Serendipitous Synthesis of (tert-Butyl-NNO-azoxy)acetonitrile: Reduction of an Oxime Moiety to a Methylene Unit

(tert‐Butyl‐NNO‐azoxy)acetonitrile (1) is a useful precursor for a number of nitrogen heterocycles. It was found that it could be obtained in good yield by treatment of the salts of (tert‐butyl‐NNO‐azoxy)(hydroxyimino)acetonitrile with NH2OTs. It is the first case of one‐step reduction of an oxime group to a methylene unit using an aminating agent. A plausible reaction mechanism is proposed. In addition, a new strategy for the tetrazole 1‐oxide ring construction was developed. This involves a diazo‐group transfer to the active‐methylene unit of compound 1, followed by intramolecular coupling of the azoxy and diazo groups. The tetrazole structures were confirmed by X‐ray diffraction analysis. (tert‐Butyl‐NNO‐azoxy)acetonitrile was obtained by a new one‐step transformation of an oxime group into a methylene unit using an aminating agent. This active‐methylene compound has played a key role in creating a new approach to the synthesis of tetrazole 1‐oxides.