3554
G. Anilkumar et al. / Tetrahedron: Asymmetry 16 (2005) 3536–3561
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4.54. Ruthenium{2,6-bis-(2-naphthoyl-[4R,5R]-4,5-diphen-
yl-4,5-dihydro-1H-imidazol-2-yl)-pyridine}{pyridine-2,6-
dicarboxylate} 15k
(CH2Cl2/MeOH 100:5); H NMR (400 MHz, CD2Cl2):
d 0.69 (d, J = 6.92, 6H), 0.81 (d, J = 6.92, 6H), 0.84
(d, J = 6.56, 6H), 0.87–0.95 (m, 4H), 1.00–1.07 (m,
2H), 1.21–1.31 (m, 4H), 1.52–1.60 (m, 4H), 1.81–1.84
(m, 2H), 2.03–2.09 (m, 2H), 3.08 (dt, J = 3.96, 10.52,
2H), 3.95 (d, J = 14.68, 2H), 4.17 (d, J = 14.68, 2H),
4.32 (d, J = 3.96, 2H), 5.42 (d, J = 3.96, 2H), 6.54 (d,
J = 7.12, 4H), 7.02–7.10 (m, 8H), 7.17–7.21 (m, 2H),
7.32–7.34 (m, 6H), 7.45 (d, J = 7.52, 2H), 7.61 (t,
J = 8.32, 1H), 7.83 (t, J = 8.32, 1H), 8.73 (d, J = 8.36,
2H); 13C NMR (100 MHz, CD2Cl2): d 15.9, 20.7, 21.9,
23.1, 25.5, 31.4, 34.3, 39.8, 47.9, 68.2, 70.6, 77.2, 80.8,
125.4, 125.9, 126.2, 127.7, 128.7, 129.1, 129.2, 129.7,
136.7, 140.1, 148.8, 150.4, 162.0, 168.6, 170.1; UV–vis
(CH2Cl2: kmax/nm, loge): 352 (3.92), 488 (4.28); HRMS:
calcd for C66H72N6O8Ru: 1178.4456. Found: 1178.4506.
Anal. Calcd (%) for C66H72N6O8RuÆH2O: C, 66.26; H,
6.23; N, 7.02. Found: C, 66.57; H, 6.36; N, 6.78.
Prepared according to general procedure B using
[Ru(p-cymene)Cl2]2 (104 mg, 0.17 mmol), 6k (286 mg,
0.34 mmol) and disodium 2,6-pyridinedicarboxylate
(72 mg, 0.34 mmol) in MeOH/H2O (15:5 mL) at 65 ꢁC
for 1 h followed by chromatography on silica gel using
2% MeOH–CH2Cl2 to afford 15k as a dark brown pow-
der (247 mg, 64%). Rf = 0.30 (CH2Cl2/MeOH 100:5);
1H NMR (400 MHz, CDCl3): d 4.79 (d, J = 4.16, 2H),
5.40 (d, J = 4.16, 2H), 6.88 (d, J = 7.16, 4H), 7.16 (d,
J = 6.96, 4H), 7.37 (t, J = 7.72, 4H), 7.47–7.59 (m,
10H), 7.76–7.86 (m, 10H), 8.55 (d, J = 8.12, 2H);
13C NMR (100 MHz, CDCl3): d 31.83, 74.35, 124.6,
125.9, 126.1, 126.7, 127.0, 127.7, 128.4, 128.5, 128.8,
128.9, 129.3, 129.6, 130.2, 131.7, 134.2, 135.0, 136.2,
140.6, 148.8, 150.5, 163.4, 170.5, 170.7; UV–vis
(CH2Cl2: kmax/nm, loge): 495 (4.37), 378 (4.05); FAB-
MS: m/z 1095 (M++1); HRMS: calcd for C64H44N6-
O6Ru: 1094.2366. Found: 1094.2395. Anal. Calcd (%)
for C64H44N6O6RuÆ2H2O: C, 68.02; H, 4.28; N, 7.44.
Found: C, 68.20; H, 4.88; N, 7.01.
4.57. Ruthenium{2,6-bis-(1-adamantoyl-[4R,5R]-4,5-di-
phenyl-4,5-dihydro-1H-imidazol-2-yl)-pyridine}{pyridine-
2,6-dicarboxylate} 15n
Prepared according to general procedure B using 6n
(150 mg, 0.18 mmol), [Ru(p-cymene)Cl2]2 (54 mg,
0.09 mmol) and Na2pydic (37 mg, 0.18 mmol) to afford
15n as a dark brown solid (130 mg, 66%). Rf = 0.35
4.55. Ruthenium{2,6-bis-(1-[(2S)-2-(6-methoxy-naphthal-
en-2-yl)-propionyl]-[4R,5R]-4,5-diphenyl-4,5-dihydro-1H-
imidazol-2-yl)-pyridine}{pyridine-2,6-dicarboxylate} 15l
1
(CH2Cl2/MeOH 100:5); H NMR (400 MHz, CD2Cl2):
d 1.56 (m, 6H), 1.65 (m, 8H), 1.82–1.85 (m, 6H), 1.90–
1.96 (m, 12H), 4.26 (d, J = 2.7, 2H), 5.53 (d, J = 2.7,
2H), 6.52 (m, 4H), 7.04–7.08 (m, 8H), 7.19 (m, 2H),
7.29–7.33 (m, 6H), 7.48 (d, J = 7.5, 2H), 7.64 (dd,
J = 8.1, 7.3, 1H), 7.83 (dd, J = 8.7, 7.5, 1H) 7.96 (d,
J = 7.7, 2H); 13C NMR (100 MHz, CD2Cl2): d 28.1,
36.1, 39.4, 44.2, 71.5, 78.8, 125.1, 125.2, 125.8, 126.2,
126.6, 128.6, 128.7, 129.2, 129.5, 134.6, 136.1, 140.6,
149.1, 150.7, 165.1, 170.0, 181.1; UV–vis (CH2Cl2:
Prepared according to general procedure B using 6l
(150 mg, 0.16 mmol), [Ru(p-cymene)Cl2]2 (49 mg,
0.080 mmol) and Na2pydic (34.0 mg, 0.16 mmol) to
afford 15l as a dark brown solid (150 mg, 78%).
