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([D6]DMSO): δ = 3.24 (s, 3 H, NCH3), 3.86 (s, 3 H, OCH3), 5.29
9.0 Hz), 135.9 (Pd–C), 137.8, 141.5, 142.4, 151.1, 162.9 (d, JC,F
=
(s, 2 H, NCH2), 7.20 (d, JH,H = 9.0 Hz, 2 H, Ar–H), 7.48–7.71 (m, 248 Hz), 165.5 (C=O) ppm. IR (KBr): ν = 1670 (C=O) cm–1.
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8 H, Ar H), 8.10 (t, JH,H = 9.0 Hz, 1 H, Ar H), 8.35 (d, JH,H
=
Synthesis of 7b: The preparation was similar to that of 7a. Pd-
(OAc)2 (0.305 g, 1.36 mmol), 2b (0.555 g, 1.36 mmol), pyridine
(0.109 g, 0.136 mmol), and LiCl (0.114 g, 2.72 mmol) were used. A
pale yellow solid was obtained. Yield: 0.270 g (55%). M.p. 263.2–
264.5 °C. C28H26Cl2N4O2Pd (627.85): calcd. C 53.56, H 4.17, N
9.0 Hz, 1 H, Ar H), 8.42 (s, 1 H, imi H), 8.77 (d, JH,H = 9.0 Hz, 1
H, NCH) ppm. 13C{1H} NMR ([D6]DMSO): δ = 37.9 (NCH3),
49.5 (NCH2), 55.9 (OCH3), 113.0, 115.5, 116.9, 118.3, 124.4, 126.1,
127.2, 128.1, 128.9, 130.4, 131.2, 134.0, 140.5, 141.9, 161.1
(COCH3), 164.7 (C=O) ppm. HRMS (ESI): calcd. for
C23H22ClN3O2 [M – Cl]+ 372.1712; found 372.1717.
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8.92; found C 53.85, H 4.19, N 8.99. H NMR (CDCl3): δ = 3.32
(s, 3 H, NCH3), 3.85 (s, 3 H, OCH3), 5.62 (s, 2 H, NCH2), 6.69–
7.07 (m, 3 H, Ar H), 7.26–7.41 (m, 6 H, Ar H), 7.55–7.64 (m, 3 H,
Ar–H), 7.74 (t, JH,H = 9.0 Hz, 1 H, Ar H), 7.93 (d, JH,H = 9.0 Hz,
Synthesis of 2c: The compound was prepared by a procedure sim-
ilar to that of 2a. A mixture of 3-phenylimidazo[1,2-a]pyridine
(3.40 g, 17.0 mmol) and 2-chloro-N-methyl-N-phenylacetamide
(3.21 g, 17.0 mmol) were used. Yield: 2.40 g (70%). 1H NMR ([D6]-
2 H, Ar H), 8.19 (d, JH,H = 9.0 Hz, 1 H, Ar H), 8.92 (d, JH,H
=
6.0 Hz, 2 H, py H) ppm. 13C{1H} NMR (CDCl3): δ = 38.0 (NCH3),
DMSO): δ = 3.25 (s, 3 H, NCH3), 5.29 (s, 2 H, NCH2), 7.48–7.75 50.9 (NCH2), 55.3 (OCH3), 110.7, 114.5, 114.8, 120.9, 122.8, 124.1,
(m, 11 H, Ar H), 8.12 (t, JH,H = 9.0 Hz, 1 H, Ar H), 8.35 (d, JH,H 125.9, 127.4, 127.8, 128.7, 130.0, 132.1, 134.9 (Pd–C), 137.6, 141.3,
= 9.0 Hz, 1 H, Ar H), 8.50 (s, 1 H, imi H), 8.85 (d, JH,H = 6.0 Hz, 142.5, 151.2, 159.9, 165.6 (C=O) ppm. IR (KBr): ν = 1668 (C=O)
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1 H, NCH) ppm. 13C{1H} NMR ([D6]DMSO): δ = 37.9 (NCH3), cm–1.
49.5 (NCH2), 113.1, 118.4, 125.0, 126.1, 127.3, 128.2, 128.9, 129.5,
Synthesis of 7c: The preparation was similar to that of 7a. Pd-
130.1, 130.4, 130.8, 134.2, 140.7, 141.9, 164.7 (C=O) ppm. HRMS
(OAc)2 (0.208 g, 0.930 mmol), 2c (0.35 g, 0.93 mmol), pyridine
(0.075 mL, 0.930 mmol), and LiCl (0.312 g, 7.45 mmol) were used.
