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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...