Fragmentation of Carbohydrate Anomeric Alkoxyl Radicals: Synthesis of Chiral Polyhydroxylated β‐Iodo‐ and Alkenylorganophosphorus(V) Compounds

A direct approach to β‐iodophosphonates and β‐iodophosphine oxides from 2,3‐dideoxy‐3‐phosphoryl carbohydrate derivatives has been achieved by using the anomeric alkoxyl radical 1,2‐fragmentation protocol. The reaction has been conducted on carbohydrate derivatives under mild conditions with (diacetoxyiodo)benzene and molecular iodine. Subsequent dehydroiodination afforded the corresponding vinylphosphonates and vinylphosphine oxides.