A pale yellow solid was obtained. Yield: 0.30 g (54%). M.p. 218.6–
(ESI): calcd. for C22H20ClN3O [M – Cl]+ 342.1606; found 342.1610.
Synthesis of 2d: The compound was prepared by a procedure sim-
ilar to that of 2a. A mixture of 3-phenylimidazoimidazo[1,2-a]pyr-
220.3 °C. C27H24Cl2N4OPd (597.82): calcd. C 54.24, H 4.05, N
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idine (3.20 g, 16.9 mmol) and 2-chloro-N-phenylacetamide (2.61 g, 9.37; found C 53.76, H 3.92, N 8.90. H NMR (CDCl3): δ = 3.33
16.9 mmol) were used. Yield: 4.40 g (74%). 1H NMR ([D6]DMSO):
δ = 5.61 (s, 2 H, NCH2), 7.05 (t, JH,H = 6.0 Hz, 1 H, Ar H), 7.30
(t, JH,H = 9.0 Hz, 2 H, Ar H), 7.53–7.75 (m, 8 H, Ar H), 8.09 (t,
(s, 3 H, NCH3), 5.65 (s, 2 H, NCH2), 7.00 (t, JH,H = 6.0 Hz, 1 H,
Ar H), 7.29–7.77 (m, 13 H, Ar H), 8.05 (d, JH,H = 6.0 Hz, 2 H, Ar
H), 8.27 (d, JH,H = 6.0 Hz, 1 H, Ar H), 8.91 (d, JH,H = 6.0 Hz, 2
JH,H = 6.0 Hz, 1 H, NCCHCH), 8.39 (d, JH,H = 9.0 Hz, 1 H, Ar H, py H) ppm. 13C{1H} NMR (CDCl3): δ = 38.0 (NCH3), 51.0
H), 8.58 (s, 1 H, imi H), 8.83 (d, JH,H = 6.0 Hz, 1 H, NCH), 11.17 (NCH2), 110.7, 114.9, 122.9, 124.1, 125.0, 126.1, 127.6, 127.8,
(s, 1 H, NH) ppm. 13C{1H} NMR ([D6]DMSO): δ = 50.2 (NCH2), 128.7, 128.9, 129.0, 130.1, 130.6, 135.8 (Pd–C), 137.6, 141.5, 142.9,
112.5, 118.4, 119.6, 124.2, 124.9, 125.1, 126.5, 127.5, 129.3, 129.7,
130.1, 130.9, 134.6, 139.0, 140.6, 164.1 (C=O) ppm. HRMS (ESI):
calcd. for C21H18ClN3O [M – H]+ 362.1060; found 362.1063.
151.2, 165.6 (C=O) ppm. IR (KBr): ν = 1670 (C=O) cm–1.
˜
Synthesis of 7cЈ: In a 20 mL Schlenk flask, [PdCl2(cod)] (0.088 g,
0.310 mmol), 2cЈ (0.117 g, 0.310 mmol), and K2CO3 (0.171 g,
1.24 mmol) were dissolved in dry pyridine (10 mL) under nitrogen.
The solution was stirred at 60 °C for 12 h. The solvent was com-
pletely removed under vacuum. The residue was redissolved in
dichloromethane and washed with water. The organic phase was
dried with anhydrous MgSO4, and the solvents were evaporated to
dryness under vacuum to give a solid. Diethyl ether was added,
Synthesis of 2cЈ: A mixture of 1-phenyl-1H-benzo[d]imidazole
(0.870 g, 4.47 mmol) and 2-chloro-N-methyl-N-phenylacetamide
(0.822 g, 4.47 mmol) in THF (30 mL) was placed in a Schlenk
flask. The mixture was heated under reflux for 48 h. After cooling,
the white solid was collected on a frit, washed with THF, and dried
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under vacuum. Yield: 0.500 g (30%). H NMR (CDCl3): δ = 3.32
(s, 3 H, NCH3), 5.73 (s, 2 H, NCH2), 7.25–7.79 (m, 14 H, Ar H), and the yellowish solid formed was collected on a frit and dried
11.29 (s, 1 H, NCHN) ppm. 13C{1H} NMR (CDCl3): δ = 38.0
(NCH3), 48.9 (NCH2), 112.9, 113.5, 124.0, 124.8, 127.0, 127.5,
127.6, 128.1, 129.2, 130.1, 130.7, 130.8, 131.8, 132.9, 141.0, 144.0,
under vacuum. Yield: 0.083 g (45%). M.p. 250.1–250.5 °C.
