Mechanistic Insight into Ketone α-Alkylation with Unactivated Olefins via C-H Activation Promoted by Metal-Organic Cooperative Catalysis (MOCC): Enriching the MOCC Chemistry.
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 catal...
| Publicado en: | Journal of the American Chemical Society Vol. 137; no. 19; pp. 6279 - 6292 |
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| Autores principales: | , , , , |
| Formato: | Artículo |
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American Chemical Society
5/20/2015
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| Acceso en línea: | Ver este registro en EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=103082615&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 103082615 longDbName: Humanities International Complete uiTag: AN controlInfo: bkinfo: jinfo: jid: 00027863 ACS jtl: Journal of the American Chemical Society issn: 00027863 maglogo: N pubinfo: dt: 5/20/2015 vid: 137 iid: 19 pid: 997 pub: American Chemical Society artinfo: ui: 103082615 10.1021/jacs.5b01502 ppf: 6279 ppct: 13 formats: tig: atl: Mechanistic Insight into Ketone α-Alkylation with Unactivated Olefins via C-H Activation Promoted by Metal-Organic Cooperative Catalysis (MOCC): Enriching the MOCC Chemistry. aug: au: Yanfeng Dang Shuanglin Qu Yuan Tao Xi Deng Zhi-Xiang Wang affil: School of Chemistry and Chemical Engineering, University of the Chinese Academy of Sciences, Beijing 100049, China Collaborative Innovation Center of Chemical Science and Engineering, Tianjin 300072, China su: Ketone synthesis Alkylation Alkenes Carbon-hydrogen bonds Organometallic compounds Density functional theory sug: subj: Ketone synthesis Alkylation Alkenes Carbon-hydrogen bonds Organometallic compounds Density functional theory ab: 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 α-alkylation with unactivated olefins via C(sp³)-H activation. Herein we present a density functional theory study to understand the mechanism of the challenging ketone α-alkylation. The transformation uses IMesRh(I)Cl(L1)(CH═CH) 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)-1bintermediate; C(sp²)-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 α-alkylation product 1d 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 L1 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 L1 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. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2015 holdings: @attributes: islocal: N |
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