Electrophilic amination

Other electron-deficient, sp3 amination reagents react by similar mechanisms to give substitution products.

[3] In aminations involving oxaziridines, nucleophilic attack takes place on the nitrogen atom of the three-membered ring.

For some substrates (α-cyano ketones, for example), the resulting alkoxide reacts further to afford unexpected products.

Alkyl-, aryl-, and heteroaryllithium reagents add to azides to afford triazene salts.

Electrophilic aminating reagents rely on the presence of an electron-withdrawing functional group attached to nitrogen.

[9] Although the enantioselectivity of the proline-catalyzed process is good, yields are low and reaction times are long.

[12] Other electrophilic aminating reagents include oxaziridines,[13] diazo compounds,[14] and in rare cases, imines.

For instance, in the presence of a copper(II) catalyst, bulky organozinc reagents react with O-acylhydroxylamines to afford hindered amines.

In the example below, deprotonation of an activated methylene compound containing an O-phosphinoylhydroxylamine led to the cyclic amine shown.

Additionally, organoboranes can serve the role of the nucleophile and often provide higher yields with fewer complications than analogous carbanions.

The wide variety of electrophilic aminating reagents precludes generalization of reaction conditions.