Table 3.

Development of the Ullmann N-Arylation

Entry	Copper source	Ligand	Substrates		Conditions	Yield (%)	Ref.
			Ar-X	Nucleophile
1	CuO (5 mol%)	L34 and L4	Aryl-I, Br	Anilines	KOH/TBAB, H2O MW, 120°C, 5 min or KOH/TBAB, H2O 90°C, 8 h	45–78	62
				Aliphatic amines		50–91
				Imidazoles	KOH/TBAB, H2O MW, 140°C, 5 min	52–89
2	CuI (5 mol%)	L32	Aryl-I, Br	Anilines	KOH/TBAB, H2O MW, 130°C, 5 min or KOH/TBAB, H2O 130°C, 5 min	47–83	63
				Aliphatic amines		54–85
			Aryl-I	Pyrazole	KOH/TBAB, H2O MW, 130°C, 5 min	54–78
3	CuO (5 mol%)	L35	Aryl-I, Br	Anilines	KOH/TBAB, H2O MW, 130°C, 5 min	43–85	64
				Aliphatic amines		18–87
4	Cu2O (5 mol%)	L27	4-Iodotoluene	Pyrazole	Cs2CO3, CH3CN 100°C, 22 h	80	65
		L13		1,2,4-Triazole	C2CO3, DMF 100°C, 22 h	80
5	CuI (10 mol%)	L33	Aryl-Br Pyridyl-Br	N-Heterocycles	Cs2CO3, DMSO 120°C	60–95	66
6	CuCl (10 mol%)	L30	Aryl-I, Br, Cl	N-Heterocycles/alkyl amines	NaOH, n-Bu4N+Br− H2O, 100°C	62–97	67
7	CuI (10 mol%)	L31	Aryl-I	Guanidine nitrate	K3PO4, MeCN 120°C	19–92	68
8	CuI (10 mol%)	L19	Aryl-I, Br	Substituted-amidine·HCl	Cs2CO3, DMF 110–120°C	64–94	69
9	CuI (10 mol%)	None or L14	o-Functional aryl-I, Br	NaN3	Cs2CO3/K2CO3 EtOH, 95°C	43–95	70
10	Cu(acac)2 (10 mol%)	L2 or L3	Aryl-I, Br Heteroaryl-Br	NH3·H2O	Cs2CO3, DMF 60–90°C	23–98	71