Abstract Chiral 2-hydroxypropanone derivatives 5a− v, 8a− d, and 10a, b were formed by benzoylformate decarboxylase (BFD) catalyzed C− C bond formation. A donor aldehyde and acetaldehyde as an acceptor were carboligated in aqueous buffer solution with remarkable ease in high chemical yield and good to high optical purity. The substrate range of this thiamin diphosphate dependent enzyme was examined to employ this benzoin ...