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	Mechanistic insight into ketone alpha-alkylation with unactivated olefins via c-h activation promoted by metal-organic cooperative catalysis (mocc): enriching the mocc chemistry
	Dang, Yanfeng1; Qu, Shuanglin1; Tao, Yuan1; Deng, Xi1; Wang, Zhi-Xiang1,2
刊名	Journal of the american chemical society
	2015-05-20
卷号	137期号:19页码:6279-6291
ISSN号	0002-7863
DOI	10.1021/jacs.5b01502
通讯作者	Wang, zhi-xiang(zxwang@ucas.ac.cn)
英文摘要	Metal-organic cooperative catalysis (mocc) has been successfully applied for hydroacylation of olefins with aldehydes via directed c(sp(2))-h functionalization. most recently, it was reported that an elaborated mocc system, containing rh(i) catalyst and 7-azaindoline (l1) cocatalyst, could even catalyze ketone alpha-alkylation with unactivated olefins via c(sp(3))-h activation. herein we present a density functional theory study to understand the mechanism of the challenging ketone alpha-alkylation. the transformation uses imesrh(i)cl(l1)(ch2=ch2) as an active catalyst and proceeds via sequential seven steps, including ketone condensation with l1, giving enamine 1b; 1b coordination to rh(i) active catalyst, generating rh(i)-1b intermediate; c(sp(2))-h oxidative addition, leading to a rh(iii)-h hydride; olefin migratory insertion into rh(iii)-h bond; reductive elimination, generating rh(i)-1c(alkylated 1b) intermediate; decoordination of 1c, liberating 1c and regenerating rh(i) active catalyst; and hydrolysis of 1c, furnishing the final alpha-alkylation product id and regenerating l1. among the seven steps, reductive elimination is the rate-determining step. the c-h bond preactivation via agostic interaction is crucial for the bond activation. the mechanism rationalizes the experimental puzzles: why only li among several candidates performed perfectly, whereas others failed, and why wilkinson's catalyst commonly used in mocc systems performed poorly. based on the established mechanism and stimulated by other relevant experimental reactions, we attempted to enrich mocc chemistry computationally, exemplifying how to develop new organic catalysts and proposing l7 to be an alternative for li and demonstrating the great potential of expanding the hitherto exclusive use of rh(i)/rh(iii) manifold to co(0)/co(ii) redox cycling in developing mocc systems.
WOS关键词	CARBON-HYDROGEN BONDS ; LIGAND-CONTROLLED REGIOSELECTIVITY ; DIRECT ARYLATION ; INTERMOLECULAR HYDROACYLATION ; C(SP(3))-H ACTIVATION ; DENSITY FUNCTIONALS ; TRANSITION-ELEMENTS ; COBALT CATALYSIS ; AROMATIC IMINES ; MULTIPLE BONDS
WOS研究方向	Chemistry
WOS类目	Chemistry, Multidisciplinary
语种	英语
出版者	AMER CHEMICAL SOC
WOS记录号	WOS:000355053100030
内容类型	期刊论文
URI标识	http://www.corc.org.cn/handle/1471x/2376610
专题	中国科学院大学
通讯作者	Wang, Zhi-Xiang
作者单位	1.Univ Chinese Acad Sci, Sch Chem & Chem Engn, Beijing 100049, Peoples R China 2.Collaborat Innovat Ctr Chem Sci & Engn, Tianjin 300072, Peoples R China
推荐引用方式 GB/T 7714	Dang, Yanfeng,Qu, Shuanglin,Tao, Yuan,et al. Mechanistic insight into ketone alpha-alkylation with unactivated olefins via c-h activation promoted by metal-organic cooperative catalysis (mocc): enriching the mocc chemistry[J]. Journal of the american chemical society,2015,137(19):6279-6291.
APA	Dang, Yanfeng,Qu, Shuanglin,Tao, Yuan,Deng, Xi,&Wang, Zhi-Xiang.(2015).Mechanistic insight into ketone alpha-alkylation with unactivated olefins via c-h activation promoted by metal-organic cooperative catalysis (mocc): enriching the mocc chemistry.Journal of the american chemical society,137(19),6279-6291.
MLA	Dang, Yanfeng,et al."Mechanistic insight into ketone alpha-alkylation with unactivated olefins via c-h activation promoted by metal-organic cooperative catalysis (mocc): enriching the mocc chemistry".Journal of the american chemical society 137.19(2015):6279-6291.

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