Thiamine‐Based Enzymes for Biotransformations

Chiral and prochiral α-oxyfunctionalized compounds, in particular carboxylic acids, aldehydes, ketones, alcohols, are indispensable building blocks for asymmetric synthesis. 2-Hydroxy ketones encompassing a chiral and prochiral center are therefore versatile building blocks for organic synthesis, as they can be easily transformed into other functionalities, such as diols, epoxides, amino alcohols and diamines. The review describes the current state of the art concerning thiamine diphosphate-dependent enzymes, which catalyze the formation of chiral 2-hydroxy ketones. Keywords: thiamine; diphosphate; enzymes; biotransformation; carboligation; structure–function relationships; pyruvate decarboxylase; benzoylformate decarboxylase; benzaldehyde lyase