Hypervalent Iodine(III)‐Catalysed Enantioselective α‐Acetoxylation of Ketones

An enantioselective catalytic synthesis of α‐acetoxylated ketones through I(I)/I(III) catalysis using a resorcinol/lactamide‐based chiral iodoarene is reported. Catalyst turnover by in situ generation of the active iodine(III) derivative is achieved by oxidation with m CPBA in the presence of acetic acid. The prior transformation of ketones to easily accessible acetyl enol ethers is beneficial and yields up to 97 % with enantioselectivities up to 88 %  ee are obtained using only low catalyst loadings of only 5 mol % under mild reaction conditions.