Mechanism for the carboxylative coupling reaction of a terminal alkyne, CO2, and an allylic chloride catalyzed by the Cu(I) complex: A DFT study

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	Mechanism for the carboxylative coupling reaction of a terminal alkyne, CO2, and an allylic chloride catalyzed by the Cu(I) complex: A DFT study
	Yuan, Rumi ; Lin, Zhenyang ; Yuan RM(袁汝明)
刊名	http://dx.doi.org/10.1021/cs5011184
	2014
关键词	Catalysis Chemical bonds Chlorine compounds Copper Copper compounds Hydrocarbons Molecules
英文摘要	DFT calculations have been carried out to study the detailed mechanisms for carboxylative-coupling reactions among terminal alkynes, allylic chlorides, and CO2 catalyzed by N-heterocyclic carbene copper(I) complex (IPr)CuCl. The competing cross-coupling reactions between terminal alkynes and allylic chlorides have also been investigated. The calculation results show that a base-assisted metathesis of (IPr)CuCl with PhC≡CH occurs as the first step to give the acetylide (IPr)Cu-C≡CPh, from which CO2 insertion and reaction with an allylic chloride molecule, respectively, lead to carboxylative-coupling and cross-coupling reactions. It was found that both the reactions of (IPr)Cu-C≡CPh and (IPr)CuOCOC≡CPh (a species derived from CO2 insertion) with an allylic chloride molecule occur through an SN2 substitution pathway. The two SN2 transition states (calculated for the carboxylative coupling and cross coupling) are the rate-determining transition states and show comparable stability. How the reaction conditions affect the preference of one pathway over the other (carboxylative coupling versus cross coupling) has been discussed in detail. (Chemical Equation Presented).
语种	英语
出版者	American Chemical Society
内容类型	期刊论文
源URL	[http://dspace.xmu.edu.cn/handle/2288/89636]
专题	化学化工－已发表论文
推荐引用方式 GB/T 7714	Yuan, Rumi,Lin, Zhenyang,Yuan RM. Mechanism for the carboxylative coupling reaction of a terminal alkyne, CO2, and an allylic chloride catalyzed by the Cu(I) complex: A DFT study[J]. http://dx.doi.org/10.1021/cs5011184,2014.
APA	Yuan, Rumi,Lin, Zhenyang,&袁汝明.(2014).Mechanism for the carboxylative coupling reaction of a terminal alkyne, CO2, and an allylic chloride catalyzed by the Cu(I) complex: A DFT study.http://dx.doi.org/10.1021/cs5011184.
MLA	Yuan, Rumi,et al."Mechanism for the carboxylative coupling reaction of a terminal alkyne, CO2, and an allylic chloride catalyzed by the Cu(I) complex: A DFT study".http://dx.doi.org/10.1021/cs5011184 (2014).