Amination reactions carbon-bromine bond formation

Of special importance to the applications of hydrazones and oximes to carbon-carbem bond formation is the observation that these derivatives are considerably more resistant to hydrolysis than are either en-amines or imines. Thus, methods for mild regeneration of the carbonyl group from these derivatives are especially significant. Among the reagents/systems developed are oxidation with bromine reaction... 

Reactions involving the formation of carbon heteroatom bonds include the industrially best known photochemical reactions. In fact, chlorination, bromination and sulfochlorination are major processes in industrial chemistry, and oxygenation has likewise an important role. Due to the focus on fine chemistry of this chapter, the discussion below is limited to laboratory-scale preparations and in particular to some bromination and oxygenation reactions illustrating the advantage of the photochemical approach, as well as to some alkoxylation, hydroxylation and amination reactions. 

Carbon-carbon bond formation takes place in reactions between iV, -dialkyl-anilines and dialkyl (2-nitroethenyl)- and (2-bromo-2-nitroethenyl)-phosphonates in acetic acid solution in the former case, the reaction is effectively one of addition across the C=C bond, and in the second case, replacement of bromine occurs with attachment of the amine moiety on the adjacent sp carbon and with no concomitant reduction. ... 

Substitution chemistry remains one of the most popular and simplest approaches to the formation of nitrogen-carbon(sp ) bonds. An example of this method involved the addition of pyrimidines to brominated esters (Scheme 3.1) [1]. The first step in this sequence was the protection of the primary amine in order to direct the reaction to the N l)-H of the pyrimidine. Once the protection was complete, addition of a strong base deprotonated the N l)-H and generated the amide that attacked the brominated ester to generate the new nitrogen-carbon(spO bond. 

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