Expanding Zirconocene Hydride Catalysis: In Situ Generation and Turnover of ZrH Catalysts Enabling Catalytic Carbonyl Reductions.

ABSTRACT: Despite the wide use and popularity of metal hydride catalysis, methods utilizing zirconium hydride catalysts remain underexplored. Here, we report the development of a mild method for the in situ preparation and use of zirconium hydride catalysts. This robust method requires only 2.5-5 mol % of zirconocene dichloride in combination with a hydrosilane as the stoichiometric reductant and does not require careful air- or moisture-free techniques. A key finding of this study concerns an amine-mediated ligand exchange en route to the active zirconocene hydride catalyst. A mechanistic investigation supports the intermediacy of an oxo-bridged dimer precatalyst. The application of this method to the reduction of a wide variety of carbonyl-containing substrates, including ketones, aldehydes

SUBMITTER: Kehner RA 

PROVIDER: S-EPMC9169672 | biostudies-literature | 2022 Feb

REPOSITORIES: biostudies-literature