An efficient and versatile synthesis of apiose and some C-1-aldehyde- and/or 2,3-O-protected derivatives

The synthesis of 2,3-O-isopropylidene-β-d-apiofuranose (58% overall yield) from l-arabinose via 3-C-(hydroxymethyl)-2,3-O-isopropylidene-d-glycero-tetrose diethyl dithioacetal is reported. Starting from l-arabinose an alternative precursor of d-apiose, 3-C-(hydroxymethyl)-2,3-O-isopropylidene-d-glycero-tetrose dimethyl acetal, was prepared from 2,3-O-isopropylidene-l-threo-tetrodialdose dimethyl acetal and formaldehyde by the aldol-Cannizzaro reaction. Unprotected d-apiose is accessible from both precursors on acid hydrolysis.