Palladium-catalyzed chemo- and enantioselective oxidation of allylic esters and carbonates.
The palladium-catalyzed oxidation of allylic esters and carbonates using a novel potassium nitronate has been developed. This method is highly chemoselective, leaving other esters, alcohols, thioethers, and amines undisturbed. The oxidation can be operated in two modes: an achiral mode, using either PPh3 or rac-2 as ligand, or a chiral and highly enantioselective mode, using 2 as ligand. The oxidative enantioselective desymmetrization of meso bis-esters provides a significantly shorter method to arrive at commonly used synthetic intermediates compared to other strategies. Highly efficient kinetic resolution is also possible using this methodology.
Department of Chemistry, Stanford University, California 94305-5080, USA. bmtrost@stanford.edu
Barry M
BM
Trost
Jeffery
J
Richardson
Kelvin
K
Yong
D000475:Alkenes / Q000138:chemical synthesis* / Q000737:chemistry; D000498:Allyl Compounds / Q000737:chemistry*; D002264:Carboxylic Acids / Q000737:chemistry*; D002384:Catalysis; D004952:Esters / Q000737:chemistry*; D007659:Ketones / Q000138:chemical synthesis*; D010084:Oxidation-Reduction; D010165:Palladium / Q000737:chemistry; D010720:Phosphines / Q000737:chemistry; D013237:Stereoisomerism
D000475:Alkenes; D000498:Allyl Compounds; D002264:Carboxylic Acids; D004952:Esters; D007659:Ketones; D010720:Phosphines; D010165:Palladium