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Serendipitous Synthesis of ( tert ‐Butyl‐ NNO ‐azoxy)acetonitrile: Reduction of an Oxime Moiety to a Methylene Unit
Author(s) -
Klenov Michael S.,
Anikin Oleg V.,
Guskov Alexey A.,
Churakov Aleksandr M.,
Strelenko Yurii A.,
Ananyev Ivan V.,
Bushmarinov Ivan S.,
Dmitrienko Artem O.,
Lyssenko Konstantin A.,
Tartakovsky Vladimir A.
Publication year - 2016
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201600584
Subject(s) - chemistry , azoxy , methylene , acetonitrile , moiety , diazo , oxime , medicinal chemistry , tetrazole , organic chemistry , stereochemistry
( 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.