Application of a New Family of P,N Ligands to the Highly Enantioselective Hydrosilylation of Aryl Alkyl and Dialkyl Ketones


  • We thank Dr. Jack Liang for assistance in the synthesis of ligand 1 and Mr. Ivory D. Hills for help with X-ray crystallography. Support has been provided by Bristol-Myers Squibb, Novartis, and Pharmacia. Funding for the MIT Department of Chemistry Instrumentation Facility has been furnished in part by NSF CHE-9808061 and NSF DBI-9729592.


original image

Comparable to or even better than the best enantioselectivities that can be obtained through asymmetric hydrogenation of dialkyl ketones are the ee values obtained in the catalytic asymmetric hydrosilylation of such ketones with the catalyst system Rh/1 (see scheme). In terms of both scope and stereoselectivity, this method compares favorably with previously described catalysts for this process as the Rh/1 system also furnishes consistently excellent ee values and yields with aryl alkyl ketones.