1
Rf = 0.45 (CH2Cl2/MeOH 100:6); H NMR (400 MHz,
CD2Cl2): d 1.50 (d, J = 6.5, 6H), 3.80 (q, J = 6.5, 2H),
3.86 (s, 6H), 4.05 (d, J = 3.1, 2H), 5.18 (d, J = 3.1,
2H), 6.02 (d, J = 7.7, 2H), 6.46 (t, J = 7.6, 4H), 6.72
(t, J = 7.4, 2H), 7.01 (unresolved d, 2H), 7.07–7.10 (m,
6H), 7.24 (unresolved dd, 2H), 7.33 (d, J = 7.8, 2H),
7.37 (m, 6H), 7.50 (t, J = 7.8, 1H), 7.59 (t, 6H), 7.93
(t, J = 8.3 Hz, 1H), 8.86 (d, J = 8.3, 2H); 13C NMR
(100 MHz, CD2Cl2): d 20.8, 45.6, 55.3, 69.9, 76.5, 78.8,
105.5, 116.9, 119.2, 125.2, 125.4, 125.5, 125.6, 125.8,
127.9, 127.9, 128.1, 128.5, 129.0, 129.1, 129.3, 129.9,
133.8, 134.1, 136.1, 140.2, 148.6, 150.6, 158.0, 162.3,
169.9, 171.9; UV–vis (CH2Cl2: kmax/nm, loge): 333
(3.65), 488 (4.27); FAB-MS: m/z 1211 (M+); Anal. Calcd
(%) for C70H56N6O8Ru: C, 69.47; H, 4.66; N, 6.94.
Found: C, 69.96; H, 4.49; N, 6.64.
k
max/nm, loge): 458 (3.96), 487 (4.22); FAB-MS: m/z
1111 (M++1); Anal. Calcd (%) for C64H60N6O6RuÆH2O:
C, 68.13; H, 5.54; N, 7.45. Found: C, 67.65; H, 5.59; N,
7.14.
4.58. Ruthenium{2,6-bis-(1-acetyl-[4R,5R]-4,5-diphenyl-
4,5-dihydro-1H-imidazol-2-yl)-pyridine}{pyridine-2,6-
dicarboxylate} 15o
Prepared according to general procedure B using
[Ru(p-cymene)Cl2]2 (152 mg, 0.25 mmol), 6o (300 mg,
0.50 mmol) and disodium 2,6-pyridinedicarboxylate
(105 mg, 0.50 mmol) in MeOH/H2O (15:5 mL) at
65 ꢁC for 1 h followed by chromatography on silica gel
using MeOH–CH2Cl2 as the gradient eluent to afford
15o as a dark brown powder (292 mg, 68%). Rf = 0.35
4.56. Ruthenium{2,6-bis-(1-(2-(1R,2S,5R)-2-isopropyl-5-
methylcyclohexyl-3-oxy-acetyl)-[4R,5R]-4,5-diphenyl-
4,5-dihydro-1H-imidazol-2-yl)-pyridine}{pyridine-2,6-
dicarboxylate} 15m
1
(CH2Cl2/MeOH 100:5); H NMR (300 MHz, CD2Cl2):
d 2.15 (s, 6H), 4.31 (d, J = 3.75, 2H), 5.22 (d, J = 3.78,
2H), 6.56 (d, J = 7.17, 4H), 7.03–7.23 (m, 10H), 7.36
(t, J = 3.75, 6H), 7.44 (d, J = 7.53, 2H), 7.60 (t,
J = 7.14, 1H), 7.83 (t, J = 8.10, 1H), 8.74 (d, J = 8.28,
2H); 13C NMR (75 MHz, CD2Cl2): d 23.7, 72.0, 76.6,
125.4, 125.8, 126.1, 126.5, 127.8, 128.6, 129.1, 129.2,
129.7, 134.7, 136.8, 140.1, 148.7, 150.4, 162.2, 168.7,
170.2; UV–vis (CH2Cl2: kmax/nm, loge): 487 (4.29);
HRMS: calcd for C46H36N6O6Ru: 870.1740, Found:
Prepared according to general procedure B using
[Ru(p-cymene)Cl2]2 (168 mg, 0.27 mmol), 6m (500 mg,
0.55 mmol) and disodium 2,6-pyridinedicarboxylate
(116 mg, 0.55 mmol) in MeOH/H2O (15:5 mL) at
65 ꢁC for 1 h followed by chromatography on silica gel
using MeOH–CH2Cl2 as the gradient eluent to afford
15m as a dark brown powder (297 mg, 46%). Rf = 0.30