Regioselective Synthesis of 1,3‐ and 1,2‐Tocopheryl Glyceride Ethers of Carboxylic Acids

Abstract

A regioselective synthetic method with which to access 1,3‐tocopheryl glyceride ethers 2 of diverse carboxylic acids was developed through Bu4NBr‐catalyzed ring‐opening of tocopheryl glycidyl ether 1. Steglich esterification of the 1,3‐tocopheryl acetyl‐glyceride ether 2a with various carboxylic acids, followed by selective deprotection of 3‐acetate by LiEt3BH reduction at –78 °C constitutes a regioselective synthetic method of 1,2‐tocopheryl glyceride ethers 4. An example of the differing self‐assembled behavior of phosphorylcholine derivatives 6c and 7c of 1,3‐ and 1,2‐tocopheryl stearoyl‐glyceride ethers in aqueous solution is also described.

Experimental and computational studies of the mechanism of base‐catalyzed ring opening of 2‐(chloromethyl)oxirane by benzoic acid

“…4 In practical applications, involving asymmetric epoxides, the regioselectivity of hydroxypropyl ester/ether formation determines the yield of the desired product. 5 This is particularly important in the development of novel drugs, 6 synthetic glycerides for drug delivery vehicles, 7 and in the synthesis of new biodegradable polycarbonates. 8 Asymmetric oxiranes (Scheme 1) possess two electrophilic reac-tion centers (C 1 and C 2 ) and ring opening by protondonating nucleophilic reagents can occur in two possible ways.…”