3
138
S. N. Podyachev et al. / Tetrahedron Letters 53 (2012) 3135–3139
2 2 3
Scheme 2. The mechanism of hydrolysis of tetraester 2 in THF/H O in the presence of Cs CO .
2
2
2
2
2
1. (a) Iwamoto, K.; Shinkai, S. J. Org. Chem. 1992, 57, 7066; (b) Creaven, B. S.;
Donlon, D. F.; McGinley, J. Coord. Chem. Rev. 2009, 253, 893.
2. (a) Ikeda, A.; Suzuki, Y.; Yoshimura, M.; Shinkai, S. Tetrahedron 1998, 54, 2497;
References and notes
1.
2.
3.
4.
5.
Supramolecular Chemistry; Steed, J. W., Atwood, J. L., Eds.; Wiley: Chichester,
UK, 2000.
Nanomaterials and Nanochemistry; Bréchignac, C., Houdy, P., Lahmani, M., Eds.;
Springer: Berlin, Heidelberg, 2007; p 339.
(
b) Budka, J.; Lhotak, P.; Michlova, V.; Stibor, I. Tetrahedron Lett. 2001, 42, 1583.
3. Cacciapaglia, B.; Casnati, A.; Mandolini, L.; Schiavone, S.; Ungaro, R. J. Chem.
Soc., Perkin Trans. 2 1993, 369.
4. Iki, N.; Narumi, F.; Fujimoto, T.; Morohashi, N.; Miyano, S. J. Chem. Soc., Perkin
Trans. 2 1998, 2745.
(a) Gade, L. H. Chem. Commun. 2000, 173; (b) Handy, S. T. Curr. Org. Chem. 2000,
4
, 363; (c) Tzadka, E.; Goldberg, I.; Vigalok, A. Chem. Commun. 2009, 2041.
Bencini, C.; Benell, A.; Caneschi, R. L.; Carlin, A. D.; Gatteschi, D. J. Am. Chem. Soc.
985, 107, 8128.
5. Procedure for the synthesis of 3a (3b): 5.0 g (4.7 mmol) of tetraester 2a [5 g
(
6 mmol) of 2b] and 18.3 g (56 mmol) of Cs
suspended in 200 ml of THF and refluxed for 1 h under an argon atmosphere.
Next, 10 ml (5 vol%) of H O was added and the reaction mixture was stirred
2 3
CO [23.4 g (72 mmol) for 3b] were
1
(a) Barja, B.; Baggio, R.; Garland, M. T.; Aramendia, P. F.; Peña, O.; Perec, M.
Inorg. Chim. Acta 2003, 346, 187; (b) Wolcan, E.; Villata, L.; Capparelli, A. L.;
Feliz, M. R. Photochem. Photobiol. Sci. 2004, 3, 322.
2
vigorously at reflux over 3 d. The first portion 3.86 g (9.1 g) of the precipitate
formed [caesium salt of the product 3a (3b)] was filtered from the hot reaction
mixture and the reaction was allowed to continue for a further 4 d (2 d). The
second crop 2.46 g (1.7 g) of the precipitate was collected and combined with
the first. After treatment of the obtained white solid with a mixture of
6
7
.
.
Otsuki, J.; Akasaka, T.; Araki, K. Coord. Chem. Rev. 2008, 252, 32.
(a) Gutsche, C. D. In Calixarenes: An Introduction, 2nd ed.; The Royal Society of
Chemistry: Cambridge, 2008; (b)Calixarenes 2001; Asfary, Z., Böhmer, V.,
Harrowfield, J., Vicens, J., Eds.; Kluwer Academic Publishers: Dordrecht, The
Netherlands, 2001.
concentrated HCl (50 ml) and H
with CH Cl
(2 Â 50 ml). The organic layer was separated, washed with H
until neutral pH and dried over MgSO . After filtration and removal of the
2
O (50 ml), the resulting solution was extracted
2
2
2
O
8
.
.
(a) Podyachev, S. N.; Sudakova, S. N.; Syakaev, V. V.; Galiev, A. K.; Shagidullin, R.
R.; Konovalov, A. I. Supramol. Chem. 2008, 20, 479; (b) Podyachev, S. N.;
Burmakina, N. E.; Sudakova, S. N.; Syakaev, V. V.; Konovalov, A. I. Supramol.
Chem. 2010, 22, 339.
(a) Hosseini, M. W. Cryst. Eng. Comm. 2004, 6, 318; (b) Hosseini, M. W. Acc.
