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. Author manuscript; available in PMC: 2010 Aug 12.
Published in final edited form as: J Am Chem Soc. 2009 Aug 12;131(31):11049. doi: 10.1021/ja903049z

Table 5.

Comparison of the Activity of Copper Catalysts versus Pd[P(o-tol)3]2 and CyPF-t-Bu in the Coupling of Ammonia with Aryl Halides.

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Entry Aryl Halide Condition A
(CuI/1)a 		Condition B
(Cu(acac)2/2)b 		Condition C
(3)		 Condition D
(Pd/CyPF-t-Bu)
1 X = I, R = 2-Me 17% 30% --e 73%
2 X = Br, R = 2-OMe trace --e --e 95%
3 X = Br, R = 4-tBu 84% 55% --e 88%
graphic file with name nihms131741t42.jpg graphic file with name nihms131741t43.jpg graphic file with name nihms131741t44.jpg
a

Reaction conditions A: 0.5 mmol aryl halide, 0.65 mmol NH4OH, 0.1 mmol CuI, 0.2 mmol L-proline, 1.5 mmol K2CO3, 1 mL DMSO, 0.05 mL H2O, 80 °C, 24 h.

b

Reaction conditions B: 1 mmol aryl halide, 300 mL NH4OH, 0.1 mmol Cu(acac)2, 0.4 mmol 2,4-pentadione, 2 mmol Cs2CO3, 2 mL DMF, 90 °C, 24 h.

c

Reaction conditions C: 1 mmol aryl halide, 0.05 mmol 3, 2 mmol K2CO3, 5 mL (1:1, MeOH/NMP), 90 °C, 24 h.

d

Reaction conditions D: 0.5 mmol aryl halide, 5 mL of 0.5 M ammonia in dioxane, 0.7 mmol NaOtBu; entry 1: 0.0025 mmol Pd[P(o-tol)3]2/CyPF-t-Bu, 5 ml of 0.5 M ammonia in dioxane, 80 °C; entry 2: 0.0005 mmol Pd[P(o-tol)3]2/CyPF-t-Bu, 5 ml of 0.5 M ammonia in dioxane, 100 °C; entry 3: 0.0025 mmol Pd[P(o-tol)3]2/CyPF-t-Bu, 5 ml of 0.5 M ammonia in dioxane, 5 mL dioxane, 80 °C.

e

No product observed by GC/MS.