NHC-Copper(I) Halide-Catalyzed Direct Alkynylation of Trifluoromethyl Ketones on Water
dc.contributor.author
dc.date.accessioned
2016-11-18T07:37:21Z
dc.date.available
2016-11-18T07:37:21Z
dc.date.issued
2016-01-01
dc.identifier.issn
0947-6539
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dc.description.abstract
An efficient and easily scalable NHC-copper(I) halide-catalyzed addition of terminal alkynes to 1,1,1-trifluoromethyl ketones, carried out on water for the first time, is reported. A series of addition reactions were performed with as little as 0.1-2.0mol% of [(NHC)CuX] (X=Cl, Br, I, OAc, OTf) complexes, providing tertiary propargylic trifluoromethyl alcohols in high yields and with excellent chemoselectivity from a broad range of aryl- and more challenging alkyl-substituted trifluoromethyl ketones (TFMKs). DFT calculations were performed to rationalize the correlation between the yield of catalytic alkynylation and the sterics of N-heterocyclic carbenes (NHCs), expressed as buried volume (%VBur), indicating that steric effects dominate the yield of the reaction. Additional DFT calculations shed some light on the differential reactivity of [(NHC)CuX] complexes in the alkynylation of TFMKs. The first enantioselective version of a direct alkynylation in the presence of C1-symmetric NHC-copper(I) complexes is also presented
dc.description.sponsorship
The authors are grateful to Polish Ministry of Science and Higher Education for financial support of the research (grant Iuventus Plus IP2012 064172). A.P. thanks the Spanish MINECO for project CTQ2014-59832-JIN, and L.C. funding from King Abdullah University of Science and Technology (KAUS)
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application/pdf
dc.language.iso
eng
dc.publisher
Wiley
dc.relation
info:eu-repo/grantAgreement/MINECO//CTQ2014-59832-JIN/ES/ESCANEO COMPUTACIONAL DE RELACIONES ESTRUCTURA%2FACTIVIDAD DE CATALIZADORES DE OXIDACION DEL AGUA PARA LA GENERACION DE H2/
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Reproducció digital del document publicat a: http://dx.doi.org/10.1002/chem.201601581
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© Chemistry-A European Journal, 2016, vol. 22, núm. 24, p. 8089–8094
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Articles publicats (D-Q)
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Tots els drets reservats
dc.subject
dc.title
NHC-Copper(I) Halide-Catalyzed Direct Alkynylation of Trifluoromethyl Ketones on Water
dc.type
info:eu-repo/semantics/article
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info:eu-repo/semantics/embargoedAccess
dc.embargo.terms
Cap
dc.date.embargoEndDate
info:eu-repo/date/embargoEnd/2026-01-01
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info:eu-repo/semantics/publishedVersion
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