Oxidation of Halides and Amines

Kimura, A. Kawashima, M. Sugizaki, N. Nemoto, and O. Mitsunobu, J. Chem. Soc., Chem. Commun., 1979, 303. 

The novel biomimetic oxidation of primary amines to imines, and hence to carbonyl compounds using 5-deazaflavin (8), has been demonstrated, though the method is not yet of significant synthetic value.  

Ketones and benzaldehydes are obtained in high yield from secondary and benzylic halides respectively, by oxidation with tetra-n-butylammonium dichromate (prepared and isolated prior to use).  

The palladium-catalysed dehydrogenation and hydrolysis of tertiary amines to aldehydes and secondary amines in good yields has been reported. 

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Oxidation of Halides and Amines. N-Trifluoromethylsulphonylaniline (3) oxidizes secondary bromides, activated by a carbonyl group, to 1,2-diketones, whereas the more reactive p-hydroxy analogue (4) will oxidize unactivated alkyl halides to aldehydes (Scheme 2). ... 

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