ELECTROPHILIC AMINATION OF CARBANIONS

The action of chloroamine and bromoamine on organometallic reagents has been reviewed102 and a comprehensive review of electrophilic aminations of carbanions has appeared103. Alkyl, alkenyl and aryllithium compounds are converted into tertiary amines 84 by reaction with the mesityl compounds 83 (R2 = Me or Et Ar = 2,4, 6-MesCeHj)104. 

This chapter on electrophilic amination using O-substituted hydroxylamines 1-5 and oximes 7 is focused on the various methods that have been reported for the amination of carbon nucleophiles. Synthetic aspects and applications of the methods for C—N bond formation are accompanied by a brief discussion of the reaction mechanisms. The preparation of O-substituted hydroxylamines and oximes has not been considered in detail. This review covers the literature up to August 2007 and is partly based on reviews on the electrophilic amination of carbanions and a-amination of carbonyl compounds. ... 

The only reported example of the use of O-phenylhydroxylamine Ig for electrophilic amination of carbanions is the conversion of phenyhnagnesium bromide into aniline. ... 

Armstrong et al. studied the electrophilic amination of carbanions with A -carboxamido-oxaziridines <2000TL2247>. A range of 3-aryl-A -carboxamido oxaziridines was evaluated and the 3-(2-cyanophenyl) oxaziridine 108 gave optimum yields of the amination products. A variety of ketone, ester, and amide enolates, as well as sulfone-, phosphonate-, and nitrile-stabilized carbonions underwent the desired amination (Table 6). 

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