DFT Study on Mechanism and Regioselectivity in Pd(II)‐Catalyzed Dehydrogenative Heck Olefination of Selenophenes

ChemistrySelect, Journal Year: 2025, Volume and Issue: 10(4)

Published: Jan. 1, 2025

Abstract The present study deals with the theoretical investigation of mechanistic and regiochemical aspects Pd(II)‐catalyzed dehydrogenative Heck olefination selenophenes. detailed reaction mechanism was established, roles catalyst regioselectivity were well rationalized. Our results clearly showed that whole involves a concerted metalation‐deprotonation (CMD) process between C 2 site selenophene Pd(OAc) in first catalytic cycle. Afterward, olefin coordinates to palladium, followed by regioselective 1,2‐migratory insertion form C─C bond. Then, β ‐hydride elimination would give final 2‐monoolefinated product. Subsequently, second cycle generates symmetrical 2,5‐diolefinated Another key finding this is its monoolefinated product act as nucleophiles, while behaves an electrophile. A global reactivity index (GRI) analysis revealed nucleophilicity ( N k ) , 3 4 5 atoms plays important role controlling selectivity at these sites. However, distortion energies play more reactions

Language: Английский

Interplay of Ligand-Controlled Reaction Pathways: DFT Analysis of Mechanisms and Selectivities in Pd-Catalyzed Semireduction of Allenamides

Molecular Catalysis, Journal Year: 2024, Volume and Issue: 560, P. 114126 - 114126

Published: April 12, 2024

Language: Английский