Mechanistic Insights into Nickel–NHC-Catalyzed Alkene Isomerization: A Computational Study on Selectivity and Reactivity

Abstract

Alkene isomerization holds significant importance in organic chemistry and various chemical industries; however, achieving a high selectivity remains a major challenge. This comprehensive computational investigation delves into the mechanistic parameters governing alkene isomerization catalyzed by a modular Ni(0)/silane system. By systematically analyzing electronic and steric influences of both the substrate and catalyst, the study unveils critical insights into factors that modulate catalytic selectivity and productivity of the isomerized products. In particular, the [3,1]-hydrogen migration pathway in olefins is studied, with a focus on E/Z stereoselectivity. Overall, our findings elucidate the subtle interplay between catalyst design and substrate structure, offering potential design principles for the development of more efficient nickel-catalyzed alkene isomerization processes within synthetic and industrial contexts

We are grateful for financial support from the Ministerio de Ciencia e Innovación (PID2021-127423NB-I00, PID2023-146849NB-I00, and PID2024-155989NB-I00 projects) and the Generalitat de Catalunya (2021-SGR-623). We thank the Spanish Ministerio de Universidades for the predoctoral fellowships FPU20/00707 to R.M.-C. and FPU24/02862 to A.A. A.P. and A.P.Q. are Serra Húnter Fellows. A.P. thanks ICREA Acadèmia 2019. Open Access funding provided thanks to the CRUE-CSIC agreement with ACS. Computational time at the MARENOSTRUM supercomputer has been provided by the Barcelona Supercomputing Centre through a grant from Red Española de Supercomputación (QH-2025-2-0006, QHS-2025-2-0016, QHS-2025-2-0023, and AECT-2025-1-0022). Open Access funding provided thanks to the CRUE-CSIC agreement with ACS