A Tandem Reaction Initiated by 1,4-Addition of Bis(iodozincio)methane for 1,3-Diketone Formation

Treatment of an gamma-acyloxy-alpha,beta-unsaturated ketone with bis(iodozincio)methane leads to a novel tandem reaction consisting of three steps: ( 1) 1,4-addition of the dizinc reagent to the enone, which affords the corresponding zinc enolate of the beta-zinciomethylated ketone; (2) intramolecular nucleophilic attack by the enolate on the ester group; and (3) Grob-type fragmentation of the addduct, accompanied by elimination of the zinc alkoxide of allyl alcohol. The overall reaction gives 1,3-diketones efficiently.