 化学进展, 2007, 19(05): 700-712.
[10] 张治国,尹红. 环氧乙烷环氧丙烷开环聚合反应动力学研究*[J]. 化学进展, 2007, 19(04): 575-582.
[11] 夏咏梅,孙诗雨,方云,闵瑞,吴红平,张玥. 微波辐射-酶耦合催化(MIECC)反应*[J]. 化学进展, 2007, 19(0203): 250-255.
[12] 张治国,尹红. 环氧乙烷和环氧丙烷开环聚合*[J]. 化学进展, 2007, 19(01): 145-152.
[13] 高群,万锕俊. 新型亲核NO共体Diazeniumdiolate及其靶向性控释材料*[J]. 化学进展, 2006, 18(09): 1101-1109.
[14] 刘振德,何煦昌. 微波辅助的Michael加成反应[J]. 化学进展, 2006, 18(09): 1121-1129.
[15] 赵群,倪沛红. pH/温度响应的两亲性嵌段共聚物的研究*[J]. 化学进展, 2006, 18(06): 768-779.