O. Molokanova et al. / Tetrahedron 65 (2009) 7220–7233
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ArH), 6.01 (d, 2H, J¼2.2 Hz, ArH), 4.59 (d, 2H, J¼11.7 Hz, ArCH2Ar),
4.56–4.46 (m, 6H, ArCH2Ar), 4.30–4.02 (m, 12H, OCH2), 3.92–3.60
(m, 28H, OCH2), 3.29 (d, 2H, J¼12.1 Hz, ArCH2Ar), 3.24 (d, 2H,
J¼11.7 Hz, ArCH2Ar), 3.14 (d, 2H, J¼11.4 Hz, ArCH2Ar), 3.13 (d, 2H,
J¼11.7 Hz, ArCH2Ar), 2.20–1.65 (m, 26H, CH2), 1.55–1.09 (m, 82H,
CH2), 1.06–0.89 (m, 24H, CH3); MS (ESI) m/z: calcd for
C200H260N16O28 (Mþ2Naþþ2CH3CN) 1732.2, observed 1732.0.
7.90 (d, 2H, J¼2.2 Hz, ArH), 7.44 (m, 4H, NH, ArH), 7.40 (s, 2H, NH),
7.35 (m, 2H, ArH), 7.90–7.00 (m under the solvent peak, 12H, NH,
ArH), 6.62 (dd, 2H, J¼8.4, 1.7 Hz, ArH), 6.48–6.33 (m, 12H, ArH), 6.30
(d, 2H, J¼2.2 Hz, ArH), 4.54 (d, 2H, J¼12.0 Hz, ArCH2Ar), 4.48 (d, 2H,
J¼11.7 Hz, ArCH2Ar), 4.47 (d, 2H, J¼11.4 Hz, ArCH2Ar), 4.39 (d,
2H, J¼11.4 Hz, ArCH2Ar), 3.96–3.50 (m, 40H, OCH2), 3.33 (d, 2H,
J¼12.4 Hz, ArCH2Ar), 3.28 (d, 2H, J¼12.1 Hz, ArCH2Ar), 3.21 (d, 2H,
J¼12.4 Hz, ArCH2Ar), 3.20 (d, 2H, J¼11.4 Hz, ArCH2Ar), 2.15–1.87 (m,
16H, CH2), 1.74–1.02 (m, 160H, CH2), 0.98 (t, 12H, J¼7.3 Hz, CH3),
0.97 (t, 12H, J¼7.3 Hz, CH3); MS (ESI) m/z: calcd for C236H332N16O28
(Mþ2NaþþCH3CN) 1963.8, observed 1963.8; (Mþ2NaþþTHF)
1979.3, observed 1979.4.
4.5.4. Bis[3]catenane 8b
Approach A: starting with tetraloop compound 5b (80.0 mg,
0.0416 mmol), tetraalkenyl tetraurea 6b (64.7 mg, 0.0396 mmol) in
dichloromethane (160 mL), Grubbs’ catalyst (6.5 mg, 0.0079 mmol),
and triethylamine (0.5 mL). Hydrogenation in THF (20 mL) using
platinum dioxide (83% Pt, 8.0 mg, 0.036 mmol). The final puri-
fication by column chromatography (silica gel, THF/n-hexane, 1:15)
followed by recrystallization from chloroform/methanol gave
the bis[3]catenane 8b as a colorless, crystalline powder; yield
48.1 mg, 35%.
4.5.6. Bis[3]catenane 8d
Approach A: starting with tetraloop compound 5d (0.1362 g,
0.0548 mmol), tetraalkenyl tetraurea 6d (0.10 g, 0.0522 mmol) in
dichloromethane (211 mL), Grubbs’ catalyst (8.6 mg, 0.0104 mmol),
and triethylamine (1 mL). Hydrogenation in THF (20 mL) using
platinum dioxide (83% Pt, 10.6 g; 0.0470 mmol). The final purifi-
cation by column chromatography (silica gel, THF/n-hexane, 1:35)
followed by recrystallization from chloroform/methanol gave the
bis[3]catenane 8d as a colorless, crystalline powder; yield 0.112 g,
49%.
Approach B: starting with bisloop compound 7b (65.6 mg,
0.0414 mmol), octaalkenyl tetraurea 4b (0.0800 g, 0.0395 mmol)
in dichloromethane (160 mL), Grubbs’ catalyst (13.0 mg,
0.0158 mmol), and triethylamine (0.5 mL). Hydrogenation in THF
(20 mL) using platinum dioxide (83% Pt, 16.0 mg; 0.0713 mmol).
