Imines, reaction with peroxyacids

Peroxyacids oxidize the imine group in (236) and related compounds to the nitrone. The 1,4-benzodiazepine (178) and its 4,5-dihydro analogue can be oxidized to the 2-oxo derivatives with chromium(VI) oxide. The benzodiazepinone (236) can be hydroxylated at the 3-position via a two-step process firstly reaction with LTA gives the 3-acetoxy derivative and this can then be hydrolyzed in high yield using sodium methoxide in methanol/methylene chloride. The 3-acetoxy derivative may also be prepared via bromina-tion with NBS and reaction with sodium acetate in situ (79JHC1449). 

Grignard reagents and organolithium reagents react with nitriles to give imine anions, but aqueous acid hydrolysis usually converts the imine anion to a ketone as the final product. Peroxyacids react with ketones to give esters in the Baeyer-Villiger reaction. 

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