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

doi:10.6023/cjoc202101003

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^,^*()

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 Wang^a^,^b, Lichen Xu^a^,^b, Yi Lu^a, Bo Jiang^a^,^*(), Wenjuan Hao^a^,^*()

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: jiangchem@jsnu.edu.cn;
E-mail: wjhao@jsnu.edu.cn
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)

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摘要/Abstract

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

引用此文

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.

Rong Wang, Lichen Xu, Yi Lu, Bo Jiang, Wenjuan Hao. Sc(OTf)₃-Catalyzed Dearomatization of Indoles for the Synthesis of 3,3'-Bisindoles[J]. Chinese Journal of Organic Chemistry, 2021, 41(4): 1582-1590.

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图/表 6

图1. 含3,3'-双吲哚骨架的生物碱

Figure 1. 3,3'-Bisindole-containing alkaloids

图式1. 3,3'-双吲哚衍生物的合成

Scheme 1. Synthesis of 3,3'-bisindoles

Entry	Cat. (mol%)	Solvent	t/℃	Yield^b/%
1	Sc(OTf)₃ (10)	1,4-Dioxane	80	78
2	Sc(OTf)₃ (20)	1,4-Dioxane	80	82
3	Sc(OTf)₃ (30)	1,4-Dioxane	80	81
4	Cu(OTf)₂ (20)	1,4-Dioxane	80	Trace
5	Mg(OTf)₂ (20)	1,4-Dioxane	80	57
6	Sc(OTf)₃ (20)	CH₃CN	80	N.D.
7	Sc(OTf)₃ (20)	EtOH	80	N.D.
8	Sc(OTf)₃ (20)	DMF	80	N.D.
9	Sc(OTf)₃ (20)	EA	80	Trace
10	Sc(OTf)₃ (20)	1,4-Dioxane	70	75
11	Sc(OTf)₃ (20)	1,4-Dioxane	90	70
	Sc(OTf)₃ (20)	1,4-Dioxane	100	63

表1. 化合物3a反应条件的优化a

Table 1. Optimization of reaction conditions for the synthesis of 3aa

图2. 3,3'-双吲哚衍生物3a的晶体结构图

Figure 2. X-ray structure of 3,3-bisindole 3a

图式2. 3,3'-双吲哚衍生物3的合成

Scheme 2. Synthesis of 3,3'-bisindoles 3

图式3. 生成化合物3a 的可能机理

Scheme 3. Proposed mechanism for the synthesis of product 3a

参考文献 9

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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

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

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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

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

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