The final purification by column chromatography (silica gel, THF/n-
hexane, 1:15) followed by recrystallization from chloroform/
methanol gave the bis[3]catenane 8b as a colorless, crystalline
powder; yield 65.6 mg, 47%. Mp >280 ꢀC (decomposition); 1H NMR
(C6D6): 10.11 (s, 2H, NH), 10.06 (s, 2H, NH), 10.03 (s, 2H, NH), 10.00
(s, 2H, NH), 8.48 (s, 2H, ArH), 8.40 (d, 2H, J¼7.8 Hz, ArH), 8.28 (d, 2H,
J¼2.0 Hz, ArH), 8.23 (s, 2H, ArH), 8.16 (s, 2H, ArH), 8.10 (d, 2H,
J¼2.0 Hz, ArH), 8.07 (d, 2H, J¼1.7 Hz, ArH), 8.06 (d, 2H, J¼2.4 Hz,
ArH), 7.59 (s, 2H, ArH), 7.52 (s, 2H, NH), 7.38 (s, 2H, ArH), 7.27 (d, 2H,
J¼8.5 Hz, ArH), 7.22–7.07 (m under the solvent peak, 10H, NH, ArH),
7.05 (s, 2H, NH), 6.82 (s, 2H, NH), 6.71 (d, 2H, J¼8.2 Hz, ArH), 6.58 (s,
2H, ArH), 6.53 (dd, 2H, J¼7.8, 1.4 Hz, ArH), 6.48 (s, 2H, ArH), 6.43 (d,
2H, J¼2.0 Hz, ArH), 6.32 (d, 2H, J¼2.0 Hz, ArH), 6.27 (d, 2H, J¼2.4 Hz,
ArH), 6.25 (d, 2H, J¼2.4 Hz, ArH), 4.53 (d, 2H, J¼11.6 Hz, ArCH2Ar),
4.50 (d, 4H, J¼11.9 Hz, ArCH2Ar), 4.40 (d, 2H, J¼11.6 Hz, ArCH2Ar),
4.14–3.49 (m, 40H, OCH2), 3.31 (d, 2H, J¼11.9 Hz, ArCH2Ar), 3.29 (d,
2H, J¼11.9 Hz, ArCH2Ar), 3.16 (d, 2H, J¼11.9 Hz, ArCH2Ar), 3.15 (d,
2H, J¼11.9 Hz, ArCH2Ar), 2.11 (m, 4H, CH2), 1.97 (m, 12H, CH2), 1.81–
1.60 (m, 16H, CH2), 1.57–1.00 (m, 92H, CH2), 0.97 (t, 24H, J¼7.3 Hz,
CH3); MS (ESI) m/z: calcd for C212H284N16O28 (MHþþNaþþ
THFþEtOH) 1816.4, observed 1816.1.
Approach B: starting with bisloop compound 7d (75.2 mg,
0.0406 mmol), octaalkenyl tetraurea 4d (0.10 g, 0.0386 mmol) in
dichloromethane (150 mL), Grubbs’ catalyst (0.0127 g, 0.0154 mmol),
and triethylamine (1 mL). Hydrogenation in THF (20 mL) using
platinum dioxide (83% Pt, 15.8 mg; 0.0695 mmol). The final purifi-
cation by column chromatography (silica gel, THF/n-hexane, 1:25)
followed by recrystallization from chloroform/methanol gave the
bis[3]catenane 8d as a colorless crystalline powder; yield 56.4 mg,
33%. Mp >130 ꢀC (decomposition); 1H NMR (C6D6): 10.03 (s, 8H,
NH), 8.24 (d, 2H, J¼2.2 Hz, ArH), 8.20 (d, 2H, J¼1.9 Hz, ArH), 8.18 (d,
2H, J¼9.2 Hz, ArH), 8.14 (s, 6H, ArH), 8.06 (s, 2H, ArH), 8.00 (s, 2H,
ArH), 7.69 (s, 2H, ArH), 7.61 (d, 2H, J¼8.0 Hz, ArH), 7.39 (s, 2H, ArH),
7.31 (s, 2H, ArH), 7.30 (s, 2H, NH), 7.21 (s, 2H, NH), 7.19–7.05 (m
under the solvent peak, 8H, ArH, NH), 6.60 (dd, 2H, J¼8.3, 1.9 Hz,
ArH), 6.53 (dd, 2H, J¼8.6,1.6 Hz, ArH), 6.48 (s, 2H, ArH), 6.43 (s,
2H, ArH), 6.38 (s, 4H, ArH), 6.30 (d, 2H, J¼1.6 Hz, ArH), 6.28 (d, 2H,
J¼2.2 Hz, ArH), 4.62–4.47 (m, 8H, ArCH2Ar), 3.97–3.60 (m, 40H,
OCH2), 3.42 (d, 2H, J¼11.4 Hz, ArCH2Ar), 3.38 (d, 2H, J¼10.5 Hz,
ArCH2Ar), 3.34 (d, 2H, J¼10.8 Hz, ArCH2Ar), 3.27 (d, 2H, J¼11.4 Hz,
ArCH2Ar), 2.20–1.95 (m, 16H, CH2), 1.70–1.08 (m, 232H, CH2), 1.05–
0.96 (m, 24H, CH3); MS (ESI) m/z: calcd for C272H404N16O28
(Mþ2Hþ) 2174.2, observed 2174.0.
