New Catalysts for the Asymmetric Hydrosilylation of Ketones Discovered by Mass Spectrometry Screening
- 27 February 2003
- journal article
- research article
- Published by American Chemical Society (ACS) in The Journal of Organic Chemistry
- Vol. 68 (7) , 2540-2546
- https://doi.org/10.1021/jo026365e
Abstract
A method for determining enantiomeric excess by mass spectrometry was employed to screen a family of chiral phosphite P,N-ligands for activity in the rhodium-catalyzed asymmetric hydrosilylation of ketones. The identification of an effective set of ligands was followed by preliminary studies of the reaction scope and mechanism. Asymmetric induction of 84−88% ee for larger-scale reactions was observed, which is close to the level of the best alternative catalysts previously discovered. The screening method was shown to be applicable to a variety of substrates without the need for special optimization.Keywords
This publication has 22 references indexed in Scilit:
- Long-Range 1H−15N Heteronuclear Shift Correlation at Natural AbundanceJournal of Natural Products, 2000
- Rhodium Complexes with Chiral Aminophosphinite Derivatives of EphedrineOrganometallics, 1999
- Catalytic Enantioselective Hydrosilylation of Ketones with Rhodium-Phosphite Complexes Containing a TADDOLate and a Dihydrooxazole UnitHelvetica Chimica Acta, 1999
- Ruthenium-Catalyzed Asymmetric Hydrosilylation of Ketones and ImineOrganometallics, 1998
- [L*Rh(NBD)Cl] (L* = Chiral Cyclic Monophosphonite): A Novel Class of Rhodium(I) Complexes and Their Evaluation in the Asymmetric Hydrosilylation of Ketones. Investigations of the Effects of Temperature and Ligand BackboneOrganometallics, 1998
- Catalytic asymmetric hydrosilylation of ketones using rhodium-(l)-complexes of chiral phosphinooxazoline ligandsTetrahedron: Asymmetry, 1996
- Catalytic Enantioselective Hydrosilylation of Aromatic Ketones Using Rhodium Complexes of TADDOL‐Derived Cyclic Phosphonites and PhosphitesHelvetica Chimica Acta, 1993
- Ring expansion of tert-butyl 1-vinylcyclopropane-1-carboxylates to .alpha.-ethylidenebutyrolactonesThe Journal of Organic Chemistry, 1992
- Cobalt-catalyzed cyclocarbonylation of acetylenes under water gas shift conditions: selective synthesis of indan-1-onesOrganometallics, 1991
- Chromium boride (CrB4) and manganese boride (MnB4): electronic structures of two unusual systems containing the tetragonal carbon netInorganic Chemistry, 1988