NHC-Copper(I) Halide-Catalyzed Direct Alkynylation of Trifluoromethyl Ketones on Water

Handle URI:
http://hdl.handle.net/10754/621704
Title:
NHC-Copper(I) Halide-Catalyzed Direct Alkynylation of Trifluoromethyl Ketones on Water
Authors:
Czerwiński, Paweł; Molga, Edyta; Cavallo, Luigi ( 0000-0002-1398-338X ) ; Poater, Albert ( 0000-0002-8997-2599 ) ; Michalak, Michał
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. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
KAUST Department:
KAUST Catalysis Center (KCC); Physical Sciences and Engineering (PSE) Division
Citation:
Czerwiński P, Molga E, Cavallo L, Poater A, Michalak M (2016) NHC-Copper(I) Halide-Catalyzed Direct Alkynylation of Trifluoromethyl Ketones on Water. Chem Eur J 22: 8089–8094. Available: http://dx.doi.org/10.1002/chem.201601581.
Publisher:
Wiley-Blackwell
Journal:
Chemistry - A European Journal
Issue Date:
4-May-2016
DOI:
10.1002/chem.201601581
Type:
Article
ISSN:
0947-6539
Sponsors:
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 (KAUST). We would like to thank Prof. Samir Zard (Ecole Polytechnique) for helpful discussion concerning the synthesis of trifluoromethyl ketones and Dr. P. Kwiatkowski and Dr. W. Chaladaj for a generous gift of samples of trifluoromethyl ketones and alkynes.
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorCzerwiński, Pawełen
dc.contributor.authorMolga, Edytaen
dc.contributor.authorCavallo, Luigien
dc.contributor.authorPoater, Alberten
dc.contributor.authorMichalak, Michałen
dc.date.accessioned2016-11-03T13:23:08Z-
dc.date.available2016-11-03T13:23:08Z-
dc.date.issued2016-05-04en
dc.identifier.citationCzerwiński P, Molga E, Cavallo L, Poater A, Michalak M (2016) NHC-Copper(I) Halide-Catalyzed Direct Alkynylation of Trifluoromethyl Ketones on Water. Chem Eur J 22: 8089–8094. Available: http://dx.doi.org/10.1002/chem.201601581.en
dc.identifier.issn0947-6539en
dc.identifier.doi10.1002/chem.201601581en
dc.identifier.urihttp://hdl.handle.net/10754/621704-
dc.description.abstractAn 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. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.en
dc.description.sponsorshipThe 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 (KAUST). We would like to thank Prof. Samir Zard (Ecole Polytechnique) for helpful discussion concerning the synthesis of trifluoromethyl ketones and Dr. P. Kwiatkowski and Dr. W. Chaladaj for a generous gift of samples of trifluoromethyl ketones and alkynes.en
dc.publisherWiley-Blackwellen
dc.subjectAlkynylationen
dc.subjectCopperen
dc.subjectKetonesen
dc.subjectN-heterocyclic carbenesen
dc.subjectOn wateren
dc.titleNHC-Copper(I) Halide-Catalyzed Direct Alkynylation of Trifluoromethyl Ketones on Wateren
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.identifier.journalChemistry - A European Journalen
dc.contributor.institutionInstitute of Organic Chemistry; Polish Academy of Sciences; 01-224 Warsaw, Kasprzaka 44/52 Polanden
dc.contributor.institutionFaculty of Chemistry; Warsaw University of Technology, Noakowskiego 3; 00-664 Warsaw Polanden
dc.contributor.institutionInstitut de Química Computacional i Catàlisi and Departament de Química; Universitat de Girona, Campus Montilivi; 17071 Girona, Catalonia Spainen
kaust.authorCavallo, Luigien
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