biostudies-literatureZhou MMDepartment of Education of Guangdong ProvinceNational Natural Science Foundation of China9431-9437https://www.ebi.ac.uk/biostudies/studies/S-EPMC9050042biostudies-literatureUnknown10(16)A detailed theoretical study on the mechanism of enanthioselective hydrosilylation of imines and ketones catalyzed by the ruthenium(ii) thiolate catalyst [Ru-S] ([L*-Ru(SDmp)]⁺[BAr₄ ^F]^-) with a chiral monodentate phosphine ligand is carried out in this work. We elucidate all the pathways leading to the main products or by products mediated by the [Ru-S] complex in order to have deep understanding of the chemoselectivity and enantioselectivity. The DFT (Density Functional Theory) calculations show that the reaction mechanism including: (1) Si-H bond cleavage by the dual activity of Ru-S bond; (2) the generation of a sulfur-stabilized silane cation; (3) the electrophilic attack of silane cation to N[double bond, length as m-dash]C/O[double bond, leRSC advancesEnantioselective hydrosilylation of unsaturated carbon-heteroatom bonds (C[double bond, length as m-dash]N, C[double bond, length as m-dash]O) catalyzed by [Ru-S] complexes: a theoretical study.PMC905004221573102Dang LZhou MMChen GfalseEnantioselective hydrosilylation of unsaturated carbon-heteroatom bonds (C[double bond, length as m-dash]N, C[double bond, length as m-dash]O) catalyzed by [Ru-S] complexes: a theoretical study.A detailed theoretical study on the mechanism of enanthioselective hydrosilylation of imines and ketones catalyzed by the ruthenium(ii) thiolate catalyst [Ru-S] ([L*-Ru(SDmp)]⁺[BAr₄ ^F]^-) with a chiral monodentate phosphine ligand is carried out in this work. We elucidate all the pathways leading to the main products or by products mediated by the [Ru-S] complex in order to have deep understanding of the chemoselectivity and enantioselectivity. The DFT (Density Functional Theory) calculations show that the reaction mechanism including: (1) Si-H bond cleavage by the dual activity of Ru-S bond; (2) the generation of a sulfur-stabilized silane cation; (3) the electrophilic attack of silane cation to N[double bond, length as m-dash]C/O[double bond, le2020-01-01T00:00:00Z2020 Mar2025-04-04T23:16:07.466Z2025-04-04T23:16:07.466ZS-EPMC90500423549724410.1039/c9ra10760f