Solvent-Assisted Ketone Reduction by a Homogeneous Mn Catalyst

Annika M. Krieger, Vivek Sinha, Guanna Li, Evgeny A. Pidko*

*Corresponding author for this work

Research output: Contribution to journalArticleAcademicpeer-review

Abstract

The choice of a solvent and the reaction conditions often defines the overall behavior of a homogeneous catalytic system by affecting the preferred reaction mechanism and thus the activity and selectivity of the catalytic process. Here, we explore the role of solvation in the mechanism of ketone reduction using a model representative of a bifunctional Mn-diamine catalyst through density functional theory calculations in a microsolvated environment by considering explicit solvent and fully solvated ab initio molecular dynamics simulations for the key elementary steps. Our computational analysis reveals the possibility of a Meerwein-Ponndorf-Verley (MPV) type mechanism in this system, which does not involve the participation of the N-H moiety and the formation of a transition-metal hydride species in ketone conversion. This path was not previously considered for Mn-based metal-ligand cooperative transfer hydrogenation homogeneous catalysis. The MPV mechanism is strongly facilitated by the solvent molecules present in the reaction environment and can potentially contribute to the catalytic performance of other related catalyst systems. Calculations indicate that, despite proceeding effectively in the second coordination sphere of the transition-metal center, the MPV reaction path retains the enantioselectivity preference induced by the presence of the small chiral N,N′-dimethyl-1,2-cyclohexanediamine ligand within the catalytic Mn(I) complex.

Original languageEnglish
Pages (from-to)1829-1835
JournalOrganometallics
Volume41
Issue number14
Early online date2022
DOIs
Publication statusPublished - 25 Jul 2022

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