9188
K. Martina et al. / Tetrahedron Letters 48 (2007) 9185–9189
Polym. Sci. 2006, 201, 1–43; (d) Liu, Y.; Chen, Y. Acc.
salt was dissolved in 15 ml of aq 0.25 N NaOH and stirred
10 min at 90 °C. The solution was cooled down to room
temperature and 80 mg of NaBH4 were added; the mixture
was further cooled down to 0 °C and acidified with 7 ml of
HCl 1 N. Finally 150 ml of acetone was added to
precipitate the desired product.
Chem. Res. 2006, 3, 275–285; (e) Hapiot, F.; Tilloy, S.;
Monflier, E. Chem. Rev. 2006, 106, 767–781; (f) Mother-
well, W. B.; Bingham, M. J.; Six, Y. Tetrahedron 2001, 57,
4663–4686; (g) Breslow, R.; Dong, S. D. Chem. Rev. 1998,
98, 1997–2011; (h) Hedges, A. R. Chem. Rev. 1998, 98,
2035–2044; (i) Uekama, K.; Hirayama, F.; Irie, T. Chem.
Rev. 1998, 98, 2045–2076.
6I-Deoxy-6I-thio-b-CD (4): The general procedure was
followed starting with 2 g (1.55 mmol) of 6I-O-(p-toluene-
sulfonyl)-b-CD and 1.17 g (15.4 mmol) of thiourea. After
20 min irradiation at 100 °C (100 W) 1.23 g of product 4
was obtained (yield 69%). Analytical data were in accor-
dance with reported values.
2. (a) Byun, H.; Zhong, N.; Bittman, R. Org. Synth. 2000, 77,
225–230; (b) Vizitu, D.; Walkinshaw, C. S.; Thatcher, G.
R. J. J. J.Org. Chem. 1997, 62, 8760–8766.
3. (a) Yuan, D.; Tahara, T.; Chen, W.; Okabe, Y.; Yang, C.;
Yagi, Y.; Nogami, Y.; Fukudome, M.; Fujita, K. J. Org.
Chem. 2003, 68, 9456–9466; (b) Teranishi, K. Tetrahedron
2003, 59, 2519–2538; (c) Law, H.; Baussanne, I.; Garcia
Fernandez, J. M.; Defaye, J. Carbohydr. Res. 2003, 451–
453; (d) Rong, D.; D’Souza, V. T. Tetrahedron Lett. 1990,
31, 4275–7278; (e) Murakami, T.; Harata, K.; Morimoto,
S. Tetrahedron Lett. 1987, 28, 321–324.
4. (a) Tian, S.; Forgo, P.; D’Souza, V. T. Tetrahedron Lett.
1996, 37, 8309–8312; (b) Fujita, K.; Nagamura, S.; Imoto,
T.; Koga, T. J. Am. Chem. Soc. 1986, 108, 2030–2034.
5. Cravotto, G.; Cintas, P. Chem. Soc. Rev. 2006, 35, 180–
196.
6A,6D-Dideoxy-6A,6D-dithio-b-CD (6): The general proce-
dure was followed starting with 2 g (1.44 mmol) of 6A,D
-
capped-b-CD (5) and 2 g (28.8 mmol) of thiourea. After
1 h irradiation at 90 °C (100 W) 1.32 g of product 6 was
obtained (yield 79%). Analytical data were in accordance
with reported values.
12. (a) Teranishi, K.; Watanabe, K.; Hisamatsu, M.; Yamada,
T. J. Carbohydr. Chem. 1998, 17, 489–494; (b) Teranishi,
K.; Tanabe, S.; Hisamatsu, M.; Yamada, T. Biosci.
Biotechnol. Biochem. 1998, 62, 1249–1252.
13. Typical procedure for the synthesis of 2I-O-(p-toluenesulfo-
nyl)-CDs: 1 mmol of a-, b- or c-CD was dissolved in 12 ml
of DMF and 0.9 mmol of TsIm with 1 g of powder
molecular sieves 4A were added, After sonication (immer-
sion-horn, 50 W, 20.4 kHz), molecular sieves were
removed by filtration through a CeliteÒ pad and the
filtrate was evaporated to dryness under reduced pressure.
The filtrate was purified by reverse-phase chromatography
with a gradient from water/methanol 95:5 to 25% meth-
anol.
6. Microwaves in Organic Synthesis; Loupy, A., Ed.; Wiley-
VCH: Weinheim, 2006.
7. (a) Trotta, F.; Martina, K.; Robaldo, B.; Barge, A.;
Cravotto, G. J. Inclusion Phenom. 2007, 57, 3–7; (b) Aime,
S.; Gianolio, E.; Palmisano, G.; Robaldo, B.; Barge, A.;
Boffa, L.; Cravotto, G. Org. Biomol. Chem. 2006, 4, 1124–
1130; (c) Cravotto, G.; Bicchi, C.; Tagliapietra, S.; Costa,
L.; Di Carlo, S.; Nervi, C. Chirality 2004, 16, 526–533; (d)
Cravotto, G.; Nano, G. M.; Palmisano, G. J. Carbohydr.
