Organometallics
Article
Scheme 2. NHC-PdII-Ox Complex 3a Catalyzed Amination of Aryl Chlorides with Alkyl Amines
4.30 (t, J = 10.0 Hz, 2H, OCH2), 3.94 (t, J = 10.0 Hz, 2H, NCH2),
3.16−3.11 (m, 4H, 4CHMe2), 1.38 (br, 12H, 2CHMe2), 1.09 (d, J =
7.0 Hz, 12H, 2CHMe2). 13C NMR (125 MHz, CDCl3): δ 165.8
(NCO), 156.9 (Ccarbene), 147.1 (NC=), 135.2 (CAr), 131.8 (CAr), 130.1
(CAr), 129.7 (CAr), 128.0 (CAr), 125.0 (CAr), 124.9 (CAr), 123.9 (CAr),
67.4 (OCH2), 54.1 (NCH2), 28.7 (CHMe2), 26.4 (CH3), 22.9 (CH3).
HRMS (ESI): calcd for C36H45Cl2N3NaOPd [M + Na]+, 734.1874;
found, 734.1837. Anal. Calcd for C36H45Cl2N3OPd·1/2CH3CO2Et: C,
60.28; H, 6.52; N, 5.55. Found: C, 60.16; H, 6.32; N, 5.81. IR (neat): ν
2961, 2359, 1643, 1461, 1414, 1381, 1252, 1109, 944, 932, 801, 756,
725 cm−1.
60.93; H, 6.53; N, 5.68. IR (neat): ν 1643, 1464, 1408, 1371, 1331,
1256, 1099, 944, 914, 887, 799, 773, 751, 735, 723 cm−1.
Compound 3e: yellow solid (518.0 mg, 0.70 mmol). 1H NMR (300
MHz, TMS, CDCl3): δ 8.34 (d, J = 8.7 Hz, 2H, HAr), 7.59 (br, 2H,
HAr), 7.44−7.41 (m, 4H, HAr), 7.12 (s, 2H, 2NCH), 6.59 (d, J = 8.7
Hz, 2H, HAr), 4.26 (t, J = 9.6 Hz, 2H, OCH2), 3.89 (t, J = 9.6 Hz, 2H,
NCH2), 3.84 (s, 3H, OCH3), 3.15 (br, 4H, 4CHMe2), 1.40 (br, 12H,
4CH3), 1.09 (d, J = 6.6 Hz, 12H, 4CH3). 13C NMR (125 MHz,
CDCl3): δ 165.3 (NCO), 162.3 (CAr), 157.3 (Ccarbene), 147.1 (NC),
135.2 (CAr), 131.7 (CAr), 130.0 (CAr), 124.9 (CAr), 123.9 (CAr), 117.4
(CAr), 113.3 (CAr), 67.2 (OCH2), 55.3 (OCH3), 53.9 (NCH2), 28.7
(CHMe2), 26.4 (CH3), 22.9 (CH3). HRMS (ESI): calcd for
C37H47Cl2N3NaO2Pd [M + Na]+, 764.1980; found, 764.1971. Anal.
Calcd for C37H47Cl2N3O2Pd: C, 59.80; H, 6.37; N, 5.65. Found: C,
59.76; H, 6.40; N, 5.60. IR (neat): ν 1633, 1600, 1514, 1464, 1411,
1351, 1252, 1176, 1099, 929, 799, 770, 756, 731, 708 cm−1.
Compound 3b: yellow solid (515.2 mg, 0.86 mmol). 1H NMR (300
MHz, TMS, CDCl3): δ 8.36 (d, J = 7.8 Hz, 2H, HAr), 7.46−7.40 (m,
3H, HAr), 7.31 (d, J = 7.2 Hz, 4H, HAr), 7.22 (t, J = 7.2 Hz, 2H, HAr),
7.11 (s, 2H, 2NCH=), 4.32 (t, J = 9.6 Hz, 2H, OCH2), 3.91 (t, J = 9.6
Hz, 2H, NCH2), 2.40 (s, 12H, 4CH3). 13C NMR (125 MHz, CDCl3):
δ 165.8 (NCO), 154.6 (Ccarbene), 137.6 (NC=), 137.0 (CAr), 132.1
(CAr), 129.7 (CAr), 129.4 (CAr), 128.4 (CAr), 127.9 (CAr), 124.9 (CAr),
123.8 (CAr), 67.4 (OCH2), 54.0 (NCH2), 19.2 (CH3). HRMS (ESI):
calcd for C28H29Cl2N3NaOPd [M + Na]+, 622.0619; found, 622.0644.
