SIOC English
化学学报
高级检索

化学学报 >

2012 , Vol. 70 >Issue 23: 2408 - 2411

DOI: https://doi.org/10.6023/A12090651

研究通讯

碘催化的串联氧化环化反应合成多取代咪唑

  • 张百群 ,
  • 万常峰 ,
  • 王强 ,
  • 张帅 ,
  • 查正根 ,
  • 汪志勇
展开
  • 合肥微尺度物质科学国家实验室(筹) 中国科学技术大学软物质化学重点实验室 中国科学技术大学化学系 合肥 230026

收稿日期: 2012-09-11

  网络出版日期: 2012-10-29

基金资助

项目受国家自然科学基金(Nos. J1030412, 20932002, 20972144, 21172205, 21272222)和中国科学技术部(No. 2010CB912103)资助.

收起

A Rapid and Efficient Access to Polysubstituted Imidazoles via Iodine-Catalyzed Tandem Oxidative Cyclization

  • Zhang Baiqun ,
  • Wan Changfeng ,
  • Wang Qiang ,
  • Zhang Shuai ,
  • Zha Zhenggen ,
  • Wang Zhiyong
Expand
  • Hefei National Laboratory for Physical Sciences at Microscale, CAS Key Laboratory of Soft Matter Chemistry and Department of Chemistry, University of Science and Technology of China, Hefei 230026

Received date: 2012-09-11

  Online published: 2012-10-29

Supported by

Project supported by the National Natural Science Foundation of China (Nos. J1030412, 20932002, 20972144, 21172205 and 21272222) and the Chinese Ministry of Science and Technology (No. 2010CB912103).

Fold

摘要

以苯乙醛和苄胺衍生物为原料, 分子碘作为催化剂, 过氧叔丁醇作为氧化剂合成了一系列的多取代咪唑. 同时对反应过程中催化剂的用量、氧化剂、溶剂和温度进行了优化, 得到如下最优反应条件: 0.3 equiv.的分子碘作为催化剂, 过氧叔丁醇作为氧化剂, 乙腈作为溶剂, 反应温度为70℃. 而苯乙酮和苄胺上的吸电子基团均有利于此氧化反应, 对反应机理也进行了探索性研究并有了较明确的认识. 与传统的咪唑合成方法相比, 该新方法反应条件更温和, 原材料更易获得.

关键词： 无金属; 碘催化; 串联氧化环化; 杂环合成; 多取代咪唑

本文引用格式

张百群 , 万常峰 , 王强 , 张帅 , 查正根 , 汪志勇 . 碘催化的串联氧化环化反应合成多取代咪唑[J]. 化学学报, 2012 , 70(23) : 2408 -2411 . DOI: 10.6023/A12090651

Abstract

Imidazoles represent one of the most important heterocycles which are known to exhibit a wide range of biological and medical activity. Existing methodologies for the synthesis of imidazoles are limited to the generality and accessibility of substrates, and the harsh reaction conditions. The development of milder and more practical protocols should be still desirable and necessary. Here we report a new method for the synthesis of polysubstituted imidazoles. A series of imidazoles was obtained directly from 2-phenylacetaldehyde or acetophenone derivatives and benzylamine derivatives via a metal-free-catalyzed tandem oxidative cyclization. The reaction was performed under mild conditions with iodine as a catalyst and TBHP as an oxidant. The effect of catalyst loading, oxidants, solvents and temperature on this transformation was investigated. The optimal reaction conditions were as follows: 0.3 equiv. of iodine as the catalyst, TBHP as the oxidant, acetonitrile as the solvent and the reaction being carried out at 70℃. Electron-withdrawing group of acetophenone derivatives and benzylamine derivatives benefit the oxidative reaction. Compared with traditional methods, this reaction was conducted under milder conditions with facile starting materials.

