Understanding ketone hydrogenation catalysis with anionic iridium(iii) complexes: the crucial role of counterion and solvation.

ABSTRACT: Catalytic asymmetric hydrogenation of ketones is an important approach to prepare valuable chiral alcohols. Understanding how transition metals promote these reactions is key to the rational design of more active, selective and sustainable catalysts. A highly unusual mechanism for asymmetric hydrogenation of acetophenone catalysed by an anionic Ir^III hydride system, including a strong counterion dependence on catalyst activity, is explored and rationalised here. The active catalyst, generated in situ from [IrCl(COD)]₂ and a bidentate ligand (P,S^R) under H₂ in the presence of a strong base (M⁺ⁱPrO^- in isopropanol, M = Li, Na, K), is the solvated M⁺[Ir(H)₄(P,S^R)] salt (P,S^R =

SUBMITTER: Kisten P 

PROVIDER: S-EPMC11583429 | biostudies-literature | 2024 Dec

REPOSITORIES: biostudies-literature