3100
G. Li et al. / Tetrahedron Letters 52 (2011) 3097–3101
Figure 2. Circular dichroism spectral changes of 0.103 mM 9 upon changing the concentration of methanol from 0 to 80%.
(1 mL). The organic extract was analyzed by gas chromatography on a Supelco
BETA-DEX™ 225 column for both the E/Z ratio and ee of 1E.
Acknowledgment
9. (a) Kajtar, M.; HorvathToro, C.; Kuthi, E.; Szejtli, J. Acta. Chim. Acad. Sci. Hung.
1982, 110, 327; (b) Tong, L. H.; Hou, Z. J.; Inoue, Y.; Tai, A. J. Chem. Soc., Perkin
Trans. 2 1992, 1253.
Financial support from the Chinese Natural Science Foundation
(No. 20772120) is gratefully acknowledged.
10. Compound 3: TLC: Rf = 0.29 (n-BuOH/EtOH/H2O = 5:4:3, v/v); 1H NMR
(600 MHz, DMSO-d6) d: 7.55 (d, 2H), 7.49–7.35 (m, 5H), 7.33–7.24 (m, 2H),
5.85–5.55 (m, 14H), 5.20 (s, 2H), 4.95–4.70 (m, 7H), 4.60–4.25 (m, 8H), 3.97 (br,
1H), 3.76–3.22 (m, 39H); 13C NMR (600 MHz, DMSO-d6) d: 165.84, 158.78,
131.38, 130.43, 128.99, 128.38, 128.08, 122.30, 120.71, 115.35, 103.12, 102.43,
102.14, 82.80, 82.06, 82.01, 81.93, 81.85, 81.62, 73.62, 73.51, 73.39, 72.88,
72.76, 72.69, 72.61, 72.52, 69.87, 69.30, 64.58, 60.39, 60.20, 60.04; ESI-MS: m/
z = 1367 ([M+Na]+). Compound 4: TLC: Rf = 0.50 (n-BuOH/EtOH/H2O = 5:4:3, v/
v); 1H NMR (600 MHz, DMSO-d6) d: 7.45 (d, 2H), 7.38 (t, 2H), 7.36–7.28 (m, 2H),
7.24 (d, 2H), 5.79–5.60 (m, 14H), 5.14 (s, 2H), 4.90–4.77 (m, 7H), 4.60–4.25 (m,
9H), 3.97 (br, 1H), 3.76–3.22 (m, 38H), 2.34 (s, 3H); 13C NMR (600 MHz, DMSO-
d6) d: 167.47, 157.07, 131.73, 128.95, 128.27, 127.83, 126.92, 122.35, 115.97,
103.11, 102.45, 102.13, 82.89, 82.03, 81.95, 81.76, 81.59, 73.63, 73.51, 73.35,
72.89, 72.76, 72.68, 72.51, 72.47, 70.24, 69.34, 64.49, 60.39, 60.18, 60.03, 13.20;
ESI-MS: m/z = 1381 ([M+Na]+). Compound 5: TLC: Rf = 0.45 (n-BuOH/EtOH/
H2O = 5:4:3, v/v); 1H NMR (600 MHz, DMSO-d6) d: 7.55–7.43 (m, 4H), 7.40 (t,
2H), 7.30 (m, 2H), 5.82–5.58 (m, 14H), 5.19 (s, 2H), 4.90–4.78 (m, 7H), 4.57–
4.27 (m, 9H), 3.97 (br, 1H), 3.76–3.24 (m, 38H), 2.26 (s, 3H); 13C NMR
(600 MHz, DMSO-d6) d: 165.98, 156.66, 132.84, 131.14, 129.01, 128.91, 128.27,
127.6, 122.31, 112.25, 103.10, 102.41, 102.14, 82.83, 82.02, 81.87, 81.61, 73.61,
73.51, 73.41, 72.89, 72.78, 72.71, 72.60, 72.51, 69.71, 69.35, 64.40, 60.39, 60.21,
60.05, 16.82; ESI-MS: m/z = 1381 ([M+Na]+). Compound 6: TLC: Rf = 0.48
(n-BuOH/EtOH/H2O = 5:4:3, v/v); 1H NMR (600 MHz, DMSO-d6) d: 9.77 (s,
1H), 7.40 (d, 1H), 7.33 (s, 1H), 7.30 (t, 1H), 7.00 (d, 1H), 5.80–5.60 (m, 14H),
4.90–4.74 (m, 7H), 4.55–4.25 (m, 8H), 3.97 (br, 1H), 3.73–3.21 (m, 39H); 13C
NMR (600 MHz, DMSO-d6) d: 166.02, 157.99, 131.26, 130.27, 120.82, 120.44,
