CuI/Oxalamide-Catalyzed Coupling Reaction of (Hetero)aryl Halides with Sodium Nitrite.

The ,'-bis(thiophen-2-ylmethyl)oxalamide (BTMO) was found to be an effective ligand for Cu-catalyzed -nitration of (hetero)aryl halides (Br, I), making the coupling reaction with sodium nitrite proceed smoothly at 100-120 °C with 1-5 mol % CuI and BTMO. Electron-rich substrates were the best coupling partners to give the desired coupling products in good to excellent yields at 100 °C. Electron-neutral substrates required heating at 120 °C to get complete conversion, while rather low conversions were observed in the case of electron-poor (hetero)aryl bromides.

Cu/Oxalic Diamide-Catalyzed Coupling of Terminal Alkynes with Aryl Halides.

-(2,6-Dimethylphenyl)--(pyridin-2-ylmethyl)oxalamide (DMPPO) was revealed to be a more effective ligand for copper-catalyzed coupling reaction of (hetero)aryl halides with 1-alkynes than previously reported ones. Only 3 mol % CuCl and DMPPO are required to make the coupling complete at 100 °C (for bromides) and 80 °C (for iodides). Both (hetero)aryl and alkyl substituted 1-alkynes worked well under these conditions, leading to the formation of internal alkynes in great diversity.