Effects of dihedral angle of biaryl-bridged bisphosphite ligands on selectivity of rhodium-catalyzed asymmetric hydroformylation

INOR 61

Christopher J. Cobley1, Jerzy Klosin, jklosin@dow.com2, Robert D. J. Froese2, Gregory T. Whiteker, whitekgt2@dow.com3, and Khalil A. Abboud4. (1) Dowpharma, Chirotech Technology Limited, The Dow Chemical Company, 321 Cambridge Science Park, Cambridge, CB4 0WG, United Kingdom, (2) The Dow Chemical Company, Midland, MI 48674, 1776 Building, Midland, MI 48674, (3) Dow AgroSciences, 9330 Zionsville Rd., Indianapolis, IN 46268, (4) Department of Chemistry, University of Florida, P.O. Box 117200, Gainesville, FL 32611-7200
As part of our development of asymmetric hydroformylation technology for application to pharmaceutical synthesis, we have recently reported several new classes of phosphorus ligands which lead to high enantio- and regioselectivity. Biaryl-bridged bisphosphite ligands exhibit high selectivity for hydroformylation of vinyl acetate and allyl cyanide. A systematic study of the effect of the dihedral angle of the bridging biaryl on hydroformylation selectivity using X-ray crystallography and DFT calculations will be presented. These results suggest that dihedral angle changes are accompanied by changes in the bite angle of the catalyst.

 

Organometallic: Catalysis
8:30 AM-12:10 PM, Sunday, 10 September 2006 Moscone Center -- Room 310, Oral

Division of Inorganic Chemistry

The 232nd ACS National Meeting, San Francisco, CA, September 10-14, 2006