The scope of organometallic reagents that may be aminated by electrophilic methods is large. Alkyl Grignard reagents, alkylithium compounds, alkylzinc compounds, and alkylcuprates have been aminated with electrophilic reagents successfully. Among sp-centered carbanions, vinyllithium compounds, vinylcuprates, and vinyl Grignard reagents react with electrophilic aminating reagents to afford enamines.
Aryl and heteroaryl organolithium reagents undergo efficient electrophilic amination under copper (I) catalyzed condition mediated by recoverable silicon reagents, termed siloxane transfer agents. 
The scope of sp-centered carbanions is limited to alkynylcuprates. Enolates and silyl enol ethers, the most widely used class of carbon nucleophiles in electrophilic amination reactions, participate in amination, adization and hydrazination reactions.
The primary application of alkylmetal reagents in electrophilic amination reactions is the synthesis of hindered amines, many of which are difficult to prepare through nucleophilic displacement with an alkyl halide (nucleophilic amination). For instance, in the presence of a copper(II) catalyst, bulky organozinc reagents react with O-acylhydroxylamines to afford hindered amines.
Allylic metal species can be used to prepare allylic amines through electrophilic amination.  Although allylic amines are usually prepared through nucleophilic amination of allylic halides, a few examples of electrophlic amination of allylic substrates are known. In the example below, an allylic zirconium reagent (obtained by hydrozirconation) is trapped with an O-alkylhydroxylamine.
The electrophilic amination of enolates yields α-amino carbonyl compounds. When chiral oxazolidinones are used in conjunction with azo compounds, enantioselectivity is observed (see above). BINAP can also be used for this purpose in the amination of silyl enol ethers.
Aryl and heteroaryl organometallic reagents undergo many of the same transformations as their aliphatic counterparts. Formation of amines, hydrazines, and azides is possible through the use of various electrophilic aminating reagents. An example employing a nitrenoid reagent is shown below.
Intramolecular amination is possible, and has been used to prepare small and medium rings. In the example below, deprotonation of an activated methylene compound containing an O-phosphinoylhydroxylamine led to the cyclic amine shown.