Serendipitous Synthesis of (<i>tert</i>‐Butyl‐<i>NNO</i>‐azoxy)acetonitrile: Reduction of an Oxime Moiety to a Methylene Unit

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 NH 2 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 compound 1 , followed by intramolecular coupling of the azoxy and diazo groups. The tetrazole structures were confirmed by X‐ray diffraction analysis.