Chem. Res. 2005, 38, 313; (c) Wuest, J. D. Chem. Commun. 2005, 5830.
4
solvent under reduced pressure the target product 3.36 g (3.2 g) was obtained
as a white powder in 71% (68%) yield.
2
2
2
6. Characterization
data
of
5,11,17,23-tetra-tert-butyl-25,27-
9
di[ethoxycarbonyl)methoxy]-26,28-di[(hydroxycarbonyl)methoxy]-2,8,14,20-
1
tetrathiacalix[4]arene (3a): Mp: 277 °C. H NMR (600.13 MHz, CDCl
3
) for the
), 1.25 (s, 18H, t-Bu),
O), 7.39 (s, 4H, ArH); for the
carboxylic acid containing fragment: d 1.27 (s, 18H, t-Bu), 4.66 (s, 4H, CH O),
) for the ester-containing
, t-Bu), 34.5 (C, t-Bu), 60.8 (CH ), 66.6 (CH O),
28.2 (C(3)Ar), 130.4 (C(2)Ar), 148.7 (C(1)Ar), 155.7 (C(4)Ar), 167.5 (C@O); for
the carboxylic acid containing fragment: d 31.1 (CH , t-Bu), 34.6 (C, t-Bu), 66.6
O), 127.6 (C(3)Ar), 131.1 (C(2)Ar), 148.7 (C(1)Ar), 154.1 (C(4)Ar), 168.0
1
1
1
0. (a) Kovbasyuk, L.; Krämer, R. Chem. Rev. 2004, 104, 3161; (b) Ni, X.-I.;
Tomiyasu, H.; Shimizu, T.; Pérez-Casas, C.; Xi, Z.; Yamato, T. J. Incl. Phenom.
Macrocycl. Chem. 2010, 68, 99.
3
ester-containing fragment: d 1.24 (t, J = 7.43 Hz, 6H, CH
3
.17 (q, 3J = 7.4 Hz, 4H, CH
4
2 2
), 4.59 (s, 4H, CH
2
1. (a) Shinkai, S.; Fujimoto, K.; Otsuka, T.; Ammon, H. L. J. Org. Chem. 1992, 57,
13
7
.47 (s, 4H, ArH). C NMR (125.86 MHz, CDCl
3
1
516; (b) Lugtenberg, R. J. W.; Egberink, R. J. M.; Engbersen, J. F. J.; Reinhoudt,
fragment: d 14.3 (CH ), 31.1 (CH
3
3
2
2
D. N. J. Chem. Soc., Perkin Trans. 2 1997, 1353.
1
2. (a) Verboom, W.; Datta, S.; Asfari, Z.; Harkema, S.; Reinhoudt, D. N. J. Org. Chem.
3
1992, 57, 5394; (b) Nayak, S. K.; Choudhary, M. K. Tetrahedron Lett. 2012, 53,
141; (c) Lazar, A. N.; Dupont, N.; Navaza, A.; Coleman, A. W. Chem. Commun.
2006, 1076.
(
(
CH
C@O). MALDI-TOF MS: m/z 1031 [M+Na] . Anal. Calcd for C52
1.88, H 6.39, S 12.71; found: C 61.87, H6.27, S 12.41.
7. Characterization data of 25,27-di[(ethoxycarbonyl)methoxy]-26,28-
di[hydroxycarbonyl)methoxy]-2,8,14,20-tetrathiacalix[4]arene (3b): Mp:
) for the ester-containing fragment: d 1.25
2
+
64 12 4
H O S : C
6
1
3. Casnati, A.; Pochini, A.; Ungaro, R.; Ugozzoli, F.; Arnaud, F.; Fanni, S.; Schwing, M.-
J.; Egberink, R. J. M.; Jong, F. D.; Reinhoudt, D. N. J. Am. Chem. Soc. 1995, 117, 2767.
4. (a) Iki, N.; Narumi, F.; Fujimoto, T.; Morohashi, N.; Miyano, S. J. Chem. Soc.,
Perkin Trans. 2 1998, 2745; (b) Lhotak, P.; Sykora, J. Collect Czech Chem.
Commun. 2000, 65, 757; (c) Lhotak, P. Eur. J. Org. Chem. 2004, 1675.
