Dehydrative Etherification Reactions of Glycerol with Alcohols Catalyzed by Recyclable Nanoporous Aluminosilicates: Telescoped Routes to Glyceryl Ethers

Catalytic strategies for the efficient transformation of abundant sustainable bioderived molecules, such as glycerol, into higher value more useful products is an important research goal. In this study, we demonstrate that atom efficient dehydrative etherification reactions of glycerol with activated alcohols are effectively catalyzed by nanoporous aluminosilicate materials in dimethylcarbonate (DMC) to produce the corresponding 1-substituted glyceryl ethers in high yield. By carrying out the reaction in acetone, it is possible to capitalize on the ability of these materials to catalyze the corresponding acetalization reaction, allowing for the development of novel, telescoped acetalization-dehydrative etherification reaction sequences to selectively produce protected solketal derivatives. These materials also catalyze the telescoped reaction of glycerol with <i>tert</i>-butanol (TBA) in acetone to produce the corresponding solketal mono <i>tert</i>-butyl ether product in high yield, providing a potential route to convert glycerol directly into a useful and sustainable fuel additive.