6I -[((N -acetyl-S -(p-hydroxycinnamoyl)-L -cysteinyl)amino]-6I -
deoxy-2I,3I -di-O-methyl-hexakis(2II–VII,3II–VII,6II–VII -tri-O-methyl)-
cyclomaltoheptaose (CD-PYP1: 7, 0.5225 g, 70% yield) as a white
foam. Rf 0.18 (EtOAc:MeOH:H2O, 10 : 1 : 1); [a]2D0 +116.0 (c = 1,
CHCl3); Protonated form-CDCl3: 1H NMR (400 MHz, CDCl3): d
Acknowledgements
This work has been supported by the Agence Nationale de la
Recherche (Contrat n◦ 05-BLAN-0188-01). We are grateful to
Cyclolab for a generous gift of b-cyclodextrin.
3
7.50 (d, 1H, JHa-Hb = 15.8 Hz, Hb), 7.36 (d, 2H, J = 8.5 Hz, Hc,
Hd), 6.94–6.88 (m, 1H, CH2NH), 6.84 (d, 2H, 3J = 8.5 Hz, He, Hf),
6.72 (d, 1H, JNH,CH = 7.5 Hz, NHAc), 6.49 (d, 1H, JHa-Hb = 15.8 Hz,
References
Ha), 5.17–5.08 (m, 7H, 7H1I–VII), 4.68–4.63 (m, 1H, AcNHCH),
1 (a) R. D. Vale and R. A. Milligan, Science, 2000, 288, 88–95; (b) J.
Howard, Nature, 1997, 389, 561–567.
2 (a) D. A. Leigh and E. M. Pe´rez, Top. Curr. Chem., 2006, 265, 185–208;
(b) C. A. Schalley, K. Beizai and F. Vo¨gtle, Acc. Chem. Res., 2001, 34,
465–476.
I–VII
3.90–3.73 (m, 14H, 7H5I–VII, 7H6I–VII), 3.73–3.25 (m, 23H, 7H4
,
7H6¢I–VII, 7H3I–VII, CH2S), 3.64, 3.62 (2 ¥ s, 21H, 7(3-OMe)), 3.50,
3.49, 3.48, 3.47 (4 ¥ s, 21H, 7(2-OMe)), 3.44, 3.38, 3.37 (3 ¥ s, 18H,
I
I
6(6-OMe)), 3.22–3.14 (m, 6H, 6H2II–VII), 3.14 (dd, 1H, JH3
=
3 (a) M. J. Frampton and H. L. Anderson, Angew. Chem., Int. Ed., 2007,
46, 1028–1064; (b) H. Tian and Q.-C. Wang, Chem. Soc. Rev., 2006, 35,
361–374; (c) V. Balzani, A. Credi, S. Silvi and M. Venturi, Chem. Soc.
Rev., 2006, 35, 1135–1149; (d) V. Balzani, A. Credi, F. M. Raymo and
J. F. Stoddart, Angew. Chem., Int. Ed., 2000, 39, 3348–3391.
4 R. Ballardini, V. Balzani, A. Credi, M. T. Gandolfi and M. Venturi,
Acc. Chem. Res., 2001, 34, 445–455.
5 S. Yagai and A. Kitamura, Chem. Soc. Rev., 2008, 37, 1520–1529.
6 (a) V. Balzani, M. Clemente-Leo´n, A. Credi, B. Ferrer, M. Venturi,
A. H. Flood and J. F. Stoddart, Proc. Natl. Acad. Sci. U. S. A., 2006,
103, 1178–1183; (b) A. M. Brouwer, C. Frochot, F. G. Gatti, D. A.
Leigh, L. Mottier, F. Paolucci, S. Roffia and G. W. H. Wurpel, Science,
2001, 291, 2124–2128.
–H2
9.7 Hz, JH1
= 3.4 Hz, H2 ), 2.02 (s, 3H, NHCOCH3); 13C NMR
I
I
I
–H2
(100 MHz, CDCl3): d 190.0 (CH2SCO), 171.1 (NHCOCH3), 170.1
(CH2NHCO), 159.9 (ArCq phenol), 142.2 (Cb), 130.8 (Cc, Cd),
125.6 (ArCq), 121.2 (Ca), 116.4 (Ce, Cf), 99.2, 99.2, 99.1, 99.1,
98.9, 98.8, 98.7 (7C1I–VII), 82.3, 82.3, 82.2, 82.2, 82.0, 81.9, 81.9,
81.8, 81.7, 81.7, 81.6, 81.5 (7C2I–VII, 7C3I–VII), 80.6, 80.3, 80.1, 80.1,
79.6 (7C4I–VII), 71.7, 71.5, 71.4, 71.3, 71.3 (7C6I–VII), 71.6, 71.1,
71.0, 70.0 (7C5I–VII), 61.7, 61.6, 61.6, 61.5, 61.5, 61.4 (7(3-OMe)),
59.6, 59.2, 58.8 (6(6-OMe)), 59.1, 58.6, 58.5, 58.5 (7(2-OMe)),
53.9 (AcNHCH), 31.6 (CH2SCO), 23.2 (NHCOCH3); Protonated
form-D2O: 1H NMR (400 MHz, D2O): d 7.60 (d, 2H, 3J = 8.3 Hz,
7 (a) H. Dodziuk, Cyclodextrin and Their Complexes: Chemistry, Analyt-
ical Methods, Applications, Wiley-VCH, Weinheim, 2006; (b) J. Szejtli,
Chem. Rev., 1998, 98, 1743–1753.
