Iron-Catalyzed 1,4-Phenyl Migration/Ring Expansion of α-Azido -Phenyl Amides.

Herein, we report a novel iron-catalyzed skeleton rearrangement of alkyl azides. Upon treatment with FeCl and N-heterocyclic carbene SIPr·HCl in the presence of HO and EtN, 2-azido-,-diphenylamides underwent 1,4-phenyl migration and ring expansion to give azepin-2-ones in good yield. The reaction proceeds via intramolecular nitrene cycloaddition followed by C-N cleavage, water addition, and electrocyclic ring opening.

Visible-Light-Driven Aryl Migration and Cyclization of α-Azido Amides.

This paper reports two new visible-light-promoted radical reactions of α-azido amides. By catalysis of [Ir(ppy)(dtbbpy)]PF with -PrNEt as the reducing agent, -aryl α-azido tertiary amides were first converted to the corresponding aminyl radicals through reduction of the azido group; the aminyl radicals then underwent N-to-N aryl migration to give α-anilinyl-functionalized amides. α-Azido secondary amides, on the other hand, reacted with the solvent ethanol and -PrNEt to afford the imidazolinone products.

Iron-catalysed 1,2-aryl migration of tertiary azides.

1,2-Aryl migration of α,α-diaryl tertiary azides was achieved by using the catalytic system of FeCl2/N-heterocyclic carbene (NHC) SIPr·HCl. The reaction generated aniline products in good yields after one-pot reduction of the migration-resultant imines.

Copper(i) chloride promoted Csp(2)-N cross-coupling of 1,2-di(pyrimidin-2-yl) disulfides with amines: an efficient approach to obtain C2-amino functionalized pyrimidines.

The copper(i)-promoted cross-coupling of 1,2-di(pyrimidin-2-yl) disulfides with aromatic amines and aliphatic amines to deliver C-N coupling products in moderate to good yields is reported in this paper. Central to this strategy is the conversion of disulfides into aryl- and alkyl amines by a copper-promoted chemoselective C-S bond cleavage.