4.5.5. Bis[3]catenane 8c
Approach A: starting with tetraloop compound 5c (51.6 mg,
0.0240 mmol), tetraalkenyl tetraurea 6c (40.0 mg, 0.0229 mmol) in
dichloromethane (92 mL), Grubbs’ catalyst (3.8 mg, 0.0046 mmol),
and triethylamine (0.5 mL). Hydrogenation in THF (20 mL) using
platinum dioxide (83% Pt, 4.7 mg; 0.021 mmol). The final purifica-
tion by column chromatography (silica gel, THF/n-hexane, 1:20)
followed by recrystallization from chloroform/methanol gave the
bis[3]catenane 8c (0.0176 g, 20% yield) as a colorless, crystalline
powder.
4.5.7. Bis[3]catenane 8e
Approach B: starting with bisloop compound 7b (70.0 mg,
0.0442 mmol), octaalkenyl tetraurea 4a (80.7 mg, 0.0421 mmol)
in dichloromethane (170 mL), Grubbs’ catalyst (13.8 mg,
0.0168 mmol), and triethylamine (1 mL). Hydrogenation in THF
(20 mL) using platinum dioxide (83% Pt, 17.2 g; 0.0758 mmol). The
final purification by column chromatography (silica gel, THF/n-
hexane, 1:9) followed by recrystallization from chloroform/meth-
anol gave the bis[3]catenane 8e as a colorless, crystalline powder;
yield 85.7 mg, 60%. Mp >340 ꢀC (decomposition); 1H NMR (C6D6):
10.05 (s, 2H, NH), 10.04 (s, 2H, NH), 10.03 (s, 2H, NH), 9.94 (s, 2H,
NH), 8.49 (s, 2H, ArH), 8.42 (d, 2H, J¼8.3 Hz, ArH), 8.20 (s, 2H, ArH),
8.17 (d, 2H, J¼2.2 Hz, ArH), 8.11 (d, 2H, J¼2.5 Hz, ArH), 8.10 (s, 2H,
ArH), 8.06 (d, 2H, J¼2.2 Hz, ArH), 7.96 (d, 2H, J¼2.5 Hz, ArH), 7.58 (s,
2H, ArH), 7.50 (s, 2H, NH), 7.42–7.36 (m, 4H, ArH), 7.27 (s, 2H, ArH),
7.20–7.00 (m under the solvent peak, 8H, ArH, NH), 6.78 (s, 2H, NH),
6.72 (s, 2H, NH), 6.66 (dd, 2H, J¼8.0, 1.9 Hz, ArH), 6.58 (s, 2H, ArH),
6.55–6.50 (m, 4H, ArH), 6.33 (d, 2H, J¼2.2 Hz, ArH), 6.23 (d, 2H,
J¼1.9 Hz, ArH), 6.05 (d, 2H, J¼2.2 Hz, ArH), 6.02 (d, 2H, J¼2.2 Hz,
ArH), 4.58–4.46 (m, 8H, ArCH2Ar), 4.28–4.16 (m, 8H, OCH2),
Approach B: prepared from bisloop compound 7c (70.0 mg,
0.0413 mmol), octaalkenyl tetraurea 4c (88.5 mg, 0.0393 mmol) in
dichloromethane
(160 mL),
Grubbs’
catalyst
(12.9 mg,
0.0157 mmol), and triethylamine (1 mL). Hydrogenation in THF
(20 mL) using platinum dioxide (83% Pt, 16.1 mg; 0.0707 mmol).
The final purification by column chromatography (silica gel, THF/n-
hexane, 1:20) followed by recrystallization from chloroform/
methanol gave the bis[3]catenane 8c as a colorless, crystalline
powder; yield 72.4 mg, 48%. Mp >300 ꢀC (decomposition); 1H NMR
(C6D6): 9.99 (s, 2H, NH), 9.94 (s, 2H, NH), 9.91 (s, 2H, NH), 9.87 (s,
2H, NH), 8.30–8.19 (m, 8H, ArH), 8.07 (s, 2H, ArH), 8.00 (m, 4H, ArH),