Palladium-Catalyzed Carbonylative Cyclization of Amines via γ-C(sp3)-H Activation: Late-Stage Diversification of Amino Acids and Peptides

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Show simple item record Hernando, Elier Villalva, Julia Martínez, Ángel Manu Alonso, Inés Rodríguez, Nuria Gómez Arrayás, Ramón Carretero, Juan C.
dc.contributor.other UAM. Departamento de Química Orgánica es_ES 2016-11-14T13:07:13Z 2016-11-14T13:07:13Z 2016-10-07
dc.identifier.citation ACS Catalysis 6.10 (2016): 6868 - 6882 es_ES
dc.identifier.issn 2155-5435 es_ES
dc.description This document is the Accepted Manuscript version of a Published Work that appeared in final form in ACS Catalysis, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see en_US
dc.description.abstract The selective γ-C(sp3)-H carbonylation of N-(2-pyridyl)sulfonyl (N-SO2Py)-protected amines has been accomplished by using palladium catalysis and Mo(CO)6 as carbonyl source. The reaction provides a powerful approach for derivatization of amine-based moieties, including amino acids, into richly functionalized γ-lactams. Not only methyl groups, but also methylene C-H bonds of cyclopropanes and conformationally biased molecules can be activated to provide ring-fused γ-lactam derivatives. This carbonylation protocol is also amenable to the late-stage diversification of more-complex multifunctional molecules such as dipeptides and tripeptides, demonstrating the key role of the N-SO2Py as directing group and its capacity to override other inherent substrate coordinating elements. In addition to providing an attractive solution to the difficulties in handling hazardous CO gas, the use of Mo(CO)6 as an air-stable solid source of CO in substoichiometric amount (0.33 equiv) ensures PdII-catalytic activity by preventing its decomposition or deactivation under excess of CO via reduction of PdII to Pd0 or saturation of the metal coordination sphere. Indeed, significantly lower efficiency is observed when the reactions are carried out under CO atmosphere (1 atm), or in the presence of increased amounts of Mo(CO)6. A series of experimental and DFT mechanistic studies provide important insights about the reaction mechanism en_US
dc.description.sponsorship We thank the Spanish Ministerio de Economía y Competitividad (MINECO, Project No. CTQ2012-35790), and MINECO/FEDER, UE (Project No. CTQ2015-66954-P) for financial support. E.H. thanks the Gobierno Vasco for a predoctoral fellowship. N.R. thanks the MICINN for a Ramón y Cajal contract and the European Commission for a Marie Curie Foundation (CIG: CHAAS-304085) en_US
dc.format.extent 15 pag. en
dc.format.mimetype application/pdf en
dc.language.iso eng en
dc.relation.ispartof ACS Catalysis en_US
dc.rights © 2016 American Chemical Society en_US
dc.subject.other 2-pyridylsulfonyl es_ES
dc.subject.other C-H carbonylation en_US
dc.subject.other γ-lactam en_US
dc.subject.other Aliphatic amine en_US
dc.subject.other Amino acid en_US
dc.subject.other Palladium catalysis en_US
dc.subject.other Peptide en_US
dc.title Palladium-Catalyzed Carbonylative Cyclization of Amines via γ-C(sp3)-H Activation: Late-Stage Diversification of Amino Acids and Peptides en_US
dc.type article en
dc.subject.eciencia Química es_ES 2017-10-08
dc.relation.publisherversion es_ES
dc.identifier.doi 10.1021/acscatal.6b01987 es_ES
dc.identifier.publicationfirstpage 6868 es_ES
dc.identifier.publicationissue 10 es_ES
dc.identifier.publicationlastpage 6882 es_ES
dc.identifier.publicationvolume 6 es_ES
dc.relation.projectID Gobierno de España. CTQ2012-35790 es_ES
dc.relation.projectID Gobierno de España. CTQ2015-66954-P es_ES
dc.relation.projectID info:eu-repo/grantAgreement/EC/FP7/304085 es_ES
dc.type.version info:eu-repo/semantics/acceptedVersion en
dc.rights.accessRights openAccess en
dc.authorUAM Hernando Martínez, Elier (264601)
dc.authorUAM Gómez Arrayas, Ramón Jesús (260197)
dc.authorUAM Carretero Gonzálvez, Juan Carlos (260121)
dc.authorUAM Rodríguez Garrido, Nuria (264625)

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