Chem. 2001, 20, 495–501; (e) Siu, M.; Yaylayan, V.;
Belanger, J.; Pare, J. Tetrahedron Lett. 2005, 21, 3737–
3739.
2I-O-(p-Toluenesulfonyl)-a-CD (7a): The general proce-
dure was followed starting with 1 g (1.02 mmol) of a-CD.
Sonication for 2 h gave 406 mg of product (36%).
Analytical data were in accordance with reported values.
2I-O-(p-Toluenesulfonyl)-b-CD (7b): The general proce-
dure was followed starting with 1 g (0.88 mmol) of b-CD.
Sonication for 1 h gave 454 mg of product (40%).
Analytical data were in accordance with reported values.
2I-O-(p-Toluenesulfonyl)-c-CD (7c): the general procedure
was followed starting with 1 g (0.77 mmol) of c-CD.
Sonication for 45 min gave 501 mg of product (46%).
Analytical data were in accordance with reported values.
14. (a) Poon, Y.; Muderawan, I. W.; Ng, S. J. Chrom. A 2006,
1101, 185–197; (b) Muderawan, I. W.; Ong, T. T.; Lee, T.
C.; Young, D. J.; Ching, C. B.; Ng, S. Tetrahedron Lett.
2005, 46, 7905–7907.
8. Yoon, J.; Hong, S.; Martin, K. A.; Czarnik, A. W. J. Org.
Chem. 1995, 60, 2792–2795.
9. 6I-Formyl-b-CD (2): The reaction was carried out under
magnetic stirring in a professional MW oven (MicroS-
YNTH-Milestone), the temperature being monitored with
a fibre-optic thermometer. 1 g (0.77 mmol) of 6I-O-(p-
toluenesulfonyl)-b-CD and 300 ll of collidine were dis-
solved in 10 ml DMSO. The mixture was irradiated with
MW (110 W) for 15 min at 135 °C. 100 ml of acetone was
then added; the precipitate was filtered off and recrystal-
lized from water/acetone 1/15, yielding 600 mg of pure
6Iformyl-b-CD (2) (yield 68%). To confirm the identity of
product 2, the dimethylhydrazone was synthesized as
follows. 1 ml of 1,1-dimethylhydrazine was added to
200 mg of 6I-formyl-b-CD; the solution was stirred at
room temperature for 12 h before it was evaporated to
dryness. 5 ml of acetone was added and the product
filtered off. 170 mg of 6I-deoxy-6I-(N,N-dimethyl)hydra-
zone-b-CD was recovered and characterized. Analytical
data were in accordance with reported values.
15. Typical procedure for the synthesis of 3I-azido-3I-deoxy-
altro-CD: The reaction was carried out under magnetic
stirring in a professional MW oven (MicroSYNTH-
Milestone), the temperature being monitored with a
fibre-optic thermometer. 0.1 mmol of 2I-O-(p-toluenesul-
fonyl)-CD derivative and 0.5 mmol of NaN3 were dis-
solved in 1 ml of H2O. The mixture was irradiated with
MW (100 W) at 100 °C till complete conversion of the
starting material. The mixture was evaporated to dryness
under reduced pressure. The product was purified by
chromatography on reverse phase with a gradient from
water to 10% methanol.
10. Yuan, D.; Immel, S.; Koga, K.; Yamaguchi, M.; Fujita,
K. Chem. Eur. J. 2003, 9, 3501–3506.
11. General procedure for the synthesis of 6I-deoxy-6I-thio-b-
CD (4) and 6A,6D-dideoxy-6A, 6D-dithio-b-CD (6): The
reaction was carried out under magnetic stirring in a
professional MW oven (MicroSYNTH-Milestone), the
temperature being monitored with a fibre-optic thermom-
eter. 1.5 mmol of 6I-O-(p-toluenesulfonyl)-b-CD (1) or of
6A,D-capped-b-CD (5) were dissolved in 16 ml of DMF
and thiourea was added. The mixture was irradiated with
MW (see detail in the synthesis of products 4 and 6). The
solvent was partially evaporated and 100 ml of acetone
was added to precipitate the product. The thiouronium
3I-Deoxy-3I-azido-altro-a-CD (8a): The general procedure
was followed starting with 100 mg of 2I-O-(p-toluenesul-
fonyl)-a-CD. The mixture was irradiated for 1 h, then
20 ll of acetic acid was added and irradiation was resumed
(100 W) at 100 °C for 1 h to give 110 mg of 8a (yield 95%)
as a white solid. 1H NMR (300 MHz, D2O) d: 5.12 (d,
J = 3.9 Hz 1H), 5.08–5.01 (m, 4H), 4.92 (d, J = 6.6 Hz,
1H), 4.30–4.22 (m, 1H), 4.10 (t, J = about 3.6 Hz, 1H),
4.05–3.72 (m, 23H), 3.70–3.49 (m, 11H). 13C NMR (D2O