Selective Cleavage and Tunable Functionalization of the C-C/C-N Bonds of N-Arylpiperidines Promoted by tBuONO.

In this paper, selective cleavage and tunable functionalization of the inert C-C/C-N bonds in N-arylpiperidines promoted by tBuONO under metal-free conditions is presented. To be specific, when the reaction was run in acetonitrile in the presence of molecular sieves, the synthetically useful acyclic N-formyl nitriles are formed. On the other hand, when alcohol was used as the reaction medium, the corresponding reactions afforded N-nitroso chain esters as dominating products via a mechanistically different pathway.