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dc.contributor.authorChatupheeraphat, Adisak
dc.contributor.authorLiao, Hsuan-Hung
dc.contributor.authorSrimontree, Watchara
dc.contributor.authorGuo, Lin
dc.contributor.authorMinenkov, Yury
dc.contributor.authorPoater, Albert
dc.contributor.authorCavallo, Luigi
dc.contributor.authorRueping, Magnus
dc.date.accessioned2018-03-11T06:54:12Z
dc.date.available2018-03-11T06:54:12Z
dc.date.issued2018-02-20
dc.identifier.citationChatupheeraphat A, Liao H-H, Srimontree W, Guo L, Minenkov Y, et al. (2018) Ligand-Controlled Chemoselective C(acyl)–O Bond vs C(aryl)–C Bond Activation of Aromatic Esters in Nickel Catalyzed C(sp2)–C(sp3) Cross-Couplings. Journal of the American Chemical Society. Available: http://dx.doi.org/10.1021/jacs.7b12865.
dc.identifier.issn0002-7863
dc.identifier.issn1520-5126
dc.identifier.pmid29461813
dc.identifier.doi10.1021/jacs.7b12865
dc.identifier.urihttp://hdl.handle.net/10754/627261
dc.description.abstractA ligand-controlled and site-selective nickel catalyzed Suzuki-Miyaura cross-coupling reaction with aromatic esters and alkyl organoboron reagents as coupling partners was developed. This methodology provides a facile route for C(sp2)-C(sp3) bond formation in a straightforward fashion by successful suppression of the undesired β-hydride elimination process. By simply switching the phosphorus ligand, the ester substrates are converted into the alkylated arenes and ketone products, respectively. The utility of this newly developed protocol was demonstrated by its wide substrate scope, broad functional group tolerance and application in the synthesis of key intermediates for the synthesis of bioactive compounds. DFT studies on the oxidative addition step helped rationalizing this intriguing reaction chemoselectivity: whereas nickel complexes with bidentate ligands favor the C(aryl)-C bond cleavage in the oxidative addition step leading to the alkylated product via a decarbonylative process, nickel complexes with monodentate phosphorus ligands favor activation of the C(acyl)-O bond, which later generates the ketone product.
dc.description.sponsorshipH.-H.L. thanks the DAAD for a doctoral fellowship. A.P. thanks the Spanish MINECO for a project CTQ2014-59832-JIN. This research was supported by the KAUST Office of Sponsored Research under Award No. URF/1/3030-01. L.C. thanks the King Abdullah University of Science and Technology (KAUST) for supporting this work. For computer time, this research used the resources of the KAUST Supercomputing Laboratory (KSL) at KAUST.
dc.publisherAmerican Chemical Society (ACS)
dc.relation.urlhttps://pubs.acs.org/doi/10.1021/jacs.7b12865
dc.titleLigand-Controlled Chemoselective C(acyl)–O Bond vs C(aryl)–C Bond Activation of Aromatic Esters in Nickel Catalyzed C(sp2)–C(sp3) Cross-Couplings
dc.typeArticle
dc.contributor.departmentKAUST Catalysis Center (KCC)
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Division
dc.contributor.departmentChemical Science Program
dc.identifier.journalJournal of the American Chemical Society
dc.contributor.institutionInstitute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, 52074 Aachen, Germany
dc.contributor.institutionInstitut de Química Computacional i Catàlisi and Departament de Química, Universitat de Girona, Campus Montilivi, 17003 Girona, Catalonia, Spain
kaust.personMinenkov, Yury
kaust.personPoater, Albert
kaust.personCavallo, Luigi
kaust.personRueping, Magnus
kaust.grant.numberURF/1/3030-01


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