Total synthesis of (+)-blastmycinone and formal synthesis of (+)-antimycin A3b

The formal synthesis of (+)-antimycin A_3b and the total synthesis of (+)-blastmycinone were achieved using, as a key step, a method developed by us for the synthesis of 2-methyl-1,3-diols via Ti(III)-mediated diastereo- and regioselective opening of trisubstituted 2,3-epoxy alcohols, to carry out the stereoselective construction of the hydroxy-acid segment. An interesting intramolecular radical translocation took place during the epoxide opening process transforming its vicinal PMB-ether in situ, into an ‘1,2-O-(p-methoxy)benzylidene’ ring.