Tandem addition of nucleophilic and electrophilic reagents to vinyl phosphinates: the stereoselective formation of organophosphorus compounds with congested tertiary carbons

Carbon anions formed via the addition of Grignard reagents to S(P)-vinyl phosphinates were modified with electrophilic reagents to afford organophosphorus compounds with diverse carbon skeletons. The electrophiles included acids, aldehydes, epoxy groups, chalcogens and alkyl halides. When alkyl halides were used, bis-alkylated products were afforded. Substitution reactions or polymerization occurred when the reaction was applied to vinyl phosphine oxides.