Catalytic Transesterification Routes to Novel Vinyl Glycolate Derivatives of Polyhydric Alcohols

Methyl vinyl glycolate (methyl 2-hydroxybut-3-enoate, MVG) has recently become obtainable from Sn catalysed cascade reactions of mono- and disaccharides. The chemical structure of MVG present several options for chemical transformations and has great potential as a renewable platform chemical for industrial added-value compounds within e.g. polymer chemistry.

Herein, we report a catalytic benign transesterification method for the synthesis of MVG ester derivatives of trimethylolpropane (TMP) and pentaerythritol (PE). The secondary alcohol group of MVG greatly complicates the reaction and requires a highly selective catalyst to direct the reaction towards high conversion while avoiding polymerization.

Thus, a range of different catalytic systems, e.g. Candida Antarctica Lipase B (CALB), Brønsted bases/acids, salicylic aldehyde as well as Lewis acids were evaluated for the reaction. Despite the challenges this leads to unique derivatives of TMP and PE with an additional chemical handle compared to classic derivatives like the methacrylate and mercaptopropionate.

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