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.
Trost
Barry M
BM
Department of Chemistry, Stanford University, California 94305-5080, USA. bmtrost@stanford.edu
Richardson
Jeffery
J
Yong
Kelvin
K
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