有机化学 ›› 2021, Vol. 41 ›› Issue (4): 1582-1590.DOI: 10.6023/cjoc202101003 上一篇    下一篇

研究论文

利用三氟甲基磺酸钪催化的吲哚去芳构化反应合成3,3'-双吲哚衍生物

王榕a,b, 徐立晨a,b, 卢逸a, 姜波a,*(), 郝文娟a,*()   

  1. a 江苏师范大学化学与材料科学学院 江苏徐州 221116
    b 江苏师范大学敬文书院 江苏徐州 221116
  • 收稿日期:2021-01-03 修回日期:2021-01-23 发布日期:2021-02-22
  • 通讯作者: 姜波, 郝文娟
  • 作者简介:
    † 共同第一作者(These authors contributed equally to this work).
  • 基金资助:
    国家自然科学基金(21602087); 江苏省品牌专业基金; 国家级大学生创新创业训练计划(201910320093Z)

Sc(OTf)3-Catalyzed Dearomatization of Indoles for the Synthesis of 3,3'-Bisindoles

Rong Wanga,b, Lichen Xua,b, Yi Lua, Bo Jianga,*(), Wenjuan Haoa,*()   

  1. a School of Chemistry & Materials Science, Jiangsu Normal University, Xuzhou, Jiangsu 221116
    b C. W. Chu College, Jiangsu Normal University, Xuzhou, Jiangsu 221116
  • Received:2021-01-03 Revised:2021-01-23 Published:2021-02-22
  • Contact: Bo Jiang, Wenjuan Hao
  • About author:
    * Corresponding authors. E-mail: ;
  • Supported by:
    National Natural Science Foundation of China(21602087); Top-notch Academic Programs Project of Jiangsu Higher Education Institutions; National College Student?s Innovation and Entrepreneurship Training Program(201910320093Z)

报道了一类新颖的三氟甲基磺酸钪催化的吲哚-2-甲醇的去芳构化反应. 该反应利用吲哚-2-甲醇衍生物在酸性催化下发生极性翻转的特性, 将其吲哚环3-位的亲核中心转变为亲电位点, 实现与另一分子吲哚发生偶联反应, 合成了一系列具有环外双键结构的3,3'-双吲哚衍生物, 产率中等到优秀. 其中N-磺酰基团的强诱导作用和大位阻效应是吲哚-2-甲醇的吲哚环发生去芳构化的关键因素. 基于实验结果及文献报道, 提出了可能的反应机理, 其中涉及吲哚-2-甲醇衍生物的去羟基化和亲核加成等. 此外, 该反应具有高官能团兼容性、条件温和、操作简便等优点.

关键词: 极性翻转, 去芳构化反应, 吲哚-2-甲醇衍生物, 3,3'-双吲哚衍生物

A new Sc(OTf)3-catalyzed dearomatization of indole-2-methanols is reported. By using the characteristics of umpolung of the preformed indole-2-methanols in the presence of acid catalysts, its nucleophilic center at 3-position of indole ring could be transformed into the electrophilic site, thereby realizing the coupling reaction with another molecule indoles, which led to the synthesis of a series of 3,3'-bisindoles with exocyclic double bond unit in moderate to excellent yields. Among them, the strong induction and large steric effects of N-sulfonyl group are the key to the dearomatization of indole ring from indole-2-methanols. Based on the experimental results and literature reports, the possible reaction mechanism is proposed, which involves the dehydroxylation and nucleophilic addition of indole-2-methanol derivatives. In addition, this protocol features high functional group compatibility, mild conditions and simple operation.

Key words: umpolung, dearomatization, indole-2-methanols, 3,3'-bisindoles