Key words： metal-free; iodine catalyst; tandem oxidative cyclization; heterocycle synthesis; polysubstituted imidazoles

参考文献

[1] (a) Rizzi, J. P.; Nagel, A. A.; Rosen, T.; Mclean, S.; Seeger, T. J. Med. Chem. 1990, 33, 2721;
(b) Sarshar, S.; Zhang, C.; Moran, E. J.; Krane, S.; Rodarte, J. C.; Benbatoul, K. D.; Dixon, R.; Mjalli, A. M. M. Bioorg. Med. Chem. 2000, 10, 2599.
[2] (a) Atwell, G. A.; Fan, J.-Y.; Tan, K.; Denny, W. A. J. Med. Chem. 1998, 41, 4744;
(b) Carunu, D. J.; Duncia, J. V.; Johnson, A. L.; Chiu, A. T.; Price, W. A.; Wong, P. C.; Timmermans, P. J. Med. Chem. 1990, 33, 1330;
(c) Messina, F.; Botta, M.; Corelli, F.; Schneider, M. P.; Fazio, F. J. Org. Chem. 1999, 64, 3767;
(d) Khanna, I. K.; Weier, R. M.; Yu, Y.; Xu, X. D.; Koszyk, F. J.; Collins, P. W.; Koboldt, C. M.; Veenhuizen, A. W.; Perkins, W. E.; Casler, J. J.; Masferrer, J. L.; Zhang, Y. Y.; Gregory, S. A.; Seibert, K.; Isakson, P. C. J. Med. Chem. 1997, 40, 1634.
[3] (a) Garrison, J. C.; Youngs, W. J. Chem. Rev. 2005, 105, 3978;
(b) Braband, H.; Kueckmann, T.; Theresa, I.; Abram, U. J. Organomet. Chem. 2005, 690, 5421;
(c) Scott, N. M.; Nolan, S. P. Eur. J. Inorg. Chem. 2005, 1815;
(d) Enders, D.; Niemeier, O.; Henseler, A. Chem. Rev. 2007, 107, 5606;
(e) Bourissou, D.; Guerret, O.; Gabbai, F. P.; Bertrand, G. Chem. Rev. 2000, 100, 39;
(f) Arnold, P. L.; Liddle, S. T. Chem. Commun. 2006, 3959.
[4] (a) Dupont, J.; Souza, R. F. d.; Suarez, P. A. Z. Chem. Rev. 2002, 102, 3667;
(b) Nara, S. J.; Naik, P. U.; Harjani, J. R.; Salunkhe, M. M. Indian J. Chem. 2006, 45, 2257;
(c) Chowdhury, S.; Mohan, R. S.; Scott, J. L. Tetrahedron 2007, 63, 2363.
[5] (a) Kamijo, S.; Yamamoto, Y. Chem.-Asian J. 2007, 2, 568;
(b) Delest, B.; Nshimyumukiza, P.; Fasbender, O.; Tinant, B.; Brynaert, J. M.; Darro, F.; Robiette, R. J. Org. Chem. 2008, 73, 6816;
(c) Kison, C.; Opatz, T. Chem.-Eur. J. 2009, 15, 843;
(d) Horneff, T.; Chuprakov, S.; Chernyak, N.; Gevorgyan, V.; Fokin, V. V. J. Am. Chem. Soc. 2008, 130, 14972;
(e) Kanazawa, C.; Kamijo, S.; Yamamoto, Y. J. Am. Chem. Soc. 2006, 128, 10662;
(f) Giles, R. L.; Sullivan, J. D.; Steiner, A. M.; Looper, R. E. Angew. Chem., Int. Ed. 2009, 48, 3116;
(g) Zhong, Y.-L.; Lee, J.; Reamer, R. A.; Askin, D. Org. Lett. 2004, 6, 929;
(h) Giles, R. L.; Nkansah, R. A.; Looper, R. E. J. Org. Chem. 2010, 75, 261.
[6] Bredereck, H.; Theilig, G. Chem. Ber. 1953, 86, 88.
[7] (a) Salvatori, M. D. R. S.; Abou-Jneid, R.; Ghoulami, S.; Martin, M.-T.; Zaparucha, A.; Al-Mourabit, A. J. Org. Chem. 2005, 70, 8208;
(b) Gwiazda, M.; Reissig, H. U. Synlett 2006, 1683;
(c) Zhong, Y.-L.; Lee, J.; Reamer, R. A.; Askin, D. Org. Lett. 2004, 6, 929;
