Highly stereocontrolled and regiocontrolled syntheses of polyoxygenated [2.2.2]oxabicyclic synthons

Abstract

Highly oxygenated cyclohexanes (known as cyclitols or carba-sugars) were synthesized regiospecifically and stereoselectively via a key inverse electron demand Diels–Alder cycloaddition of electron poor 2-pyrones with electron rich tert-butyldimethylsilyl vinyl ether. The resulting [2.2.2]oxabicyclic lactones proved to be versatile synthons; syn-dihydroxylations were achieved with very high stereocontrol, with up to five stereocenters being produced from commercially available or easily prepared planar starting materials.