R. AuzØly-Velty, M. Sollogoub et al.
silica gel (cyclohexane/EtOAc, 4:1 then 3:1) to give 8 (844 mg, 62%) as a
white foam. Dimer 8 (780 mg, 134 mmol) was dissolved in 1,2-dimethoxy-
ethane (19.5 mL) and treated with p-toluenesulfonyl hydrazide (2.04 g,
10.9 mmol). The reaction mixture was heated at reflux and a solution of
sodium acetate in water (1.85 g in 13 mL H2O) was added dropwise.
After heating at reflux for 6 h, the reaction mixture was concentrated, di-
luted in EtOAc (20 mL) and washed with H2O (15 mL). The aqueous
layer was extracted with EtOAc (315 mL). The organic layers were
combined, washed with brine (40 mL), dried with MgSO4 and concentrat-
ed. The crude product was purified by column chromatography on silica
gel (cyclohexane/EtOAc, 4:1, then 3:1) to give 10 (717 mg, 92%) as a
white foam. Rf =0.42 (cyclohexane/EtOAc 2:1); 1H NMR (400 MHz,
CDCl3): d=1.45–1.57 (m, 4H; 4OCH2CH2CH2CH2O), 2.48 (brs; 2
OH), 3.31 (brd, J=4.2 Hz, 4H; 4OCH2CH2CH2CH2O), 3.36–4.12 (m,
92H; 142-H, 143-H, 144-H, 145-H, 286-H, 8OCH2CH2O),
4.32–4.60 (m, 46H; 46CHPh), 4.62–4.83 (m, 19H; 19CHPh), 4.90–
5.02 (m, 7H; 7CHPh), 5.03–5.27 (m, 15H; 101-H, 5CHPh), 5.34–
5.44 (m, 4H; 41-H), 7.10–7.30 ppm (m, 190H; CH arom.); 13C NMR
(100 MHz, CDCl3): d=26.1 (CH2), 26.2 (CH2), 26.8 (CH2), 26.9 (CH2),
69.2–69.7 (OCH2), 70.4 (OCH2), 71.0 (OCH2), 71.1–71.9 (CH), 72.4–72.9
(CH2Ph), 73.1–73.4 (CH2Ph), 74.7–75.9 (CH2Ph), 78.5–79.8 (CH), 80.7–
81.1 (CH), 97.9–98.9 (C-1), 127.4–128.3 (CH arom.), 137.8–138.5 (C
arom. quat.), 138.8–139.3 ppm (CH arom. quat.); MS (MALDI-TOF):
m/z (%): 5855.4 (100) [M+ꢀNa]; elemental analysis calcd (%) for
chromatography on silica gel (cyclohexane/EtOAc, 4:1) to give 12
(245 mg, 77%) as a white foam. Rf =0.57 (Cy/EtOAc 3:1); 1H NMR
(400 MHz, CDCl3): d=1.45–1.47 (m, 8H; 8OCH2CH2CH2CH2O), 3.24
(t, 8H; 8OCH2CH2CH2CH2O), 3.32–4.20 (m, 83H; 67CH, 16
OCH2CH2O), 4.32–4.63 (m, 50H; 50CHPh), 4.73–4.89 (m, 16H; 16
CHPh), 4.92–5.07 (m, 8H; 41-H, 4CHPh), 5.09 (t, 3J1,2 =3.4 Hz, 2H;
21-H), 5.13 (t, 3J1,2 =3.3 Hz, 2H; 21-H), 5.22 (d, 2J=10.5 Hz; 2
2
CHPh), 5.24 (d, J=10.6 Hz; 2CHPh), 5.34 (m, 4H; 21-H, 2CHPh),
5.40 (t, 3J1,2 =3.3 Hz, 2H; 21-H), 5.44 (d, 3J1,2 =3.6 Hz, 1H; 11-H),
3
5.46 (d, J1,2 =3.7 Hz, 1H; 11-H), 7.05–7.30 ppm (m, 190H; CH arom.);
13C NMR (100 MHz, CDCl3): d=26.2 (CH2), 26.3 (CH2), 69.1–69.4
(OCH2), 70.2–70.9 (OCH2), 71.2–71.7 (CH), 72.2–73.3 (CH2Ph), 74.6–76.2
(CH2Ph), 78.3–79.4 (CH), 80.4–81.0 (CH), 97.9–98.9 (C-1), 127.4–128.3
(CH arom.), 138.1–138.5 (C arom. quat.), 139.0–139.3 ppm (CH arom.
