The first highly enantio- and diastereoselective vinylogous aldol reaction between propionyl acetate-derived Brassard鈥檚 diene and aldehydes was accomplished by titanium鈥搇ithium combined Lewis acid, affording 未-hydroxy-纬-methyl-尾-methoxy acrylates. This methodology was utilized in convenient and concise construction of the polypropionate moiety in cystothiazole A and melithiazole C.