Understanding asymmetric hydrogenation of alkenes catalyzed by first-row transition metal, Fe: a first-principles exploration

Abstract

First-principles analyses have been performed for understanding the mechanistic details of Fe catalysed asymmetric hydrogenation of alkenes in presence of silane that has recently been realized experimentally. The catalytic hydrogenation is supposed to proceed through initial hydride transfer from Fe-H to the C=C bond of alkene, followed by σ-bond metathesis with in-situ generated hydrosilane to afford the chiral alkane product and an iron silyl species which then reacts with H2 to regenerate the iron hydride species via another σ-bond metathesis. The mechanistic details, and origin of the regioselectivity and stereoselectivity of these reactions are understood on the basis of detailed potential energy surface analysis, charge transfer and noncovalent interactions involved therein, strain energy and isodesmic studies in solvated stage. Finally, the general aspects are highlighted for guiding further experimental studies for having precise control over the reaction scheme.