3
Hc, Hd), 7.59 (d, 1H, JHa-Hb = 15.0 Hz, Hb), 6.91 (d, 2H, J =
8 M. V. Rekharsky and Y. Inoue, Chem. Rev., 1998, 98, 1875–1917.
8.3 Hz, He, Hf), 6.58 (bd, 1H, JHa-Hb = 15.0 Hz, Ha), 5.28–5.11
(m, 7H, 7H1I–VII), 4.52–4.43 (m, 1H, AcNHCH), 4.17–3.07 (m,
44H, 7H5I–VII, 7H6I–VII, 7H4I–VII, 7H6¢I–VII, 7H3I–VII, CH2S, 7H2I–VII),
3.57, 3.56, 3.53, 3.51 (4 ¥ s, 21H, 7(3-OMe)), 3.50, 3.48, 3.47, 3.45
(4 ¥ s, 21H, 7(2-OMe)), 3.42, 3.40, 3.38, 3.38 (4 ¥ s, 18H, 6(6-
OMe)), 2.08 (s, 3H, NHCOCH3); 13C NMR (100 MHz, D2O): d
187.8 (CH2SCO), 174.3 (NHCOCH3), 173.6 (CH2NHCO), 159.7
(ArCq phenol), 142.6 (Cb), 130.9 (Cc, Cd), 125.4 (ArCq), 120.9 (Ca),
116.5 (Ce, Cf), 99.3, 99.2, 99.0, 98.7, 98.6, 98.4, 97.6 (7C1I–VII), 81.6,
81.5, 81.4, 81.3, 81.0, 80.9, 80.8, 80.6, 80.5 (7C2I–VII, 7C3I–VII), 80.3,
80.2, 80.0, 79.9, 79.8, 79.6, 78.3 (7C4I–VII), 71.4, 71.2, 71.0, 70.9,
70.7 (7C6I–VII, 7C5I–VII), 61.3, 61.1, 60.9, 60.9, 60.8, 60.6, 60.5 (7(3-
OMe)), 59.0, 59.0, 58.8, 58.8, 58.7, 58.6, 58.5, 58.3, 58.3, 58.2
(6(6-OMe), 7(2-OMe)), 54.3 (AcNHCH), 29.2 (CH2SCO), 22.2
(NHCOCH3); Deprotonated form: 1H NMR (400 MHz, D2O,
pH = 10.1): d 7.60 (d, 1H, JHa-Hb = 15.2 Hz, Hb), 7.53 (d, 2H,
3J = 8.0 Hz, Hc, Hd), 6.61 (d, 2H, 3J = 8.0 Hz, He, Hf), 6.37 (bd,
9 For reviews see: (a) G. Wenz, B.-H. Han and A. Muller, Chem. Rev.,
2006, 106, 782–817; (b) A. Harada, A. Hashidzume and Y. Takashima,
Adv. Polym. Sci., 2006, 201, 1–43; (c) A. Harada, Acc. Chem. Res.,
2001, 34, 456–464; (d) S. A. Nepogodiev and J. F. Stoddart, Chem.
Rev., 1998, 98, 1959–1976; (e) G. Wenz, Angew. Chem., Int. Ed. Engl.,
1994, 33, 803–822.
¨
10 For some recent examples see: (a) R. E. Dawson, S. F. Lincoln and
C. J. Easton, Chem. Commun., 2008, 3980–3982; (b) X. Ma, D. Qu,
F. Ji, Q. Wang, L. Zhu, Y. Xu and H. Tian, Chem. Commun., 2007,
1409–1411; (c) L. Zhu, X. Ma, F. Ji, Q. Wang and H. Tian, Chem.–
Eur. J., 2007, 13, 9216–9222; (d) Q.-C. Wang, X. Ma, D.-H. Qu and H.
Tian, Chem.–Eur. J., 2006, 12, 1088–1096; (e) A. G. Cheetham, M. G.
Hutchings, T. D. W. Claridge and H. L. Anderson, Angew. Chem.,
Int. Ed., 2006, 45, 1596–1599; (f) D.-H. Qu, Q.-C. Wang, X. Ma and
H. Tian, Chem.–Eur. J., 2005, 11, 5929–5937; (g) H. Murakami, A.
Kawabuchi, R. Matsumoto, T. Ido and N. Nakashima, J. Am. Chem.
Soc., 2005, 127, 15891–15899; (h) D.-H. Qu, Q.-C. Wang, J. Ren and H.
