Reactions of the N-isopropyl-α-chloroketimines with PIV dithioacids

Abstract

A primary iminium salt formed in the reaction of P^IV dithioacids with N-isopropyl-α-chloroketimines is transformed into products of nucleophilic substitution of the chlorine atom by dithiophosphorus group (S_N pathway), if the imine carbon atom is bonded to the donor and small-volume methyl group, or undergoes reduction of the CCl bond (C-Cl→C-H) (Red pathway), when it is bonded with the bulky acceptor phenyl group. The same effect of substituents was discovered, when replacing methyl group with phenyl one in the position 2 of N-tert-butyl-2-chloraldimines: S_N: Red ratio is 1: 0 in the case of Me and 1: 9 in the case of Ph. The iminium salts were transformed into new type ketones containing a phosphor functionality.