title: A theoretically-guided optimization of a new family of modular P,S-ligands for iridium-catalyzed hydrogenation of minimally functionalized olefins.
abstract: A library of modular iridium complexes derived from thioether-phosphite/phosphinite ligands has been evaluated in the asymmetric iridium-catalyzed hydrogenation of minimally functionalized olefins. The modular ligand design has been shown to be crucial in finding highly selective catalysts for each substrate. A DFT study of the transition state responsible for the enantiocontrol in the Ir-catalyzed hydrogenation is also described and used for further optimization of the crucial stereodefining moieties. Excellent enantioselectivities (enantiomeric excess (ee) values up to 99 %) have been obtained for a range of substrates, including E- and Z-trisubstituted and disubstituted olefins, α,β-unsaturated enones, tri- and disubstituted alkenylboronic esters, and olefins with trifluoromethyl substituents.
authors.affiliation: Departament de Química Física i Inorgànica, Universitat Rovira i Virgili, C/Marcel⋅li Domingo, s/n., 43007 Tarragona (Spain).
authors.forename: Jèssica
authors.initials: J
authors.lastname: Margalef
authors.forename: Xisco
authors.initials: X
authors.lastname: Caldentey
authors.forename: Erik A
authors.initials: EA
authors.lastname: Karlsson
authors.forename: Mercè
authors.initials: M
authors.lastname: Coll
authors.forename: Javier
authors.initials: J
authors.lastname: Mazuela
authors.forename: Oscar
authors.initials: O
authors.lastname: Pàmies
authors.forename: Montserrat
authors.initials: M
authors.lastname: Diéguez
authors.forename: Miquel A
authors.initials: MA
authors.lastname: Pericàs
mesh_terms: D000475:Alkenes / Q000737:chemistry*; D002384:Catalysis; D006865:Hydrogenation; D007495:Iridium / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D000475:Alkenes; D007495:Iridium
keywords: asymmetric synthesis; density functional theory; hydrogenation; iridium; ligands