ChemInform Abstract: Cosolvent‐Promoted Electrophilic Amination of Organozinc Reagents.

Abstract

Amines Q 0120Cosolvent-Promoted Electrophilic Amination of Organozinc Reagents. -By use of a cosolvent, the amount of CuCN and waste is reduced and the yields are improved.-(DASKAPAN*, T.; YESILBAG, F.; KOCA, S.; Appl. Organomet. Chem. 23 (2009) 6, 213-218; Fac. Sci., Ankara Univ., TR-06100 Ankara, Turk.; Eng.) -Bartels 41-061

Copper-Catalyzed Electrophilic Amination of sp2 and sp3 C−H Bonds

“…Early aminations took advantage of sp 2 nitrogen-containing compounds such as azides [65][66][67][68] and diazene dicarboxylates. [69][70][71][72][73][74][75][76][77][78][79][80][81][82][83] More recently, oxime esters [84][85][86][87][88][89] and nitroso compounds [90][91][92][93][94][95][96] have been used. However, for electrophilic amination reactions using sp 2 nitrogen-containing compounds, the formation of the corresponding amine requires reduction of the N−N or N−O bond.…”

Synthesis of amines by the electrophilic amination of organomagnesium, -zinc, -copper, and -lithium reagents

“…Primary arylamines can be obtained in high yields by the use of a dipolar aprotic cosolvent (Scheme 25). [99][100][101] Addition of a P-, N-, or S-donor ligand causes a significant reduction in the quantity of copper catalysts and a remarkable increase in the yield of amine (Scheme 26). 101 There is no need to use a copper catalyst to obtain primary arylamines in good yields, if the amination of arylzinc reagents with acetone oxime O-tosylate 5b, in the presence of a cosolvent, is performed at 40 ºC.…”