Origins of enantioselectivity in reductions of ketones on cinchona alkaloid modified platinum.
A model to explain the stereoselectivities of reductions of activated ketones on cinchona alkaloid modified platinum is proposed and is supported by calculations by density functional and force field methods. The model involves nucleophilic catalysis by the cinchona alkaloid. The zwitterionic adduct between a cinchona alkaloid and ketone is adsorbed on Pt through the quinoline ring and two heteroatoms and is subsequently reduced with inversion. The model rationalizes the observed stereoselectivities for hydrogenation of carbonyl compounds.
Vayner
Grigoriy
G
Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095-1569, USA.
Houk
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KN
Sun
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D002930:Cinchona Alkaloids / Q000737:chemistry*; D007659:Ketones / Q000737:chemistry*; D008958:Models, Molecular; D009944:Organoplatinum Compounds / Q000737:chemistry*; D010084:Oxidation-Reduction; D010984:Platinum / Q000737:chemistry*; D013237:Stereoisomerism; D013499:Surface Properties
D002930:Cinchona Alkaloids; D007659:Ketones; D009944:Organoplatinum Compounds; D010984:Platinum