Serendipitous Synthesis of (tert‐Butyl‐NNO‐azoxy)acetonitrile: Reduction of an Oxime Moiety to a Methylene Unit. Issue 22 (12th July 2016)

• Record Type: Journal Article
• Authors: 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.
• Is Part Of: European journal of organic chemistry. Issue 22(2016)
• Page Start: 3845
• Page End: 3855
• Publication Date: 2016-07-12
• Subjects: Synthetic methods -- Reduction -- Amination -- Nitrogen heterocycles -- Diazo compounds; Chemistry, Organic -- Periodicals; Organic compounds -- Synthesis -- Periodicals; Bioorganic chemistry -- Periodicals; Chemistry, Physical organic -- Periodicals; 547
• DOI: 10.1002/ejoc.201600584
• Languages: English
• ISSNs: 1434-193X

Abstract

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.