 Alkyl Grignard reagents, alkylithium compounds, alkylzinc compounds, and alkylcuprates have been aminated with electrophilic reagents successfully.Among sp2-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.