C27H24Cl2N4OPd (597.82): calcd. C 54.24, H 4.05, N 9.37; found
C 54.29, H 4.25, N 8.96. 1H NMR (CDCl3): δ = 3.35 (s, 3 H,
163.9 (C=O) ppm. HRMS (ESI): calcd. for C22H20ClN3O NCH3), 5.58 (s, 2 H, NCH2), 7.28–7.63 (m, 14 H, Ar H), 7.75 (t,
[M – Cl]+ 342.1606; found 342.1604.
JH,H = 9.0 Hz, 1 H, Ar H), 7.94 (d, JH,H = 9.0 Hz, 2 H Ar H), 8.75
(d, JH,H = 3.0 Hz, 2 H Ar H) ppm. 13C{1H} NMR (CDCl3): δ =
37.9 (NCH3), 49.8 (NCH2), 110.9, 111.6, 123.5, 123.8, 124.4, 127.7,
127.9, 128.7, 129.3, 129.5, 130.1, 135.2, 135.4, 136.9, 138.1, 142.6,
Synthesis of 7a: Dry DMF (10 mL) was added to a 20 mL Schlenk
flask that contained Pd(OAc)2 (0.226 g, 1.01 mmol), 2a (0.4 g,
1.01 mmol), and pyridine (0.081 mL, 1.01 mmol). The mixture was
stirred at ambient temperature for 12 h. The solvent was completely
151.1, 164.0 (Pd–C), 165.6 (C=O) ppm. IR (KBr): ν = 1670 (C=O)
˜
cm–1.
removed under vacuum, and
a solution of LiCl (0.336 g,
8.08 mmol) in anhydrous ethanol (10 mL) was added to the brown
residue, which was stirred vigorously for 30 min. The precipitate
was washed with diethyl ether, filtered through a frit, and dried
under vacuum. An air-stable yellow solid was obtained. Yield:
0.36 g (56%). M.p. 198.1–200.2 °C. C27H23Cl2FN4OPd (615.81):
Synthesis of 8a: In a 20 mL Schlenk flask, 7a (0.20 g, 0.324 mmol)
and PPh3 (0.0851 g, 0.324 mmol) in dichloromethane (10 mL) were
stirred at ambient temperature overnight. The mixture was filtered
through silica, and the solvent was completely removed under vac-
uum. The residue was washed with THF in which the side product
trans-[PdCl2(PPh3)3] dissolved. The off-white solid was filtered
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calcd. C 52.66, H 3.76, N 9.10; found C 52.19, H 3.72, N 8.79. H
NMR (CDCl3): δ = 3.32 (s, 3 H, NCH3), 5.62 (s, 2 H, NCH2), 7.01 through a frit and dried under vacuum. Yield: 0.14 g (55%). M.p.
(t, JH,H = 6.0 Hz, 1 H, Ar H), 7.19–7.75 (m, 12 H, Ar H), 7.99– 234.6–235.4 °C. C40H33Cl2FN3OPPd (799.00): calcd. C 60.13, H
1
8.04 (m, 2 H, Ar H), 8.16 (d, JH,H = 9.0 Hz, 1 H, Ar H), 8.90 (d, 4.16, N 5.26; found C 60.33, H 4.50, N 5.24. H NMR (CDCl3): δ
JH,H = 6.0 Hz, 2 H, py H) ppm. 13C{1H} NMR (CDCl3): δ = 38.0
(NCH3), 50.9 (NCH2), 110.8, 115.1, 116.1 (d, JC,F = 21.8 Hz),
= 3.08 (s, 3 H, NCH3), 5.16–5.60 (m, 2 H, NCH2), 7.05–7.72 (m,
27 H, Ar–H), 8.00 (d, JH,H = 9.0 Hz, 1 H, Ar H) ppm. 31P{1H}
122.6, 124.2, 124.8, 125.0, 127.7, 127.8, 130.0, 132.6 (d, JC,F
=
NMR (CDCl ): δ = 28.3 ppm. IR (KBr): ν = 1670 (C=O) cm–1.
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Eur. J. Inorg. Chem. 2014, 1492–1501
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© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim