Nucleophilic reactivity of organophosphorus compounds. Part II. The reactions of phosphorus acids with keten OO-, ON-, OS-, and SS-acetals, orthoesters, and ketenimines

Abstract

The reactions of phosphoric, phosphonic, phosphomonothioic, and phosphodithioic acids with the title substrates are reported. Many of these reactions are of synthetic utility in the alkylation of phosphorus acids. The preparation of a keten acetal and an orthoester from (+)- or (–)-octan-2-ol are reported and their reactions with all three types of phosphorus acid proceed predominantly (88–100%) with inversion. The results are interpreted in terms of an ion-pair mechanism for the alkylation step of the reaction.