Nucleophilic reactions of (silylamino)phosphines

Abstract

(Silylamino)phosphines (I) react smoothly with ketones and aldehydes via nucleophilic attack by phosphorus, followed by a {1,4} silyl migration from nitrogen to oxygen. Compounds of structure II are isolated when R is SiMe(,3). When R is Me, however, II reacts further with the carbonyl compound to produce phosphine oxides III. Compound I(R = Me(,3)Si) reacts with (alpha),(beta)-unsaturated ketones and aldehydes in a 1,4 manner, producing silyl enol ethers. The cyclic (silylamino)phosphine Me(,2)SiCH(,2)CH(,2)SiMe(,2)NPMe(,2) reacts analogously with acetone and(' ) methyl vinyl ketone with ring expansion to yield phosphinimines with 8- and 10-membered rings, respectively. The results of reactions of I(R = Me(,3)Si) with ethyl bromoacetate, allyl bromide, carbon disulfide, and chloroformates are also described.