Mechanistic understanding enables chemoselective sp3 over sp2 C–H activation in Pdcatalyzed carbonylative cyclization of amino acids
Entity
UAM. Departamento de Química OrgánicaPublisher
Royal Society of ChemistryDate
2021-01-04Citation
10.1039/D0CY02328K
Catalysis Science and Technology 11.4 (2021): 1590-1601
ISSN
2044-4753 (print); 2044-4761 (online)DOI
10.1039/D0CY02328KFunded by
We thank the Ministerio de Economía, Industria y Competitividad (Project CTQ2015-66954-P, MINECO/FEDER, UE) and Ministerio de Ciencia, Innovación y Universidades/ FEDER (Agencia Estatal de Investigación/Project PGC2018- 098660-B-I00) for financial supportProject
Gobierno de España. CTQ2015-66954-P; Gobierno de España. PGC2018-098660-B-I00Editor's Version
https://doi.org/10.1039/D0CY02328KSubjects
Alkenylation; 8-Aminoquinoline; Rhodium; QuímicaRights
© 2021 The Royal Society of ChemistryAbstract
Mechanistic insights into the factors that control chemoselectivity in competing C(sp2 )–H and C(sp3 )–H activation pathways in the palladium-catalyzed carbonylative cyclization of γ-arylated valine type derivatives, gained by experimental observations and DFT studies, have been leveraged to reverse the remarkable selectivity of Pd for arene C(sp2 )–H activation over C(sp3 )–H cleavage. These studies suggest that ε-C(sp2 )–H bond cleavage is significantly faster and more reversible than the γ-C(sp3 )–H bond activation, whereas subsequent AcOH/CO exchange and CO insertion from the C(sp3 )-palladacycle lead to more stable intermediates from which the reaction is irreversible. Control of chemoselectivity has been achieved by playing on the reaction conditions to favour thermodynamic over kinetic control. Addressing this fundamental limitation of C–H functionalization under Pd-catalysis has enabled the access to different heterocyclic frameworks (i.e., γ-lactams instead of benzazepinone skeletons) from the same starting substrate
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Supporting Information
Google Scholar:Martínez-Mingo, Mario
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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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