1
1
2
27 °C. H NMR (600 MHz, CDCl
3
3
3
(
t, J = 7.3 Hz, 6H, CH
3
), 4.19 (q, 3J = 7.2 Hz, 4H, CH
2 2
), 4.65 (s, 4H, CH O), 6.96 (t,
3
J = 7.3 Hz, 2H, H(4)Ar), 7.46 (d, J = 7.3 Hz, 4H, H(3)Ar); for the carboxylic acid
1
1
5. (a) Patai, S., Ed. The Chemistry of Carboxylic Acids and Esters, London, 1969.;
3
containing fragment: 4.75 (s, 4H, CH
H, ArH), 7.50 (d, J = 7.3 Hz, 4H, ArH’). C NMR (125.9 MHz, CDCl
ester-containing fragment: d 14.3 (CH ), 61.1 (CH ), 66.4 (CH O), 125.2
C(3)Ar), 129.0 (C(1)Ar), 134.6 (C(2)Ar), 158.8 (C(4)Ar), 168.1 (C@O); for the
carboxylic acid containing fragment: d 67.7 (CH O), 125.2 (C(3)Ar), 128.5
C(1)Ar), 135.0 (C(2)Ar), 157.1 (C(4)Ar), 169.0 (C@O). MALDI-TOF MS: m/z 807
2
O), 6.20 (br s, 2H, OH), 6.95 (t, J = 7.3 Hz,
(
b) Patai, S., Ed. The Chemistry of Acid Derivatives, New York, 1979.
6. (a) Ungaro, R.; Pochini, A.; Andreetti, G. D. J. Incl. Phenom. Macrocycl. Chem.
984, 2, 199; (b) Arnaud-Neu, F.; Collins, E. M.; Deasy, M.; Ferguson, G.; Harris,
13
2
3
) for the
3
2
2
1
(
S. J.; Kaitner, B.; Lough, A. J.; McKervey, M. A.; Marques, E.; Ruhl, B. L.; Schwing-
Weill, M. J.; Seward, E. M. J. Am. Chem. Soc. 1989, 111, 8681.
2
(
[
1
1
7. (a) Iki, N.; Morohashi, N.; Narumi, F.; Fujimoto, T.; Suzuki, T.; Miyano, S.
Tetrahedron Lett. 1999, 40, 7337; (b) Akdas, H.; Jaunky, W.; Graf, E.; Hosseini, M.
W.; De Cian, A.; Fischer, J. Tetrahedron Lett. 2000, 41, 3601.
8. (a) Böhmer, V.; Vogt, W.; Harris, S. J.; Leonard, R. G.; Collins, E. M.; Deasy, M.;
McKervey, M. A.; Owens, M. J. Chem. Soc., Perkin Trans. 1 1990, 431; (b)
Steemers, F. J.; Verboom, W.; Reinhoudt, D. N.; Van der Tol, E. B.; Verhoeven, J.
W. J. Am. Chem. Soc. 1995, 117, 9408; (c) Steemers, F. J.; Meuris, H. G.; Verboom,
W.; Reinhoudt, D. N. J. Org. Chem. 1997, 62, 4229.
+
32 12 4
M+Na] . Anal. Calcd for C36H O S : C 55.09, H 4.11, S 16.34; found: C 55.44,
H 3.72, S 16.18.
8. Price, W. S. NMR Studies of Translational Motion; Cambridge University Press,
009. 393.
2
29. Fujii, Y.; Yamada, H.; Mizuta, M. J. Phys. Chem. 1988, 92, 6768.
+
30. The X-ray diffraction data for compounds 3a, 3aÁ2Cs 2MeOH and 3b (CCDC
839353, 839354 and 839355, respectively) were collected on a Bruker Smart
APEX II CCD diffractometer in
monochromated Mo K (k = 0.71073 Å) radiation at 296(2) K.
1. Crystallographic data for 3a: O, M = 1027.29, monoclinic,
ÁH
a = 10.571(2) Å, b = 28.163(5) Å, c = 18.826(4) Å,
V = 5477(2) Å , T = 296(2) K, space group C2/c, Z = 4,
x and u-scan modes using graphite
1
2
9. Arnaud-Neu, F.; Barrett, J. G.; Harris, S. J.; Owens, M.; McKeney, M. A.; Schwing-
Weillt, M.-J.; Schwinté, P. Inorg. Chem. 1993, 32, 2644.
0. Yamato, T.; Pérez-Casas, C.; Yoshizawa, A.; Rahman, S.; Elsegood, M. R. J.;
Redshaw, C. J. Incl. Phenom. Macrocycl. Chem. 2009, 63, 301.
a
3
C
52
H
64
O
S
12 4
2
b = 102.265(2)°,
= 0.233 mm , 29,753
3
À1
l