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.This work was supported by the Ministerio de Economía y Competitividad (Investigation Programs, grant numbers CTQ2010‐18244 and CTQ2007‐67492) and by the Gobierno de Canarias (grant numbers SolSub20081000192 and ProID20100088). D.H.‐G. thanks the Ministerio de Economía y Competitividad for a fellowship.Peer Reviewe