Palladium-Catalyzed Carbonylative Cyclization of Amines via γ-C(sp3)-H Activation: Late-Stage Diversification of Amino Acids and Peptides
Entidad
UAM. Departamento de Química OrgánicaFecha de edición
2016-10-07Cita
10.1021/acscatal.6b01987
ACS Catalysis 6.10 (2016): 6868 - 6882
ISSN
2155-5435DOI
10.1021/acscatal.6b01987Financiado por
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)Proyecto
Gobierno de España. CTQ2012-35790; Gobierno de España. CTQ2015-66954-P; info:eu-repo/grantAgreement/EC/FP7/304085Versión del editor
http://dx.doi.org/10.1021/acscatal.6b01987Materias
2-pyridylsulfonyl; C-H carbonylation; γ-lactam; Aliphatic amine; Amino acid; Palladium catalysis; Peptide; QuímicaNota
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 http://pubs.acs.org/doi/abs/10.1021/acscatal.6b01987Derechos
© 2016 American Chemical SocietyResumen
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
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Google Scholar:Hernando, Elier
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Villalva, Julia
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Martínez, Ángel Manu
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Alonso Montero, María Inés
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Rodríguez Garrido, Nuria
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Gómez Arrayas, Ramón Jesús
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Carretero Gonzálvez, Juan Carlos
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