8502
S. Durot et al. / Tetrahedron 64 (2008) 8496–8503
d
¼8.54 (d, J¼8.3 Hz, 2H), 8.27 (d, J¼8.3 Hz, 2H), 8.28–7.86 (m, 10H),
5.35 (s), 3.58 (br m, 4H), 2.97 (br m, 4H), 2.24 (br m, 4H), 1.32
7.31 (d, 8.4 Hz, 4H), 7.24 (d, J¼8.5 Hz, 12H), 7.18 (d, J¼8.9 Hz, 4H),
7.13 (d, J¼8.6 Hz, 12H), 6.88 (d, J¼8.9 Hz, 4H), 6.17 (d, J¼8.4 Hz, 4H),
5.48 (s, 4H), 5.17 (s, 4H), 3.76–3.65 (m, 20H),1.27 (s, 54H). HR ES-MS
m/z¼1979.9833 [MꢁPF6]þ, calcd for CuC126H136N10O8¼1979.9833.
(s, 54H). HR ES-MS: m/z¼2091.0241 [MꢁPF6]þ, calcd for
C137H137CuN13O4¼2091.0207.
Acknowledgements
4.4.2. Metallo-rotaxane (2þ)
We are grateful to the European Communities (MOLDYNLOGIC)
and to the CNRS for financial support.
The same procedure was used as in the case of 1þ. The metallo-
rotaxane 2þ was obtained as a red solid (55 mg, 67%). 1H NMR
(300 MHz, CD2Cl2):
d
¼8.70 (d, J¼8.4 Hz, 2H), 8.43 (d, J¼8.3 Hz, 2H,),
References and notes
8.30 (s, 2H), 8.03 (s, 2H), 7.92 (d, J¼8.4 Hz, 2H), 7.73 (d, J¼8.3 Hz,
2H), 7.56 (d, J¼8.4 Hz, 4H), 7.52 (s, 2H), 7.25 (d, J¼8.6 Hz, 12H), 7.19
(d, 4H), 7.18 (d, 4H), 7.14 (d, J¼8.6 Hz, 12H), 6.90 (d, J¼9.0 Hz, 4H),
6.54 (d, J¼8.1 Hz, 4H), 5.95 (d, J¼8.7 Hz, 4H), 5.18 (s, 4H), 5.15
(s, 4H), 3.83 (s, 4H), 3.72 (m, 4H), 3.59 (m, 8H), 3.50 (m, 4H),
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4.4.3. Rotaxane (23)
Macrocycle 21 (50.8 mg, 7.5ꢂ10ꢁ2 mmol) was dissolved in
a mixture of degassed dichloromethane and acetonitrile (1.3 mL,
3/1). To this solution was added [Cu(CH3CN)4]PF6 (28 mg,
7.5ꢂ10ꢁ2 mmol). The mixture turned brown immediately. After 30
min of stirring under argon bipyridine 7 (20 mg, 7.5ꢂ10ꢁ2 mmol)
was added. The colour of the reaction mixture turned instan-
taneously to deep red. Stirring was continued for 1 h, and stopper
5 (81.5 mg, 15ꢂ10ꢁ2 mmol), Na2CO3 (3.2 mg, 3.0ꢂ10ꢁ2 mmol), and
[Cu(MeCN)4]PF6 (42 mg, 11.2ꢂ10ꢁ2 mmol), were then added, and
the reaction mixture was stirred for 16 h. To observe the end of the
reaction, another addition of stopper 5 (30 mg, 5.5 10ꢁ2 mmol),
Na2CO3 (3.2 mg, 3.0ꢂ10ꢁ2 mmol), and [Cu(CH3CN)4]PF6 (21 mg,
5.6ꢂ10ꢁ2 mmol) and 4 h of stirring were necessary. For the
demetallation of 3þ, some dichloromethane (5 mL) and water
(5 mL), and KCN (40 mg, 0.6 mmol) were added. After vigorous
stirring for 30 min, the phases were separated, the aqueous layer
was extracted three times with 5 mL portions of dichloromethane
and the combined organic layers were dried and the solvent
removed under reduced pressure. The crude product was firstly
purified by chromatography (Al2O3, CH2Cl2/MeOH (92/8)) followed
by two preparative plate experiments (Al2O3, CH2Cl2/MeOH (99:1)).
The desired rotaxane 23 was recovered in 12% yield as a yellow
solid. 1H NMR (400 MHz, CD2Cl2):
d
¼8.68 (d, J¼8.0 Hz, 2H), 8.54
(d, J¼1.5 Hz, 2H), 8.35 (d, J¼7.8 Hz, 2H), 8.32 (s, 2H), 8.24
(d, J¼1.5 Hz, 2H), 8.20 (d, J¼8.4 Hz, 2H), 7.99 (d, J¼8.2 Hz, 2H), 7.89
(t, J¼7.8 Hz, 1H), 7.84–7.76 (m, 8H), 7.56 (dd, J¼8.0 Hz, J¼2.0 Hz,
2H), 7.36 (dd, J¼8 Hz, J¼2.0 Hz, 2H), 7.20 (d, J¼8.6 Hz, 12H), 7.06
(d, J¼8.6 Hz, 12H), 7.00 (d, J¼8.8 Hz, 4H), 6.73 (d, J¼8.7 Hz, 4H), 5.27
(s, 4H), 5.03 (s, 4H), 3.69 (t, 4H, J¼5.9 Hz), 2.92 (m, 4H), 2.06 (m, 4H),
1.28 (s, 54H). HR ES-MS: m/z¼2029.0956 [MþH]þ calcd for
35. Aprahamian, I.; Miljanic, O. S.; Dichtel, W. R.; Isoda, K.; Yasuda, T.; Kato, T.;
Stoddart, J. F. Bull. Chem. Soc. Jpn. 2007, 80, 1856–1869.
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Chem. Soc. 2006, 128, 10388–10390.
C
137H138N13O4: 2029.0989.
4.4.4. Metallo-rotaxane (3þ)
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The reaction was conducted under inert atmosphere. Rotaxane
23 (14 mg, 6.9ꢂ10ꢁ6 mol) was dissolved in a mixture of dich-
loromethane and acetonitrile (3 mL, 2:1) and was added
[Cu(CH3CN)4]PF6 (2.6 mg, 6.9ꢂ10ꢁ6 mol). The solution turned im-
mediately deep red. The reaction mixture was then stirred for 1 h
and the solvents were evaporated to give a red solid. The com-
plexation process occurred quantitatively as evidenced by 1H NMR.
1H NMR (300 MHz, CD2Cl2):
d
¼8.68–8.30 (complex, 8H), 8.2–7.6
(complex, 12H), 7.40 (d, J¼7.7 Hz, 4H), 7.29 (d, J¼8.5 Hz, 12H), 7.18
(d, J¼8.5 Hz, 12H), 6.94 (d, J¼7.5 Hz, 4H), 6.16 (d, J¼7.5 Hz, 4H),
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5829–5832.