咪唑并吡啶在离子液中环境友好型的C-3位硒化反应

doi:10.6023/cjoc201904057

摘要/Abstract

发展了一种环境相对友好的、咪唑并吡啶衍生物和有机硒化合物C-3位的硒化反应, 目标产物能以中等到优的收率获得. 初步机理研究表明, 该硒化反应经历了亲电加成反应机制, 具有反应条件温和、底物范围宽泛、易于放大量生产等特点. 因此, 该策略在合成含氮和含硒分子中具有重要的应用前景.

关键词: 硒化, 咪唑并吡啶, C-3官能化, 亲电机理

An relative eco-friendly protocol for the direct C-3 selenation of imidazo[1,2-a]pyridines with vorious organoselenides has been developed, gaving the desired products in moderate to excellent yields. Preliminary experimental results are consistent with a C-3 electrophilic functionalization mechanism. The features with relative green reaction conditions, broad substrate scope, and easy scale-up operation would make this strategy promising and important for the preparation of nitrogen and selenium containing molecules.

Key words: selenation, imidazo[1,2-a]pyridines, C-3 functionalization, electrophilic mechanism

引用此文

王薪, 穆石强, 孙婷, 孙凯. 咪唑并吡啶在离子液中环境友好型的C-3位硒化反应[J]. 有机化学, 2019, 39(10): 2802-2807.

Wang Xin, Mu Shiqiang, Sun Ting, Sun Kai. Eco-friendly C-3 Selenation of Imidazo[1,2-a]pyridines in Ionic Liquid[J]. Chinese Journal of Organic Chemistry, 2019, 39(10): 2802-2807.

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图/表 7

Figure 1. Examples of imidazo[1,2-a]pyridine-based drug

Entry	Iodine source	Oxidant	Solvent	Yield^b/% of 3a/4
1	KI	TBHP	EtOAc	41/0^c
2	KI	TBHP	EtOH	23/0^c
3	KI	TBHP	H₂O	0/0^c
4	KI	TBHP	DMSO	55/0^c
5	KI	TBHP	Ionic liquid I	67/0^d
6	KI	TBHP	Ionic liquid II	43/0^e
7	I₂	TBHP	Ionic liquid I	51/Trace^f
8	I₂	No	Ionic liquid I	84/Trace^g
9	I₂	No	Ionic liquid I	33/23^h
10	I₂	No	Ionic liquid I	56/Traceⁱ

Table 1. Survey of the reaction conditionsa

Table 2. Substrate scope of imidazo[1,2-a]pyridinesa,b

Table 3. Selenation of imidazo[1,2-a]pyridines with vorious organoselenidesa

Scheme 1. Gram-scale C-3 selenation of 1a

Scheme 2. Reactions determining the reaction mechanism

Scheme 3. Plausible mechanism

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