Organic synthesis with a migrating functional group: scope and limitations of diphenylphosphinoyl migration

Abstract

Diphenylphosphinoyl (Ph2PO) migration occurs during the acid-catalysed dehydration of β-Ph2PO-alcohols having primary or secondary alkyl groups, alkenyl groups, or aryl groups at the migration terminus and, in another series of compounds, a five- or a four-membered ring at the migration origin. The allylphosphine oxide products form anions which add electrophiles, chiefly carbonyl compounds, mostly at the α-position (to phosphorus) but at the γ-position in some cases. A method to cause α-addition is described.