Abstract: Processes using 2-deoxyribose-5-phosphate aldolase (DERA) are described for the preparation of 2-deoxyfucose and related compounds. In one embodiment, DERA is used to catalyze the condensation of acetaldehyde as donor and a 2(R)-hydroxy-3-(hydroxy or mercapto)-propionaldehyde derivative to form a 2-deoxysugar whose hydroxyls have the configuration of fucose. In another embodiment, DERA is used to catalyze the condensation of two moles of acetaldehyde as donor and one mole of a 2-substituted acetaldehyde acceptor to form a 2,4,6-trideoxyhexose via a 4-substituted-3-hydroxybutanal intermediate.