Synthesis and Reactivity of Stable Silyl-Substituted Nitrilimines

Article abstract of DOI:10.1021/jo00005a026

The reaction of chlorophosphanes and chlorosilanes with the lithium salts of the (bis(diisopropylamino)thiophosphoranyl)-, bis(diisopropylamino)phosphanyl)-, (trimethylsilyl)-, and (triisopropylsilyl)diazomethane (1, 4, 5, 6) has been studied.Four isolable nitrilimines XYNNY (X=(iPr2N)2P(S), Y=SiiPr3, 10a; X=(iPr2N)2P, Y=SiPh3, 14a; X=(iPr2N)2P, Y=SiiPr3, 15a; X=Y=SiiPr3, 18a) and three observable nitrilimines (X=(iPr2N)2P(S), Y=SiMe3, 8a; X=(iPr2N)2P(S), Y=SiPh3, 9a; X=(iPr2N)2P, Y=SiMe3, 13a) have been obtained.The factors influencing the stability of nitrilimines are analyzed.Several examples of thermal nitrilimine-diazo rearrangements and photochemical nitrilimine-carbodiimide rearrangements are described.The regioselectivity of the reaction of the observable nitrilimines with methyl acrylate and methyl propiolate is compared to that reported for transient nitrilimines.An example of 1,3-addition of butyllithium to nitrilimine is given.