Asymmetric Hydrosilylation of Aryl Ketones Catalyzed by Copper Hydride Complexed by Nonracemic Biphenyl Bis-phosphine Ligands

Abstract

When complexed by selected ligands in either the BIPHEP or the SEGPHOS series, CuH is an extremely reactive catalyst capable of effecting asymmetric hydrosilylations of aromatic ketones at temperatures between −50 and −78 °C. Inexpensive silanes serve as stoichiometric sources of hydride. Substrate-to-ligand ratios exceeding 100,000:1 have been documented. The level of induction is usually in the >90% ee category. The nature of the reagent has been investigated using spectroscopic and chemical means, although its composition remains unclear.