Paper
Organic & Biomolecular Chemistry
(0.678 mmol) of the amine 28] and di-n-butyltin dilaurate 167.8, 169.2; HRMS (ESI) m/z [M + H]+: C61H84N3O8, calcd for
(25.3 μL, 0.041 mmol) in CH2Cl2 (0.5 mL) and then the 986.6258, found 986.6211; [M + Na]+: C61H83N3O8Na, calcd
mixture was stirred at room temperature for 16 h. The solvent 1008.6078, found 1008.6021.
was evaporated under reduced pressure and then the residue
was purified (SiO2; EtOAc–hexanes, 4 : 6) to afford a white solid
1
(21.0 mg, 10%). M.p. 252–253 °C; H NMR (400 MHz, CDCl3):
Acknowledgements
δ = 0.80–0.90 (m, 2H), 1.29 (s, 54H), 1.53–1.65 (overlapping
with the signal for water, 2H), 3.39–3.70 (m, 22H), 4.33–4.41 We thank the National Science Council of Taiwan (NSC-102-
(m, 8H), 7.05–7.15 (m, 24H), 7.20–7.27 (m, 14H), 7.39 (d, J = 2119-M-002-007) and National Taiwan University (NTU-102-
8.8 Hz, 2H), 7.86 (s, 1H), 8.33 (s, 1H); 13C NMR (100 MHz, R890913) for financial support.
CDCl3): δ = 23.9, 29.7, 31.4, 32.8, 34.3, 63.2, 63.3, 69.2, 69.5,
70.6, 70.6, 70.8, 73.2, 73.3, 116.8, 117.9, 124.0, 128.3, 130.8,
131.6, 131.6, 136.7, 136.8, 137.1, 137.1, 141.2, 142.0, 144.1,
Notes and references
144.1, 148.3, 148.3, 153.7, 171.3 (five signals were missing,
possibly because of signal overlap); HRMS (ESI) m/z [M + Na]+:
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C105H130N2O10Na, calcd 1601.9623, found 1602.0217.
[2]Rotaxane 35. A solution of the urea derivative 10
(56.7 mg, 0.160 mmol), the macrocycle
5 (197 mg,
0.400 mmol), and NaTFPB (355 mg, 0.400 mmol) in CH2Cl2
(0.8 mL) was added to a solution of the isocyanate 13 [trans-
formed from 164 mg (0.800 mmol) of 3,5-di-tert-butylaniline]
and di-n-butyltin dilaurate (30.3 µL, 0.048 mmol) in CH2Cl2
(0.8 mL) and then the mixture was stirred at room temperature
for 16 h. The solvent was evaporated under reduced pressure
and then the residue was purified (SiO2; EtOAc–hexanes, 4 : 6)
to afford a colorless oil (74.5 mg, 43%). 1H NMR (400 MHz,
CDCl3): δ = 1.31 (s, 18H), 1.33 (s, 18H), 3.35–3.50 (m, 4H),
3.61–3.70 (m, 8H), 4.38 (s, 4H), 4.49–4.60 (m, 8H), 4.91 (s, 2H),
6.73 (d, J = 8.4 Hz, 2H), 6.86 (d, J = 8.4 Hz, 2H), 7.00–7.10 (m,
9H), 7.12 (d, J = 1.6 Hz, 1H), 7.18 (d, J = 1.6 Hz, 2H), 7.30 (s,
2H), 7.40 (d, J = 7.6 Hz, 2H), 7.46 (s, 1H), 7.57 (s, 1H), 7.63 (s,
1H), 7.76 (t, J = 7.6 Hz, 1H); 13C NMR (100 MHz, CD3COCD3): δ
= 31.4, 31.5, 34.8, 34.8, 66.5, 69.0, 70.6, 70.9, 71.8, 73.0, 112.9,
113.2, 116.0, 117.1, 118.1, 120.6, 127.7, 128.2, 128.3, 128.4,
136.0, 137.4, 137.7, 137.7, 139.1, 139.2, 151.0, 151.5, 151.7,
153.7, 157.6 (one signal was missing, possibly because of
signal overlap); HRMS (ESI) m/z [M + H]+: C66H87N4O9, calcd
1079.6473, found 1079.7648.
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[2]Rotaxane 36. A solution of 3,5-di-tert-butylbenzoic acid
(216 mg, 0.922 mmol) and N,N′-dicyclohexylcarbodiimide
(190 mg, 0.922 mmol) in CH2Cl2 (1.75 mL) was stirred at 0 °C
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evaporated under reduced pressure and then the residue was
purified (SiO2; MeOH–EtOAc–hexanes, 4 : 48 : 48) to afford a
colorless oil (40.0 mg, 11%). 1H NMR (400 MHz, CD3COCD3): δ
= 1.25 (s, 18H), 1.32 (s, 18H), 3.30–3.52 (m, 14H), 3.85 (d, J =
5.6 Hz, 2H), 4.39 (s, 4H), 4.45 (s, 4H), 4.59 (s, 4H), 6.99 (d, J =
1.6 Hz, 2H), 7.20 (d, J = 8 Hz, 4H), 7.26 (m, 5H), 7.31 (t, J =
1.6 Hz, 1H), 7.37 (d, J = 7.6 Hz, 2H), 7.60–7.62 (m, 2H) 7.66 (d,
J = 1.6 Hz, 2H), 7.75 (t, J = 7.6 Hz, 1H); 13C NMR (100 MHz,
CD3COCD3): δ = 31.9, 32.0, 35.4, 35.6, 43.9, 44.1, 70.4, 71.4,
71.5, 72.3, 72.8, 73.8, 121.1, 121.8, 122.9, 124.0, 125.9, 129.1,
129.3, 135.5, 138.0, 138.2, 138.6, 139.7, 151.1, 151.3, 158.9,
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2916 | Org. Biomol. Chem., 2014, 12, 2907–2917
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