Syntheses of Polymerizable Monoacylglycerols and 1,2-Diacyl-sn-glycerols

The first chemical syntheses of polymerizable monoacylglycerol and 1,2-diacyl-sn-glycerol are reported. The monodienoylglycerol is obtained in 80% yield from 1,2-O-isopropylidene-sn-glycerol and dienoyl fatty acid. The dienoic acid is accessible in 60% yield from the base-catalyzed hydrolysis of dienoyl ester, which is synthesized from the Wittig−Horner reaction of aldehyde and trimethyl 4-phosphonocrotonate. The acylation is carried out in the presence of 4-(dimethylamino)pyridine and dicyclohexylcarbodiimide. The use of excess protected glycerol relative to fatty acid affords the acylated product in high yield. The final step is the deprotection of isopropylidene group using dilute HCl solution. The 1,2-diacyl-sn-glycerol is synthesized by acylation of 3-(4-methoxybenzyl)-sn-glycerol with dienoyl fatty acid in the presence of 4-(dimethylamino)pyridine and dicyclohexylcarbodiimide. The removal of the 4-methoxybenzyl group by dimethylboron bromide catalyzed hydrolysis is especially useful in the synthesis...