Tian, Org. Lett., 2004, 6, 2085–2088; (i) Q.-C. Wang, D.-H. Qu, J. Ren,
K. Chen and H. Tian, Angew. Chem., Int. Ed., 2004, 43, 2661–2665;
(j) C. A. Stanier, S. J. Alderman, T. D. W. Claridge and H. L. Anderson,
Angew. Chem., Int. Ed., 2002, 41, 1769–1772.
11 For some recent examples see: (a) D. P. Ferris, Y.-L. Zhao, N. M.
Khashab, H. A. Khatib, J. F. Stoddart and J. I. Zink, J. Am. Chem.
Soc., 2009, 131, 1686–1688; (b) Y.-L. Zhao and J. F. Stoddart, Langmuir,
2009, 25, 8442–8446; (c) Z. Wang, Z. Li and Z. Liu, J. Phys. Chem. C,
2009, 113, 3899–3902; (d) P. V. Jog and M. S. Gin, Org. Lett., 2008, 10,
3693–3696; (e) Y. Liu, Z.-X. Yang and Y. Chen, J. Org. Chem., 2008,
73, 5298–5304; (f) R. Lu, C. Yang, Y. Cao, L. Tong, W. Jiao, T. Wada,
Z. Wang, T. Mori and Y. Inoue, J. Org. Chem., 2008, 73, 7695–7701;
(g) K. Yamauchi, Y. Takashima, A. Hashidzume, H. Yamaguchi and A.
Harada, J. Am. Chem. Soc., 2008, 130, 5024–5025; (h) Y. Inoue, P. Kuad,
Y. Okumura, Y. Takashima, H. Yamaguchi and A. Harada, J. Am.
Chem. Soc., 2007, 129, 6396–6397; (i) I. Tomatsu, A. Hashidzume and
A. Harada, Angew. Chem., Int. Ed., 2006, 45, 4605–4608; (j) R. J.
Coulston, H. Onagi, S. F. Lincoln and C. J. Easton, J. Am. Chem. Soc.,
2006, 128, 14750–14751.
1H, JHa-Hb = 15.2 Hz, Ha), 5.30–5.12 (m, 7H, 7H1I–VII), 4.51–4.43
I–VII
(m, 1H, AcNHCH), 4.13–3.15 (m, 44H, 7H5I–VII, 7H6I–VII, 7H4
,
7H6¢I–VII, 7H3I–VII,CH2S, 7H2I–VII), 3.60, 3.58, 3.56, 3.50 (4 ¥ s, 21H,
7(3-OMe)), 3.49, 3.48, 3.47 (3 ¥ s, 21H, 7(2-OMe)), 3.43, 3.42,
3.39, 3.38 (4 ¥ s, 18H, 6(6-OMe)), 2.09 (s, 3H, NHCOCH3); 13C
NMR (100 MHz, D2O, pH = 10.1): d 188.0 (CH2SCO), 174.6
(NHCOCH3), 173.8 (CH2NHCO), 172.3 (ArCq phenolate), 145.2
(Cb), 131.9 (Cc, Cd), 120.1 (Ce, Cf), 119.4 (ArCq), 115.7 (Ca),
99.8, 99.3, 99.1, 98.8, 98.6, 97.7 (7C1I–VII), 81.7, 81.5, 81.3, 81.1,
81.1, 80.8, 80.5, 80.4, 80.4, 80.1, 79.9, 79.7, 79.6, 79.4, 79.3, 79.2
(7C3I–VII, 7C2I–VII, 7C4I–VII), 71.7, 71.6, 71.4, 71.2, 71.0, 70.9, 70.7
(7C6I–VII, 7C5I–VII), 61.3, 61.1, 60.9, 60.8, 60.6, 60.5 (7(3-OMe)),
59.0, 59.0, 58.8, 58.8, 58.7, 58.6, 58.6, 58.3, 58.3, 58.2 (6(6-OMe),
7(2-OMe)), 54.7 (AcNHCH), 28.8 (CH2SCO), 21.9 (NHCOCH3);
LRMS (FAB+): m/z [M + Na]+ = 1727.8; HRMS (FAB+): m/z
[M + Na]+ calculated for C76H124N2O38SNa 1727.7451, observed
1727.7384.
12 (a) A. Mallick, P. Purkayastha and N. Chattopadhyay, J. Photochem.
Photobiol., C, 2007, 8, 109–127; (b) A. Douhal, Chem. Rev., 2004, 104,
1955–1976; (c) V. Ramamurthy and D. F. Eaton, Acc. Chem. Res., 1988,
21, 300–306.
13 (a) K. Kpegba, M. Murtha and N. Nesnas, Bioorg. Med. Chem. Lett.,
2006, 16, 1523–1526; (b) S. Mun˜oz Botella, M. A. Mart´ın, B. del
Castillo, J. C. Mene´ndez, L. Va´squez and D. A. Lerner, J. Pharm.
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