Autor segons l'article: García-Padilla, E; Escofet, I; Maseras, F; Echavarren, AM
Departament: Química Analítica i Química Orgànica
Autor/s de la URV: ECHAVARREN PABLOS, ANTONIO / García Padilla, Eduardo
Paraules clau: 1,6-enynes approximation carbocations catalyzed cycloisomerization correlation-energy cycloisomerization dft calculations enynes exploration gold(i) catalysis gold-carbene platinum skeletal rearrangement Allenenes Cycloisomerization Density-functional methods Dft calculations Enynes Gold(i) catalysis
Resum: We identify the dominant structures of the intermediates of gold(I)-catalyzed cyclizations of 1,5-enynes and 1,5-allenenes through computational analysis as gold(I) cyclopropylcarbenes, endocyclic vinylgold complexes and previously unreported non-classical carbocationic minima. In contrast to 1,6-enynes, the exocyclic carbocations are found to be less stable. Cyclopropylcarbene structures are consistently favoured as the most stable intermediates for all studied substitution patterns. We validate the computational methods used by using DLPNO-CCSD(T) energies as a benchmark, indicating that the B3LYP-D3 and M06-D3 functionals are most accurate for energy determination, while NPA charges are mostly insensitive to functional. The evolution of a 1,6-enyne in a single-cleavage or double-cleavage rearrangement is attributed to the barrierless evolution of a common cyclopropyl–gold(I) carbocation non-stationary geometry. Our findings provide insights into reaction pathways and substrate dependence of the cycloisomerization processes.
Àrees temàtiques: Chemistry (all) Chemistry (miscellaneous) Chemistry, multidisciplinary General chemistry Química
Accès a la llicència d'ús: https://creativecommons.org/licenses/by/3.0/es/
Adreça de correu electrònic de l'autor: eduardo.garcia@estudiants.urv.cat antoniomaria.echavarren@urv.cat
ISSN: 2192-6506
Identificador de l'autor: 0000-0001-9715-7992 0000-0002-6418-7930
Data d'alta del registre: 2024-01-13
Versió de l'article dipositat: info:eu-repo/semantics/publishedVersion
Referència a l'article segons font original: Chempluschem.
Referència de l'ítem segons les normes APA: García-Padilla, E; Escofet, I; Maseras, F; Echavarren, AM (2023). Puzzling Structure of the Key Intermediates in Gold(I)-catalyzed Cyclization Reactions of Enynes and Allenenes. Chempluschem, (), -. DOI: 10.1002/cplu.202300502
URL Document de llicència: https://repositori.urv.cat/ca/proteccio-de-dades/
Entitat: Universitat Rovira i Virgili
Any de publicació de la revista: 2023
Tipus de publicació: Journal Publications
Repositori URV