Serendipitous Synthesis of (tert‐Butyl‐NNO‐azoxy)acetonitrile: Reduction of an Oxime Moiety to a Methylene Unit. Issue 22 (12th July 2016) - Klenov, Michael S.
Abstract : ( 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 NH2 OTs. 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 compound1, followed by intramolecular coupling of the azoxy and diazo groups. The tetrazole structures were confirmed by X‐ray diffraction analysis. Abstract : ( 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.