Sequential Functionalization of Alkynes and Alkenes Catalyzed by Gold(I) and Palladium(II) N-Heterocyclic Carbene Complexes

Handle URI:
http://hdl.handle.net/10754/623590
Title:
Sequential Functionalization of Alkynes and Alkenes Catalyzed by Gold(I) and Palladium(II) N-Heterocyclic Carbene Complexes
Authors:
Gómez-Herrera, Alberto; Nahra, Fady; Brill, Marcel; Nolan, Steven P. ( 0000-0001-9024-2035 ) ; Cazin, Catherine S. J. ( 0000-0002-9094-8131 )
Abstract:
The iodination of terminal alkynes for the synthesis of 1-iodoalkynes using N-iodosuccinimide in the presence of a AuI-NHC (NHC=N-heterocyclic carbene) catalyst is reported. A series of aromatic alkynes was transformed successfully into the corresponding 1-iodoalkynes in good to excellent yields under mild reaction conditions. The further use of these compounds as organic building blocks and the advantageous choice of metal-NHC complexes as catalysts for alkyne functionalization were further demonstrated by performing selective AuI-catalyzed hydrofluorination to yield (Z)-2-fluoro-1-iodoalkenes, followed by a Suzuki–Miyaura cross-coupling with aryl boronic acids catalyzed by a PdII-NHC complex to access trisubstituted (Z)-fluoroalkenes. All methodologies can be performed sequentially with only minor variations in the optimized individual reaction conditions, maintaining high efficiency and selectivity in all cases, which therefore, provides straightforward access to valuable fluorinated alkenes from commercially available terminal alkynes.
Citation:
Gómez-Herrera A, Nahra F, Brill M, Nolan SP, Cazin CSJ (2016) Sequential Functionalization of Alkynes and Alkenes Catalyzed by Gold(I) and Palladium(II) N-Heterocyclic Carbene Complexes. ChemCatChem 8: 3381–3388. Available: http://dx.doi.org/10.1002/cctc.201600868.
Publisher:
Wiley-Blackwell
Journal:
ChemCatChem
KAUST Grant Number:
OSR-2015-CCF-1974–03
Issue Date:
22-Aug-2016
DOI:
10.1002/cctc.201600868
Type:
Article
ISSN:
1867-3880
Sponsors:
The authors gratefully acknowledge the Royal Society (University Research Fellowship to C.S.J.C.), Syngenta (studentship to A.G.H.), King Saud University (S.P.N.) and the EPSRC (EP/K503162/1) for funding. We are also grateful to Umicore for the loan of Pd complexes and to the EPSRC National Mass Spectrometry Service Centre at Swansea University for HRMS analyses. This publication is based upon work supported by the King Abdullah University of Science and Technology (KAUST) Office of Sponsored Research (OSR) under Award No. OSR-2015-CCF-1974–03.
Additional Links:
http://onlinelibrary.wiley.com/doi/10.1002/cctc.201600868/full
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Full metadata record

DC FieldValue Language
dc.contributor.authorGómez-Herrera, Albertoen
dc.contributor.authorNahra, Fadyen
dc.contributor.authorBrill, Marcelen
dc.contributor.authorNolan, Steven P.en
dc.contributor.authorCazin, Catherine S. J.en
dc.date.accessioned2017-05-15T10:35:10Z-
dc.date.available2017-05-15T10:35:10Z-
dc.date.issued2016-08-22en
dc.identifier.citationGómez-Herrera A, Nahra F, Brill M, Nolan SP, Cazin CSJ (2016) Sequential Functionalization of Alkynes and Alkenes Catalyzed by Gold(I) and Palladium(II) N-Heterocyclic Carbene Complexes. ChemCatChem 8: 3381–3388. Available: http://dx.doi.org/10.1002/cctc.201600868.en
dc.identifier.issn1867-3880en
dc.identifier.doi10.1002/cctc.201600868en
dc.identifier.urihttp://hdl.handle.net/10754/623590-
dc.description.abstractThe iodination of terminal alkynes for the synthesis of 1-iodoalkynes using N-iodosuccinimide in the presence of a AuI-NHC (NHC=N-heterocyclic carbene) catalyst is reported. A series of aromatic alkynes was transformed successfully into the corresponding 1-iodoalkynes in good to excellent yields under mild reaction conditions. The further use of these compounds as organic building blocks and the advantageous choice of metal-NHC complexes as catalysts for alkyne functionalization were further demonstrated by performing selective AuI-catalyzed hydrofluorination to yield (Z)-2-fluoro-1-iodoalkenes, followed by a Suzuki–Miyaura cross-coupling with aryl boronic acids catalyzed by a PdII-NHC complex to access trisubstituted (Z)-fluoroalkenes. All methodologies can be performed sequentially with only minor variations in the optimized individual reaction conditions, maintaining high efficiency and selectivity in all cases, which therefore, provides straightforward access to valuable fluorinated alkenes from commercially available terminal alkynes.en
dc.description.sponsorshipThe authors gratefully acknowledge the Royal Society (University Research Fellowship to C.S.J.C.), Syngenta (studentship to A.G.H.), King Saud University (S.P.N.) and the EPSRC (EP/K503162/1) for funding. We are also grateful to Umicore for the loan of Pd complexes and to the EPSRC National Mass Spectrometry Service Centre at Swansea University for HRMS analyses. This publication is based upon work supported by the King Abdullah University of Science and Technology (KAUST) Office of Sponsored Research (OSR) under Award No. OSR-2015-CCF-1974–03.en
dc.publisherWiley-Blackwellen
dc.relation.urlhttp://onlinelibrary.wiley.com/doi/10.1002/cctc.201600868/fullen
dc.subjectalkynesen
dc.subjectcarbenesen
dc.subjectcross-couplingen
dc.subjectgolden
dc.subjectpalladiumen
dc.titleSequential Functionalization of Alkynes and Alkenes Catalyzed by Gold(I) and Palladium(II) N-Heterocyclic Carbene Complexesen
dc.typeArticleen
dc.identifier.journalChemCatChemen
dc.contributor.institutionEaStCHEM School of Chemistry; University of St Andrews; St Andrews KY16 9ST UKen
dc.contributor.institutionDepartment of Inorganic and Physical Chemistry; Ghent University; Krijgslaan 281 - S3 9000 Gent Belgiumen
dc.contributor.institutionChemistry Department; College of Science; King Saud University; PO Box 2455 Riyadh 11451 Saudi Arabiaen
kaust.grant.numberOSR-2015-CCF-1974–03en
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