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.

Regioselective Synthesis of 1,3-and 1,2-Tocopheryl Glyceride Ethers of Carboxylic Acids. -Selective deprotection of 1,2-tocopheryl glyceride ethers (V) succeeds with Super-Hydride, but the method suffers from a certain degree of acyl group migration even at low temperature and extremely short reaction time (formic acid quenching). -(CHOI, B. S.; CHOI, J.; BAK, S.; KOO*, S.; Eur. J. Org. Chem. 2015, 3, 514-524, http://dx.