钴催化1-三甲硅基-2-芳基乙炔的α位芳基化反应

doi:10.6023/cjoc202603046

摘要/Abstract

发展了一种二乙酰丙酮钴和双二苯基膦甲烷协同催化1-三甲硅基-2-芳基乙炔化学、区域和立体选择性的芳基化反应, 有效合成了具有多种官能团的1,2-芳基烯基硅类化合物. 该方法具有良好的官能团容忍性、中等至良好的收率、易于克级规模制备, 且产物中存在的烯基硅结构单元能够实现多种合成转化的优点. 同时, 该工作也开发了3,4-二氢- 1(2H)-异喹啉酮类化合物的新合成应用.

关键词: 钴催化, 炔烃, 化学选择性, 区域选择性, 立体选择性, 芳基化

A synergistic catalytic, chemo-, regio- and stereoselective arylation reaction of 1-trimethylsilyl-2-arylacetylene using cobalt diacetylacetonate and diphenylphosphine methane has been developed, effectively synthesizing 1,2-diaryl- vinylsilyl compounds with multiple functional groups. This method has the advantages of good functional group tolerance, moderate to good yield, easy preparation on a gram scale, and the presence of vinyl silicon structural units in the product can achieve multiple synthetic transformations. At the same time, this work also developed new synthetic applications of 3,4-dihydro-1(2H)-isoquinolinone compounds.

Key words: cobalt-catalyzed, alkynes, chemselectivity, regioselectivity, stereoselectivity, arylation

引用此文

陈丽萍, 马瑞, 池建军, 金彧帆, 王清, 汪洋, 朱雪华, 庞玉博. 钴催化1-三甲硅基-2-芳基乙炔的α位芳基化反应[J]. 有机化学, 2026, 46(7): 2760-2769.

Liping Chen, Rui Ma, Jianjun Chi, Yufan Jin, Qing Wang, Yang Wang, Xuehua Zhu, Yubo Pang. Cobalt-Catalyzed α-Arylation of 1-Trimethylsilyl-2-aryl Acetylene[J]. Chinese Journal of Organic Chemistry, 2026, 46(7): 2760-2769.

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图/表 6

图式1. 炔基硅烷类化合物芳基化反应的研究现状以及本文的研究内容

Scheme 1. Current research progress of arylation reactions of alkynyl silane compounds and the research content of this article

Entry	Ligand (equiv.)	Solvent	Temp./℃	Yeild^b/% (3aa/4aa)	Z/E ratio (3aa)
1	dppe (0.1)	MeCN	80	5	>20/1
2	dppe (0.1)	MeCN	100	56 (1/1)	>20/1
3	dppe (0.1)	MeCN	120	58 (1/1)	>20/1
4	dppe (0.1)	THF	100
5	dppe (0.1)	IPAc	100
6	dppe (0.1)	DMA	100	Trace
7	dppe (0.1)	Toluene	100
8	dppe (0.1)	EtOH	100
9	dppp (0.1)	MeCN	100	50 (1/1.5)	>20/1
10	dppb (0.1)	MeCN	100	37 (1/2)	>20/1
11	dppm (0.1)	MeCN	100	63	>20/1
12	dppm (0.2)	MeCN	100	78	>20/1

表1. 反应条件优化a

Table 1. Optimization of reaction conditions

图式2. 炔烃底物拓展

Scheme 2. Scope of 1-trimethylsilyl-2-arylacetylene

图式3. 芳基硼酸的兼容性考察

Scheme 3. Investigating the compatibility of arylboronic acids

图式4. 反应的衍生化和自由基猝灭实验

Scheme 4. Derivatives of reactions and mechanism study

图式5. 可能的反应历程

Scheme 5. Proposed reaction mechanism

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