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

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.