Achiral Hydroxypyruvaldehyde Phosphate as a Platformfor Multi-Aldolases Cascade Synthesis of Diuloses and for a QuadrupleAcetaldehyde Addition Catalyzed by 2‑Deoxyribose-5-PhosphateAldolases

The 1,4-dicarbonyl unit is found in numerous molecules of biological interest, many of which are also polyhydroxylated. We developed a general, one-pot, multistep, stereoselective enzymatic method to prepare diuloses of structural diversity from achiral hydroxypyruvaldehyde phosphate (HPP) as the common electrophile for various aldolases. Surprisingly, for 2-deoxyribose-5-phosphate aldolases, HPP was an acceptor of choice for the multiple addition of acetaldehyde, widening the scope of longer-chain aldol adducts.