Anal. Calcd. for C28H29Cl2N3OPd·1/2CH3CO2Et: C, 55.87; H, 5.16;
N, 6.52. Found: C, 56.05; H, 5.24; N, 6.43. IR (neat): ν 2357, 1655,
1638, 1472, 1410, 1371, 1259, 1216, 1106, 1022, 945, 928, 785, 706
cm−1.
Compound 3f: yellow solid (497.0 mg, 0.68 mmol). 1H NMR (300
MHz, TMS, CDCl3): δ 8.36 (dd, J = 9.0, 5.4 Hz, 2H, HAr), 7.61 (t, J =
7.8 Hz, 2H, HAr), 7.42 (d, J = 7.8 Hz, 4H, HAr), 7.12 (s, 2H,
2NCH), 6.77 (t, J = 8.7 Hz, 2H, HAr), 4.30 (t, J = 9.9 Hz, 2H,
OCH2), 3.92 (t, J = 9.9 Hz, 2H, NCH2), 3.16−3.07 (m, 4H,
4CHMe2), 1.38 (d, J = 6.3 Hz, 12H, 4CH3), 1.09 (d, J = 6.9 Hz, 12H,
4CH3). 13C NMR (125 MHz, CDCl3): δ 164.83 (NCO), 164.77 (d,
JC−F = 251.5 Hz, CAr), 156.6 (Ccarbene), 147.1 (NC), 135.1 (CAr),
132.2 (d, JC−F = 9.1 Hz, CAr), 130.2 (CAr), 125.0 (CAr), 124.0 (CAr),
121.3 (d, JC−F = 3.0 Hz, CAr), 115.2 (d, JC−F = 21.9 Hz, CAr), 67.6
(OCH2), 54.1 (NCH2), 28.7 (CHMe2), 26.4 (CH3), 22.9 (CH3).
HRMS (ESI): calcd for C36H44Cl2FN3NaOPd [M + Na]+, 752.1780;
found, 752.1713. Anal. Calcd for C36H44Cl2FN3OPd: C, 59.14; H,
6.07; N, 5.75. Found: C, 59.13; H, 6.08; N, 5.74. IR (neat): ν 2961,
2855, 1517, 1451, 1381, 1356, 1282, 1239, 1103, 1086, 949, 833, 798,
767, 751, 740, 730, 705 cm−1.
Compound 3c: yellow solid (526.7 mg, 0.84 mmol). 1H NMR (300
MHz, TMS, CDCl3): δ 8.39 (d, J = 7.2 Hz, 2H, HAr), 7.48−7.43 (m,
1H, HAr), 7.27−7.20 (m, 2H, HAr), 7.12−7.07 (m, 6H, HAr
+
2NCH), 4.33 (t, J = 9.6 Hz, 2H, OCH2), 3.95 (t, J = 9.6 Hz, 2H,
NCH2), 2.45 (s, 6H, 2CH3), 2.36 (s, 12H, 4CH3). 13C NMR (125
MHz, CDCl3): δ 165.8 (NCO), 154.4 (Ccarbene), 139.0 (NC=), 136.6
(CAr), 135.2 (CAr), 132.0 (CAr), 129.8 (CAr), 129.1 (CAr), 127.8 (CAr),
125.0 (CAr), 123.9 (CAr), 67.4 (OCH2), 54.0 (NCH2), 21.2 (CH3),
19.1 (CH3). HRMS (ESI): calcd. for C30H33Cl2N3NaOPd [M + Na]+:
650.0933; found: 650.0899. Anal. Calcd for C28H29Cl2N3OPd·
CH3CO2Et: C, 56.95; H, 5.76; N, 5.86. Found: C, 56.84; H, 5.74;
N, 5.87. IR (neat): ν 2319, 1643, 1483, 1411, 1375, 1331, 1262, 1229,
1106, 1030, 945, 929, 857, 776, 710 cm−1.