116.11, 103.15, 102.41, 102.13, 82.77, 82.01, 81.93, 81.82, 81.67, 73.63, 73.49,
73.41, 73.36, 72.87, 72.73, 72.62, 72.51, 69.34, 64.32, 60.38, 60.18, 60.09; ESI-
MS: m/z = 1277 ([M+Na]+). Compound 7: TLC: Rf = 0.45 (n-BuOH/EtOH/
H2O = 5:4:3, v/v); 1H NMR (600 MHz, DMSO-d6) d: 9.63 (s, 1H), 7.20 (d, 1H
ArH), 7.07 (t, 1H), 6.98(d, 1H), 5.80–5.60 (m, 14H), 4.90–4.75 (m, 7H), 4.52 (d,
1H), 4.46 (t, 1H), 4.44–4.38 (m, 4H), 4.31 (t, 1H), 4.26 (dd, 1H), 3.94 (br, 1H),
3.74–3.25 (m, 39H), 2.26 (s, 3H); 13C NMR (600 MHz, DMSO-d6) d: 167.64,
156.29, 131.61, 126.53, 125.58, 120.98, 118.54, 103.10, 102.46, 102.37, 102.07,
82.91, 82.10, 82.02, 81.97, 81.68, 81.59, 73.64, 73.48, 73.37, 73.32, 72.87, 72.75,
72.68, 72.54, 72.50, 69.43, 64.35, 60.37, 60.12, 60.01, 13.09; ESI-MS: m/
z = 1291 ([M+Na]+).Compound 8: TLC: Rf = 0.47 (n-BuOH/EtOH/H2O = 5:4:3, v/
v); 1H NMR (600 MHz, DMSO-d6): d: 9.68 (s, 1H), 7.37 (d, 1H), 7.32 (t, 1H), 7.18
(d, 1H), 5.80–5.60 (m, 14H), 4.90–4.75 (m, 7H), 4.55–4.25 (m, 8H), 3.95 (br, 1H),
3.73–3.20 (m, 39H), 2.15 (s, 3H); 13C NMR (600 MHz, DMSO-d6) d: 166.09,
155.83, 131.18, 130.60, 128.63, 120.51, 115.31, 103.15, 102.42, 102.14, 82.77,
82.07, 82.02, 81.93, 81.88, 81.68, 73.63, 73.50, 73.43, 73.38, 72.87, 72.74, 72.62,
72.52, 72.46, 69.38, 64.09, 60.38, 60.30, 60.20, 60.11, 16.58; ESI-MS: m/z = 1291
([M+Na]+). Compound 9: TLC: Rf = 0.52 (n-BuOH/EtOH/H2O = 5:4:3, v/v); 1H
NMR (600 MHz, DMSO-d6) d: 7.54 (d, 1H ArH), 7.40 (s, 1H), 7.19 (d, 1H), 5.80–
5.60 (m, 14H), 4.90–4.77 (m, 7H), 4.55 (d, 1H), 4.50–4.26 (m, 7H), 4.08 (dd, 2H),
4.01 (br, 1H), 3.80–3.20 (m, 39H), 1.33 (t, 3H); 13C NMR (600 MHz, DMSO-d6) d:
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7. A series of sensitizer-appended CDs were synthesized by the reactions of
native CD with the corresponding benzoyl chlorides in pyridine and purified
by repeated recrystalization or reversed-phase column. NMR and HR-MS10
studies were performed to confirm the structure of these chiral sensitizing
hosts. The solubility of these hosts were poor in general in pure water, but
were considerably improved by adding 5–50% methanol to the aqueous
solutions.
8. General procedure for photolysis: Aqueous methanol solutions (5 mL) containing
1Z (1.5 mM) and modified cyclodextrin (0.05–0.15 mM, determined by the
solubility) were irradiated at 254 nm in quartz tubes under an argon
atmosphere at temperatures À5 °C by using a ultraviolet lamp (TUV PL-L
60 W) from Philips. Each photolyzed sample was poured into a 10% aqueous
KOH solution (5 mL), and the resulting mixture was extracted with pentane