Aziridines. synthesis from oximes

The synthesis of aziridines by the reduction of ketoximes with lithium aluminium hydride or sodium aluminium (dimethoxyethoxy) hydride ( Red-AI ) is possible when the oxime has a neighbouring double bond or phenyl group cyclohexanone oximes give amines under these conditions. A new simple, and rapid aziridine synthesis from cyclohexanones uses the above reducing agents on the trimethyl... 

Azirines (three-membered cyclic imines) are related to aziridines by a single redox step, and these reagents can therefore function as precursors to aziridines by way of addition reactions. The addition of carbon nucleophiles has been known for some time [52], but has recently undergone a renaissance, attracting the interest of several research groups. The cyclization of 2-(0-tosyl)oximino carbonyl compounds - the Neber reaction [53] - is the oldest known azirine synthesis, and asymmetric variants have been reported. Zwanenburg et ah, for example, prepared nonracemic chiral azirines from oximes of 3-ketoesters, using cinchona alkaloids as catalysts (Scheme 4.37) [54]. 

Azirines have also been shown to be likely intermediates in the Campbell aziridine synthesis.62 This reaction is analogous to the Neber reaction in which the intermediate azirine is hydrolyzed to the aminoketone. Here the proposed azirine intermediate prepared from oxime (144) reacts with a Grignard reagent to give the aziridine (145). 

Ethylenimines or aziridines [lb] can be considered cyclic imines and are only briefly covered in Section 5. The preparation of heterocyclic imine systems, semicarbazones, hydrazones, azines, and oximes, is omitted from this chapter. The synthesis of carbodiimides is presented in Chapter 9. 

Palacios, R Ochoa de Retana, A.M. Alonso, J.M. Regioselective synthesis of fluoroalkylated 3-aminophosphorus derivatives and aziridines from phosphorylated oximes and nucleophilic reagents. J. Org. Chem. 2006, 71, 6141. 

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