quat.); MS (MALDI-TOF): m/z (%): 5999.8 (100) [M+ꢀNa]; elemental
analysis calcd (%) for C366H396O74
A
C 72.81, H 6.78.
Acknowledgements
The authors would like to thank Cyclolab (Hungary) for a generous
supply of b-CD. M.S. would also like to personally thank Prof. Pierre
Sinaþ for his support.
C358H382O72(H2O)2 (5866): C 73.22, H 6.62; found: C 72.91, H 6.72.
A
Dimer 11: At 08C and under argon, nBu4NI (2.8 mg, 7.5 mmol) and NaH
(60% dispersion in oil, 18 mg, 450 mmol) were added to a solution of 10
(436 mg, 75 mmol) in THF (3 mL). The reaction mixture was stirred at
08C under argon for 20 min, then 7 (115 mg, 450 mmol) was added. The
mixture was stirred at RT under argon for 15 h, then NaH (60% disper-
sion in oil, 18 mg, 450 mmol) and the 7 (115 mg, 450 mmol) were added.
After 8 h, the reaction mixture was treated with MeOH (5 mL), evapo-
rated and finally diluted with CH2Cl2 (15 mL). The organic layer was
washed with a saturated solution of NH4Cl (10 mL). The aqueous layer
was extracted with CH2Cl2 (315 mL). The organic layers were com-
bined, washed with brine (40 mL), dried with MgSO4, filtered and con-
centrated. The crude mixture was purified by column chromatography on
silica gel (cyclohexane/EtOAc, 6:1, then 3:1) to give 11 (417 mg, 93%).
Rf =0.60 (cyclohexane/EtOAc 3:1, eluted twice); 1H NMR (400 MHz,
CDCl3): d=1.45–1.60 (m, 4H; 4OCH2CH2CH2CH2O), 3.30–3.38 (m,
4H; 4OCH2CH2CH2CH2O), 3.40–3.75 (m, 33H; 17CH, 16
OCH2CH2O), 3.85–4.15 (m, 67H; CH), 4.40–4.62 (m, 52H; 52CHPh),
4.78–4.87 (m, 12H; 12CHPh), 5.00–5.35 (m, 30H; 141-H, 12CHPh,
4OCH2CH=CH2), 5.89 (dddd, 3Jtrans =19.5 Hz, 3Jcis =10.5 Hz, 3J=9 Hz,
2H; 2OCH2CH=CH2), 7.12–7.30 ppm (m, 190H; CH arom.); 13C
NMR (100 MHz, CDCl3): d=26.2 (CH2), 26.9 (CH2), 29.7 (CH2), 30.1
(CH2), 68.9–69.7 (OCH2), 70.3–70.5 (OCH2), 70.9 (OCH2), 71.2–71.6
(CH), 71.9–73.3 (CH2Ph), 75.0–75.7 (CH2Ph), 77.7–79.4 (CH), 80.7–80.9
(CH), 98.2–98.6 (C-1), 116.8, 116.85 (OCH2CH=CH2), 127.3–128.3 (CH
arom.), 134.7, 134.8 (OCH2CH=CH2), 138.1–138.4 (C arom. quat.),
139.1–139.3 ppm (CH arom. quat.); MS (MALDI-TOF): m/z (%):
6023.36 (100) [M+ꢀNa]; elemental analysis calcd (%) for C368H398O74-
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53 mmol) was dissolved in 1,2-dimethoxyethane (8 mL) and treated with
AHCTREUNG
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8856
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Chem. Eur. J. 2007, 13, 8847 –8857