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
收稿日期: 2021-01-03
修回日期: 2021-01-23
网络出版日期: 2021-02-22
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
Received date: 2021-01-03
Revised date: 2021-01-23
Online published: 2021-02-22
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
王榕 , 徐立晨 , 卢逸 , 姜波 , 郝文娟 . 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[J]. 有机化学, 2021 , 41(4) : 1582 -1590 . DOI: 10.6023/cjoc202101003
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
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