Efficient ligand-mediated Ullmann coupling of anilines and azoles

A process for making a compound of Formula III

• wherein:
• in Formula III, from 0-1 of the carbon atoms of the 6-membered ring are replaced with N;
• comprising:
• reacting an aniline of Formula IV with an azole of Formula V in the presence of Cu(I)X1 and a bidentate ligand:
• wherein:
• in Formula IV, from 0-1 of the carbon atoms are replaced with N;
• X1 is selected from Cl, Br, I, and SCN;
• X2 is selected from Br or I;
• R1 is selected from H, Cl, F, Br, I, C1-4 alkyl, C1-4 alkoxy, C1-4 alkylene-O—C1-4 alkyl, NH2, NH(C1-4 alkyl), N(C1-4 alkyl)2, C1-4 alkylene-NH2, C1-4 alkylene-NH(C1-4 alkyl), C1-4 alkylene-N(C1-4 alkyl)2, C3-10 carbocycle substituted with 0-2 R3, and 5-6 membered heterocycle comprising carbon atoms and 1-4 heteroatoms selected from N, O, and S and substituted with 0-2 R3;
• R2 is selected from H, Cl, F, Br, I, C1-4 alkyl, C1-4 alkoxy, C1-4 alkylene-O—C1-4 alkyl, NH2, NH(C1-4 alkyl), N(C1-4 alkyl)2, C1-4 alkylene-NH2, C1-4 alkylene-NH(C1-4 alkyl), C1-4 alkylene-N(C1-4 alkyl)2, C3-10 carbocycle substituted with 0-2 R3, and 5-6 membered heterocycle comprising carbon atoms and 1-4 heteroatoms selected from N, O, and S and substituted with 0-2 R3;
• R3 is selected from Cl, F, Br, I, C1-4 alkyl, C1-4 alkoxy, C1-4 alkylene-O—C1-4 alkyl, NH2, NH(C1-4 alkyl), N(C1-4 alkyl)2, C1-4 alkylene-NH2, C1-4 alkylene-NH(C1-4 alkyl), C1-4 alkylene-N(C1-4 alkyl)2, and NO2;
• r is 1 or 2;
• and,
• the bidentate ligand is a hydrolytically stabile ligand that is known to ligate with Cu(I) and comprises two heteroatoms selected from N and O.