Stable synthetic equivalents of N-unsubstituted imines: Part 1. Synthesis

Zinc-Catalyzed Chemoselective Reduction of Nitriles to N-Silylimines through Hydrosilylation: Insights into the Reaction Mechanism

“…Like 3a–3w , the N-silylimines 2i′ and 2i″ under standard reaction conditions, after workup, yielded the respective oximes 3i′ and 3i″ in high yields (Scheme S1, b). N -Acylimines and N -methylenecarbamic esters are essential in organic chemistry, including cycloadditions and natural product synthesis. , Similarly, N -sulfonylimines are the necessary starting materials for Diels-Alder chemistry. , The N-silylimines could also be converted into N -acylimine ( 5a or 5b ), N -methylenecarbamic ester ( 6a ), and N -sulfonylimine ( 7a or 7b ) in the presence of pivaloyl chloride or 4-nitrobenzoyl chloride, ethyl chloroformate, and methanesulfonyl chloride or p -toluenesulfonyl chloride (Scheme S1, c).…”

“…Various procedures have been developed for the hydrosilylation of different functional groups such as alkene, ,, alkyne, ,, imine, − carbonyls, and carboxylic derivatives. − Additionally, there are numerous reports on catalytic double hydrosilylation of nitriles to 1,1-disilylamines. ,, However, partial mono-hydrosilylation of nitriles to N-silyl aldimines remains a significant challenge. Due to N-silylimines being much more reactive than nitriles, these are further reduced to give the disilylamine products. ,, In addition, N-silylimines are very unstable . These N-silylated imines are suitable precursors in medicinal chemistry, nitrogen-containing organic compounds, and silicon-containing polymers. , N-silylimines are key intermediates for further functionalization .…”