A nonenzymatic acid/peracid catalytic cycle for the Baeyer-Villiger oxidation.
The combined action of carbodiimide and hydrogen peroxide upon exposure to carboxylic acid catalysts serves to generate transient peracids that can be engaged in the Baeyer-Villiger rearrangement of ketones to lactones. Up to 35 turnovers of the catalytic cycle may be achieved. The conditions are especially useful in the context of reactive cyclohexanones, and allow the use of H2O2 as the terminal oxidant. A singular example of a chiral catalyst demonstrates, in principle, that enantioselective catalysis will be possible with this strategy for catalyst turnover.
Peris
Gorka
G
Department of Chemistry, Yale University, New Haven, Connecticut 06520, USA.
Miller
Scott J
SJ
D002264:Carboxylic Acids / Q000737:chemistry*; D002384:Catalysis; D003512:Cyclohexanones / Q000737:chemistry; D006861:Hydrogen Peroxide / Q000737:chemistry; D007659:Ketones / Q000138:chemical synthesis / Q000737:chemistry; D007783:Lactones / Q000138:chemical synthesis* / Q000737:chemistry; D010084:Oxidation-Reduction
D002264:Carboxylic Acids; D003512:Cyclohexanones; D007659:Ketones; D007783:Lactones; D006861:Hydrogen Peroxide