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2014 , Vol. 72 >Issue 7: 836 - 840

DOI: https://doi.org/10.6023/A14040237

研究通讯

Sc(OTf)3/Bis(oxazoline)复合物催化的2-芳基-1,3-茚二酮与2-乙烯基吲哚的不对称Diels-Alder反应：高效构建四氢咔唑螺茚酮衍生物

  • 谭芬 ,
  • 陈加荣 ,
  • 王萍 ,
  • 肖文精
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  • a 华中师范大学 农药与化学生物学教育部重点实验室和化学学院 武汉 430079;
    b 湖北中医药大学 药学院 武汉 430065

收稿日期: 2014-04-01

  网络出版日期: 2014-05-07

基金资助

项目受国家自然科学基金（Nos.21072069，21002036，21232003和21202053）与973计划（2011CB808600）资助.

收起

Asymmetric Diels-Alder Reaction of 2-Arylidene-1,3-indanediones with 2-Vinylindoles Catalyzed by a Sc(OTf)3/Bis(oxazoline) Complex：Enantioselective Synthesis of Tetrahydrocarbazole Spiro Indanedione Derivatives

  • Tan Fen ,
  • Chen Jiarong ,
  • Wang Ping ,
  • Xiao Wenjing
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  • a Key Laboratory of Pesticide & Chemical Biology Ministry of Education and College of Chemistry, Central China Normal University, Wuhan, 430079;
    b College of Pharmacy, Hubei University of Chinese Medicine, Wuhan, 430065

Received date: 2014-04-01

  Online published: 2014-05-07

Supported by

Project supported by the National Natural Science Foundation of China (Nos. 21072069, 21002036, 21232003, and 21202053) and the National Basic Research Program of China (973 program, 2011CB808600).

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摘要

报道了Sc（OTf）3/Bis（oxazoline）复合物催化的2-芳基-1，3-茚二酮与2-乙烯基吲哚的不对称Diels-Alder反应，简便、高效的构建了一系列手性四氢咔唑螺茚酮衍生物. 通过考察不同的金属盐和手性配体、溶剂、温度等因素对反应的影响，获得了优良的收率（up to 92% yield）和优异的对映选择性（up to 94% ee）. 该反应条件温和，具有宽广的底物适用范围和较好的官能团兼容性.

关键词： Diels-Alder反应; 不对称合成; Lewis酸催化; 1,3-茚二酮; 四氢咔唑

本文引用格式

谭芬 , 陈加荣 , 王萍 , 肖文精 . Sc(OTf)3/Bis(oxazoline)复合物催化的2-芳基-1,3-茚二酮与2-乙烯基吲哚的不对称Diels-Alder反应：高效构建四氢咔唑螺茚酮衍生物[J]. 化学学报, 2014 , 72(7) : 836 -840 . DOI: 10.6023/A14040237

Abstract

Spirocyclic scaffolds are prevalent in numerous naturally occurring products and pharmaceuticals, which exhibit important biological and pharmacological activities. In this communication, a Sc(OTf)3/Bis(oxazoline) complex catalyzed asymmetric Diels-Alder reaction of 2-arylidene-1,3-indanediones with 2-vinylindoles has been developed. The reaction provides a convenient and practical approach to biologically useful and synthetically important spiro-tetrahydrocarbazoles in good yields with high enantioselectivities (16 examples, up to 92% yield, 94% ee). A representative procedure for this asymmetric Diels-Alder reaction is described below: Sc(OTf)3 (0.02 mmol) and chiral tridentate diphenyl-pybox ligand IV (0.02 mmol) were dissolved in toluene (1.5 mL) and stirred for 30 minutes at room temperature. 2-Arylidene-1,3-indanediones (0.20 mmol) was added to the above-mentioned solution and stirred at 5 ℃ for another 30 minutes. The solution of 2-vinylindoles (0.20 mmol) in toluene (0.5 mL) was then added to the reaction system and the mixture was stirred until the complete consumption of substrates (as monitored by TLC). The reaction mixture was purified directly by flash column chromatography on silica gel (petroleum ether/ethyl acetate=15:1～10:1) to give the corresponding products.

Key words： Diels-Alder reaction; asymmetric synthesis; Lewis acid catalysis; 1,3-indanedione; tetrahydrocarbazole

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