One‐Pot Highly Stereoselective Synthesis of Cyano Aziridines via the CuCl‐Catalyzed Aminochlorination of α,β‐Unsaturated Nitriles and Intramolecular S_N2 Substitution

Abstract

An efficient one-pot system has been developed for the synthesis of cyano aziridine by using a,bunsaturated nitriles as the alkene substrates and N,N-dichloro-p-toluenesulfonamide (4-TsNCl 2 ) as the nitrogen source. A good scope of alkene substrates was achieved for this reaction. The one-pot reaction, via aminohalogenation and intramolecular S N 2 substitution, was very convenient to carry out at room temperature without the protection of inert gases. Modest to good yields and excellent have been obtained. This method provides an easy route to the cyano aziridine. The structure of the resulting products has been unambiguously confirmed by X-ray structural analysis.

Synthetic methods Part (II): oxidation and reduction methods

“…values so obtained varied with substrate and sulfonimidamide, but reached 94% in one instance (Scheme 22). Han, Pan and co-workers have described a protocol for Cu-catalysed aziridination of a,b-unsaturated nitriles, using N,N-dichlorotoluenesulfonamide as nitrogen source and oxidant 99 (in contrast to their diamination protocol, 88 acetonitrile is not incorporated in this instance). Finally, Morales, Pe´rez and co-workers have employed 1,3,5-tris(thiocyanatomethyl)mesitylene as a ligand, investigating the corresponding Cu complex as a nitrene transfer agent.…”

One-pot stereoselective synthesis of α,β-differentiated diamino esters via the sequence of aminochlorination, aziridination and intermolecular SN2 reaction

“…The aminohalogenation reaction has been well studied in the past decade [29–32], and the corresponding vicinal haloamine product can be easily converted into aziridines [33–34] and α,β-dehydroamino acid derivatives [35] in the presence of an organic amine. Recently, we found that treating haloamine with benzylamine resulted in an unexpected α,β-diamino product, instead of the aziridine or the α,β-dehydroamino product.…”