(d) Sisko, J.; Kassick, A. J.; Mellinger, M.; Filan, J. J.; Allen, A.; Olsen, M. A. J. Org. Chem. 2000, 65, 1516.
[8] (a) Collman, J. P.; Zhong, M.; Zhang, C.; Costanzo, S. J. Org. Chem. 2001, 66, 7892;
(b) Altman, R. A.; Buchwald, S. L. Org. Lett. 2006, 8, 2779;
(c) Cristau, H. J.; Cellier, P. P.; Spindler, J. F.; Taillefer, M. Chem.-Eur. J. 2004, 10, 5607;
(d) Liu, L.; Frohn, M.; Xi, N.; Dominguez, C.; Hungate, R.; Reider, P. J. J. Org. Chem. 2005, 70, 10135;
(e) Lv, X.; Wang, Z.; Bao, W. Tetrahedron 2006, 62, 4756;
(f) Collman, J. P.; Zhong, M. Org. Lett. 2000, 2, 1233;
(g) Lan, J.-B.; Chen, L.; Yu, X.-Q.; You, J.-S.; Xie, R.-G. Chem. Commun. 2004, 188;
(h) Kantam, M. L.; Venkanna, G. T.; Sridhar, C.; Sreedhar, B.; Choudary, B. M. J. Org. Chem. 2006, 71, 9522.
[9] (a) Sharma, S. D.; Hazarika, P.; Konwar, D. Tetrahedron Lett. 2008, 49, 2216;
(b) Kidwai, M.; Mothsra, P. Tetrahedron Lett. 2006, 47, 5029;
(c) Wolkenberg, S. E.; Wisnoski, D. D.; Leister, W. H.; Wang, Y.; Zhao, Z.-J.; Lindsley, C. W. Org. Lett. 2004, 6, 1453;
(d) Usyatinsky, A. Y.; Khmelnitsky, Y. L. Tetrahedron Lett. 2000, 41, 5031.
[10] (a) Li, Y.-Z.; Li, B.-J.; Lu, X.-Y.; Lin, S.; Shi, Z.-J. Angew. Chem., Int. Ed. 2009, 48, 3817;
(b) Borduas, N.; Powell, D. A. J. Org. Chem. 2008, 73, 7822;
(c) Wang, L.; Fu, H.; Jiang, Y.-Y.; Zhao, Y.-F. Chem.-Eur. J. 2008, 14, 10722;
(d) Boldron, C.; Gamez, P.; Tooke, D. M.; Spek, A. L.; Reedijk, J. Angew. Chem., Int. Ed. 2005, 44, 3585;
(e) Jiang, H.; Huang, H.; Cao, H.; Qi, C. Org. Lett. 2010, 12, 5561.
[11] Li, C.-J. Acc. Chem. Res. 2009, 42, 335.
[12] (a) Yan, Y.; Wang, Z. Chem. Commun. 2011, 47, 9513;
(b) Wang, Q.; Wan, C.; Gu, Y.; Zhang, J.; Gao, L.; Wang, Z. Green Chem. 2011, 13, 578;
(c) Zhang, J.-T.; Yu, C.-M.; Wang, S.-J.; Wan, C.-F.; Wang, Z.-Y. Chem. Commun. 2010, 46, 5244;
(d) Zhang, J.; Zhu, D.; Yu, C.; Wan, C.; Wang, Z. Org. Lett. 2010, 12, 2841;
(e) Wan, C.; Zhang, J.; Wang, S.; Fan, J.; Wang, Z. Org. Lett. 2010, 12, 2338;
(f) Wan, C.; Gao, L.; Wang, Q.; Zhang, J.; Wang, Z. Org. Lett. 2010, 12, 3902.
[13] CCDC 900085 (3a) contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via www.ccdc.cam.ac. uk/data_request/.
[14] (a) Li, Q.; Fan, A.; Lu, Z.; Cui, Y.; Lin, W.; Jia, Y. Org. Lett. 2010, 12, 4066;
(b) Wan, X.; Xing, D.; Fang, Z.; Li, B.; Zhao, F.; Zhang, K.; Yang, L.; Shi, Z. J. Am. Chem. Soc. 2006, 128, 12046.
[15] (a) Wei, W.; Shao, Y.; Hu, H.; Zhang, F.; Zhang, C.; Xu, Y.; Wan, X. J. Org. Chem. 2012, 77, 7157;
(b) Jiang, H.; Huang, H.; Cao, H.; Qi, C. Org. Lett. 2010, 12, 5561;
(c) Lamani, M.; Prabhu, K. R. Chem.-Eur. J. 2012, 18, 14638;
(d) Zhang, X.; Wang, L. Green Chem. 2012, 14, 2141. Yan, Y.; Zhang, Y.; Feng, C.; Zha, Z.; Wang, Z. Angew. Chem., Int. Ed. 2012, 51, 8079.
Options
文章导航

/

〈 〉