Compound 5g: pale yellow liquid (173.6 mg, 0.85 mmol). 1H NMR
(500 MHz, TMS, CDCl3): δ 7.10 (t, J = 8.0 Hz, 1H, HAr), 6.35 (dd, J
= 8.0, 2.0 Hz, 1H, HAr), 6.31 (s, 1H, HAr), 6.27 (dd, J = 8.0, 2.0 Hz,
1H, HAr), 3.12 (t, J = 5.5 Hz, 4H, CH2NCH2), 2.90 (s, 6H, 2NCH3),
1.72−1.67 (m, 4H, CH2CH2NCH2CH2), 1.57−1.53 (m, 2H,
NCH2CH2CH2). 13C NMR (125 MHz, CDCl3): δ 153.5 (CAr),
151.6 (CAr), 129.3 (CAr), 106.0 (CAr), 104.9 (CAr), 101.9 (CAr), 51.2
(NCH2), 40.8 (NCH3), 26.0 (NCH2CH2), 24.4 (NCH2CH2CH2). IR
(neat): ν 2935, 2849, 2789, 1607, 1504, 1448, 1355, 1232, 1123, 992,
924, 819, 756, 688 cm−1. MS (ESI): 205 [M + H]+. HRMS (ESI):
calcd for C13H21N2 [M + H]+, 205.1699; found, 205.1690.
Compound 3d: yellow solid (488.4 mg, 0.67 mmol). 1H NMR (500
MHz, TMS, CDCl3): δ 8.19 (d, J = 8.0 Hz, 2H, HAr), 7.59 (br, 2H,
HAr), 7.42 (d, J = 7.0 Hz, 4H, HAr), 7.11 (s, 2H, 2NCH), 6.89 (d, J =
8.0 Hz, 2H, HAr), 4.27 (t, J = 10.0 Hz, 2H, OCH2), 3.90 (t, J = 10.0
Hz, 2H, NCH2), 3.14−3.12 (m, 4H, 4CHMe2), 2.35 (s, 3H, CH3),
1.38 (s, 12H, br, 4CH3), 1.09 (d, J = 6.5 Hz, 12H, 4CH3). 13C NMR
(125 MHz, CDCl3): δ 165.9 (NCO), 157.1 (Ccarbene), 147.1 (NC=),
142.1 (CAr), 135.2 (CAr), 130.1 (CAr), 129.7 (CAr), 128.7 (CAr), 124.9
(CAr), 123.9 (CAr), 122.3 (CAr), 67.3 (OCH2), 54.0 (NCH2), 28.7
(CHMe2), 26.4 (CH3), 22.9 (CH3), 21.6 (CH3). HRMS (ESI): calcd
for C37H47Cl2N3NaOPd [M + Na]+, 748.2031; found, 748.1983. Anal.
Calcd for C37H47Cl2N3OPd: C, 61.12; H, 6.52; N, 5.78. Found: C,
1
Compound 10m: thick yellow liquid (222.9 mg, 0.99 mmol). H
NMR (500 MHz, CDCl3, TMS): δ 7.11 (t, J = 8.0 Hz, 2H, HAr), 6.87
(d, J = 6.5 Hz, 2H, HAr), 6.70 (d, J = 8.0 Hz, 1H, HAr), 6.45 (dd, J =
8.0, 1.5 Hz, 1H, HAr), 6.42 (t, J = 2.0 Hz, 1H, HAr), 6.33 (dd, J = 8.0,
2.0 Hz, 1H, HAr), 5.59 (s, 1H, NH), 2.88 (s, 6H, 2NCH3), 2.27 (CH3).
13C NMR (125 MHz, CDCl3): δ 151.6 (CAr), 143.9 (CAr), 143.5 (CAr),
1591
dx.doi.org/10.1021/om401028d | Organometallics 2014, 33, 1587−1593