Catalytic enantioselective Baeyer-Villiger oxidations of 3-substituted cycl
obutanones with cumene hydroperoxide as oxidant have successfully been perf
ormed in the presence of chiral magnesium catalysts. The combination of ena
ntiopure BINOL and a variety of Mg reagents is able to promote the oxidatio
n of ketones with good enantiomeric excesses. MgI2 or MeMgI as metal source
were found to give the best enantioselectivities.