N-碘丁二酰亚胺(NIS)催化3-取代吲哚衍生物的合成

doi:10.6023/cjoc202202020

摘要/Abstract

发展了一个以N-卤丁二酰亚胺为催化剂的吲哚与α,β-不饱和酮的迈克尔加成反应体系. 首先以吲哚对查尔酮的迈克尔加成反应为模板反应, 探索了该反应的优化条件. 实验结果表明, 该反应的优化条件是以10 mol% N-碘丁二酰亚胺(NIS)为催化剂, CH₃CN为溶剂, 在室温下搅拌反应18 h, 查尔酮与吲哚可以顺利反应, 获得了1,3-二苯基-3-(1H-吲哚-3-基)-1-丙酮, 分离收率可达90%. 其次探索了该优化条件的底物适应性, 实验结果显示, 该优化条件可以使吲哚、1-甲基吲哚、6-甲基吲哚与查尔酮以及苯亚甲基丙酮等多种α,β-不饱和酮反应, 生成目标产物, 收率在51%~90%之间. 该反应的条件温和, 操作简单.

关键词: N-碘丁二酰亚胺(NIS), 催化, 吲哚, α,β-不饱和酮, 迈克尔加成

A catalytic procedure for Michael addition reaction of indole or its derivatives with α,β-unsaturated ketones catalyzed by N-halosuccinimide has been successfully developed. Firstly, the Michael addition reaction of indole with chalcone was used as the template reaction, and the optimal conditions of the reaction were explored. The experimental results show that the optimal condition employs 10 mol% N-iodosuccinimide (NIS) as catalyst, CH₃CN as solvent, room temperature as reaction temperature and 18 h as reaction time. Under this optimized conditions, the reaction of chalcone and its derivatives with various α,β-unsaturated ketone can proceed smoothly to obtain the aimed product. The yields of these reactions ranged from 51% to 90%. The reaction conditions are mild and the reaction operation is simple.

Key words: N-iodosuccinimide (NIS), catalysis, indole, α,β-unsaturated ketone, Michael addition

引用此文

钱存卫, 韩容, 沈芷欣, 李倩, 陈选荣. N-碘丁二酰亚胺(NIS)催化3-取代吲哚衍生物的合成[J]. 有机化学, 2022, 42(8): 2496-2503.

Cunwei Qian, Rong Han, Zhixing Shen, Qian Li, Xuanrong Chen. N-Iodosuccinimide (NIS) Promoted Synthesis of 3-Substituted Indole Derivatives[J]. Chinese Journal of Organic Chemistry, 2022, 42(8): 2496-2503.

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图/表 4

图式1. N-卤丁二酰亚胺催化的部分有机合成反应

Scheme 1. Some N-nalosuccinimide promoted organic synthesis

Entry	Catalyst	Temperature/℃	Solvent	Yield^b/%
1	NCS	60	CH₃CN	26
2	NBS	60	CH₃CN	43
3	NIS	60	CH₃CN	91
4	—	60	CH₃CN	0
5	NIS	60	CH₃OH	80
6	NIS	60	THF	60
7	NIS	60	H₂O	55
8	NIS	60	Hexane	0
9	NIS	60	Toluene	0
10	NIS	r.t.	CH₃CN	76
11	NIS	80	CH₃CN	95
12^c	NIS	80	CH₃CN	73
13^d	NIS	80	CH₃CN	82
14^e	NIS	r.t.	CH₃CN	70
15^f	NIS	r.t.	CH₃CN	84
16^g	NIS	r.t.	CH₃CN	90

表1. 反应条件优化 a

Table 1. Optimization of reaction conditions

表2. 3-取代吲哚类化合物的合成a

Table 2. Synthesis of 3-substituted indole derivatives

图式2. 可能的反应机理

Scheme 2. Possible reaction mechanism

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