三甲基溴硅烷诱导的N-保护吲哚的区域选择性二聚合成2,3′-吲哚基二氢吲哚

doi:10.6023/cjoc202109011

摘要/Abstract

报道了一种三甲基溴硅烷促进的通过碳-碳键交叉偶联反应合成N-甲基吲哚二聚体的方法. 在温和条件下以最高95%的收率方便地合成了一系列2,3′-吲哚基二氢吲哚类化合物. 克级反应证明了该方法的实用性. 初步研究了目标产物的紫外-可见吸收和荧光光谱性质.

关键词: 吲哚, 二聚, 交叉偶联, 吲哚基二氢吲哚

A dimerization of N-methylindoles by trimethylsilyl bromide promoted C—C bond cross coupling reactions is described. A series of 2,3'-linked indolylindolines are smoothly installed under mild reaction conditions with up to 95% yields. The gram scale reactions demonstrate the practicality of this protocol. The UV-vis absorption and fluorescence spectra properties of target products are preliminarily studied.

Key words: indole, dimerization, cross-coupling, indolylindoline

引用此文

唐爱玲, 金伟伟, 刘晨江. 三甲基溴硅烷诱导的N-保护吲哚的区域选择性二聚合成2,3′-吲哚基二氢吲哚[J]. 有机化学, 2021, 41(12): 4758-4765.

Ailing Tang, Weiwei Jin, Chenjiang Liu. Trimethylsilyl Bromide-Induced Regioselective Dimerization of N-Protected Indoles to 2,3'-Linked Indolylindolines[J]. Chinese Journal of Organic Chemistry, 2021, 41(12): 4758-4765.

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图/表 8

Scheme 1. Various routes to proposed mechanism

Entry	Base	Solvent	Additive	Yield of 2a^b/%
1	K₂CO₃	DCM	TMSCl	61
2	KOH	DCM	TMSCl	24
3	K₃PO₄•3H₂O	DCM	TMSCl	63
4	K₃PO₄•3H₂O	CHCl₃	TMSCl	59
5	K₃PO₄•3H₂O	DCM/CHCl₃	TMSCl	68
6	K₃PO₄•3H₂O	DCM/CHCl₃	TfOH	50
7	K₃PO₄•3H₂O	DCM/CHCl₃	TMSOTf	55
8	K₃PO₄•3H₂O	DCM/CHCl₃	TMSI	29
9	K₃PO₄•3H₂O	DCM/CHCl₃	TMSBr	79
10^c	K₃PO₄•3H₂O	DCM/CHCl₃	TMSBr	35
11^d	K₃PO₄•3H₂O	DCM/CHCl₃	TMSBr	78
12	—	DCM/CHCl₃	TMSBr	n.r.
13	K₃PO₄•3H₂O	DCM/CHCl₃	—	n.r.

Table 1. Optimization of reaction conditionsa

Table 2. Substrate scopea,b

Scheme 2. Gram-scale reactions

Figure 1. (A) UV-vis absorption spectra of 2a, 2b, 2j, 2t, 2v and 2z in DCM (1.0×10–4 mol/L), and (B) fluorescence spectra of 2a, 2b, 2j, 2t, 2v and 2z in DCM (1.0×10–4 mol/L, excitation wavelength λex=300 nm)

Figure 2. (A) UV-vis absorption spectra and (B) fluorescence spectra of 2t in CH3CH2OH, CH3CN, CH3OH, DCM, DMF, DMSO, toluene and THF at concentration of 1.0×10–4 mol/L (excitation wavelength λex=291 nm)

Entry	Radical scavengers (2 equiv.)	Yield/%
1	BHT	95
2	1,1-Diphenylethylene	66
3	Standard conditions	79

Table 3. Mechanistic studies

Scheme 3. Proposed mechanism

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