Hoch-Campbell aziridine synthesis

The Hoch-Campbell aziridine synthesis entails treatment of ketoximes with excess Grignard reagents and subsequent hydrolysis of the organometallic complex.  

In 1934, French chemist Hoch reported that the action of phenylmagnesium bromide on the oxime of propiophenone (3) at elevated temperature gave two products. One was aziridine 4 and the other was erroneously assigned as hydroxylamine 5. In the subsequent years (1939 onward), Campbell at the University of Notre Dame determined that the purported hydroxylamine 5 was actually P-hydroxylamine 6. The scope of the Grignard reagents was extended to both aryl and aliphatic Grignard reagents. 

The aforementioned mechanism is supported by the following experimental data. When oxime 13 was treated with Grignard reagent, 3% of the indole 15 was isolated, indicating the possible existence of nitrene intermediate 14. A 2-phenylazirine intermediate, on the other hand, has been isolated and characterized from the reaction under carefully controlled conditions (adding Grignard reagent to the oxime in toluene).  

An intramolecular trapping variant of the Hoch-Campbell aziridine synthesis was reported by Taguchi et When 2-(l-p-chlorophenylcyclohexyl)cyclohexanone (16) 

The third variation of the Hoch-Campbell reaction is the replacement of the 

Dermer, O. C. Ham, G. E. Ethyleneimine and Other Aziridines, Academic Press New York, 1969, pp65 68. (Review). 

Tzikas, A. Tamm, C. Boiler, A. Fiirst, A. Helv. Chim. Acta 1976, 59, 1850. 

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Graham reaction—additive oxidation Hoch-Campbell aziridine synthesis Payne rearrangement Wenker synthesis Aziridine synthesis... 

Hinsberg Synthesis of Thiophene Derivatives Hiyama (see Nozaki-Hiyama Coupling Reaction) Hoch-Campbell Aziridine Synthesis Hoesch (see Houben-Hoesch Reaction)... 

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