Catalytic C–S, C–Se, and C–P Cross-Coupling Reactions Mediated by a CuI/CuIII Redox Cycle
dc.contributor.author
dc.date.accessioned
2013-12-03T08:09:16Z
dc.date.available
2013-12-03T08:09:16Z
dc.date.issued
2012
dc.identifier.issn
0276-7333
dc.identifier.uri
dc.description.abstract
A well-defined macrocyclic aryl-CuIII complex (1) readily reacts with a series of R–SH, Ar–SH, Ar–SeH, and (RO)2(O)–PH (R = alkyl) nucleophiles to quantitatively afford the corresponding aryl alkyl thioethers, biaryl thioethers, biaryl selenide, and aryl dialkyl phosphonates, respectively. Competition experiments using bifunctional substrates revealed the important impact of lower pKa values in order to discriminate between functional groups, although other influencing parameters such as steric effects have been identified. The catalytic version of these reactions is achieved using aryl bromide and aryl chloride model substrates, affording C–S, C–Se, and C–P coupling compounds in excellent to moderate yields. Low-temperature UV–vis and NMR monitoring of the reactions of complex 1 with a variety of nucleophiles support the formation of a ground-state 1–nucleophile adduct. A mechanistic proposal for reaction of 1 with S-nucleophiles involving key nucleophile deprotonation and aryl-nucleophile reductive elimination steps is finally described
dc.description.sponsorship
We thank Dr. A. Casitas for fruitful discussions. We acknowledge financial support from the European Research Council for Project ERC-2011-StG-277801 to X.R., MICINN of Spain (CTQ2009-08464/BQU to M.C., CT2009-08328 to T.P., and Ph.D. FPI grant to M.F.), Consolider-Ingenio CSD2010-00065, and the Catalan DIUE of the Generalitat de Catalunya (2009SGR637). X.R. and M.C. acknowledge ICREA-Academia awards. We thank STR's from UdG for technical support
dc.format.mimetype
application/pdf
dc.language.iso
eng
dc.publisher
American Chemical Society
dc.relation
MICINN/PN 2010-2012/CTQ2009-08464
MICINN/PN 2010-2016/CSD2010-00065
AGAUR/2009-2014/2009 SGR-637
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Reproducció digital del document publicat a: http://dx.doi.org/10.1021/om3006323
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© Organometallics, 2012, vol. 31, núm. 22, p. 7976-7982
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Articles publicats (D-Q)
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Tots els drets reservats
dc.title
Catalytic C–S, C–Se, and C–P Cross-Coupling Reactions Mediated by a CuI/CuIII Redox Cycle
dc.type
info:eu-repo/semantics/article
dc.rights.accessRights
info:eu-repo/semantics/embargoedAccess
dc.embargo.terms
Cap
dc.date.embargoEndDate
info:eu-repo/date/embargoEnd/2026-01-01
dc.relation.projectID
info:eu-repo/grantAgreement/EC/FP7/277801/EU/Sustainable C-X and C-H Functionalization Catalyzed by Copper(III) Species/SUSCATCU3
dc.type.version
info:eu-repo/semantics/publishedVersion
dc.identifier.doi
dc.contributor.funder
dc.relation.FundingProgramme
dc.relation.ProjectAcronym
dc.identifier.eissn
1520-6041