Development of a rhodium-catalyzed asymmetric intermolecular hydroacylation reaction: From chiral phosphine ligands to phosphoramidites and novel hydroxyproline-based phosphite-phosphoramidites

ORGN 581

René T. Stemmler, rene.stemmler@rwth-aachen.de1, Dirk Reinartz, reinartz@itmc.rwth-aachen.de2, Giancarlo Franciò, francio@itmc.rwth-aachen.de2, Walter Leitner, leitner@itmc.rwth-aachen.de2, and Carsten Bolm, carsten.bolm@oc.rwth-aachen.de1. (1) Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, D-52074 Aachen, Germany, (2) Institute of Technical Chemistry and Macromolecular Chemistry, RWTH Aachen University, Worringerweg 1, D-52074 Aachen, Germany

The rhodium-catalyzed hydroacylation is a useful and atom economic reaction for the synthesis of ketones from aldehydes and olefins. We recently developed the first asymmetric intermolecular variant of this reaction. Among several chiral phosphine ligands screened in the hydroacylation of norbornadiene with salicylaldehyde, members of the Walphos family were found to be effective for the enantioselective and diastereoselective formation of exo-norbornenyl ketones. On the other hand, the application of MonoPhos and other phosphoramidites as ligands led to the diastereoselective formation of enantioenriched endo-norbornenyl ketones. Finally, novel hydroxyproline-derived phosphite-phosphoramidites were found to be applicable in the asymmetric intermolecular hydroacylation reaction.

 

Materials, Devices and Switches, Metal-Mediated Reactions, Asymmetric Reactions, Total Synthesis, Biologically-Related Molecules and Processes
7:00 PM-9:00 PM, Wednesday, April 9, 2008 Morial Convention Center -- La Louisiane, Blrm. C, Poster

Sci-Mix
8:00 PM-10:00 PM, Monday, April 7, 2008 Morial Convention Center -- Hall A, Sci-Mix

Division of Organic Chemistry

The 235th ACS National Meeting, New Orleans, LA, April 6-10, 2008