Table 1.

Coupling of Heteroaryl Halides with Primary Alkylamines Catalyzed by Pd(OAc)₂ and CyPF-t-Bu (1:1).^a

Entry	Ar	X	R	Cat. (%)	Conditions	Yield (%)b
1	2-Py	Cl	Octyl	0.001	100 °C, 48 h	86
2		Br	Octyl	0.0005	110 °C, 12 h	84
3		I	Octyl	0.005	110 °C, 12 h	96
4		Cl	Bn	0.001	100 °C, 10 h	85
5		Br	Bn	0.0005	110 °C, 12 h	83
6		Cl	Cyclohexyl	0.01	70 °C, 12 h	98
7		Br	Cyclohexyl	0.005	60 °C, 12 h	96
8		I	sec-Bu	0.05	110 °C, 12 h	98
9d		Cl	1-Methylbenzylf	0.05	100 °C, 24 h	99
10	3-Me-2-Py	Cl	Octyl	0.005	90 °C, 24 h	96
11	3-Py	Cl	Octyl	0.005	90 °C, 24 h	93
12c		Cl	Octyl	0.005	100 °C, 24 h	99
13		Br	Octyl	0.005	100 °C, 36 h	99
14		Cl	Bn	0.01	100 °C, 24 h	95
15		Br	Bn	0.005	100 °C, 48 h	99
16		Br	secBu	0.005	100 °C, 48 h	93
17		I	isoBu	0.05	100 °C, 12 h	96
18		Cl	Cyclohexyl	0.01	100 °C, 48 h	79
19		I	Cyclohexyl	0.05	100 °C, 12 h	78
20		Cl	tert-Bu	1.0	70 °C, 16 h	67
21d		Cl	1-Methylbenzylg	0.05	100 °C, 24 h	91
22	4-Py	Cl	Octyl	0.01	90 °C, 24 h	83
23		Br	Octyl	0.005	100 °C, 3 6h	93
24		I	Octyl	0.05	100 °C, 48 h	80
25		Cl	Phenylcarbonyl	1.0	70 °C, 10 h	75
26	2-Pyrazinyl	Cl	Octyl	0.005	100 °C, 16 h	82
27		I	Octyl	0.05	100 °C, 36 h	83
28e	1,3-Pyrimidyl-5-	Br	Cyclohexyl	1.0	100 °C, 48 h	80
29	3-Quinolinyl	Cl	Cyclohexyl	0.01	100 °C, 48 h	60
30	1-isoQuinolinyl	Cl	Octyl	0.005	90 °C, 15 h	91
31	4-isoQuinolinyl	Br	Octyl	0.005	100 °C, 36 h	93

^aReactions conducted with a 1:1 ratio of metal to ligand, 1 mmol aryl halide, 1.2 equiv amine, and 1.4 equiv NaOtBu in 1 mL DME.

^bIsolated yield;

^cReaction performed without using a drybox.

^dfrom phenethylamine that is stated to be 99% ee.

^eUsing K₃PO₄ as the base.

^f96% ee.

^g95% ee.