Novel Oxidative Generation of Ammonium Ylides and the Subsequent Silicon Polonovski Reaction

Abstract

We have demonstrated a novel oxidative generation of ammonium ylides by employing allylic amines having a silyl group. Treatment of N-(α-silylmethyl)-N-allylic amines with an oxidant, followed by acetic anhydride, brought about a tandem Brook rearrangement/silicon Polonovski reaction via the generation of ammonium ylides to give the corresponding amides, whereas the reaction of N-(α-cyano-α-silylmethyl)-N-allylic amines with an oxidant afforded the corresponding formamides.

Tandem Brook Rearrangement/Silicon Polonovski Reaction <i>via</i> Oxidative Generation of Ammonium Ylides

“…This motivated us to test a modification of the silicon Polonovski reaction, under mild conditions by using functionalized tertiary amines 26 .…”