M. Meiland et al. / Carbohydrate Research 345 (2010) 257–263
263
round bottom flask equipped with a Soxhlet apparatus filled with
molecular sieves (3 Å) and a condenser, the solution was stirred
at reflux for 5 h under argon atmosphere. After removing the sol-
vent under reduced pressure and drying under vacuum sample 2
was obtained (590 mg, 95%). 1H NMR (400 MHz, DMSO-d6): d
7.75 (d, 2H, o-HPBA), 7.45 (t, 1H, p-HPBA), 7.35 (t, 2H, m-HPBA),
5.50 (d, 1H, OH-20), 5.43 (d, 1H, OH-30), 5.15 (d, 1H, OH-3), 4.59
(t, 1H, OH-6), 4.56 (d, 1H, H-10), 4.38 (d, 1H, OH-3), 4.16 (dd, 1H,
H-60a), 4.11 (d, 1H, H-1), 3.94 (t, 1H, H-60b), 3.76 (dd, 1H, H-6a),
3.71 (3H, H-6b/-40/-50), 3.46–3.38 (5H, H-4/-30 + OMe), 3.37–3.26
(2H, H-3/-5), 3.17 (m, 1H, H-20), 3.03 (m, 1H, H-2); 13C NMR
(100.6 MHz, DMSO-d6): d 133.8 (o-C), 130.8 (p-C), 127.4 (m-C),
103.6 (C-1), 103.0 (C-10), 78.9 (C-4), 74.8 (C-5), 74.4 (C-3), 74.3
(C-30), 74.2 (C-40), 73.8 (C-20), 73.2 (C-2), 67.6 (C-50), 63.3 (C-60),
60.0 (C-6), 56.0 (OMe).
added. Under diminished pressure the toluene was removed. The
step was repeated twice with additional toluene (2 ꢀ 10 cm3). Re-
moval of solvents under reduced pressure and drying under vac-
uum yielded sample 4 (125 mg, 93%). 13C NMR (100.6 MHz,
DMSO-d6): d 135.1–127.8 (o-, m-, p-C), 103.0–102.7 (C-1i), 80.2
(C-4i) 78.7 (C-2/-3i-PBA), 75.0–73.0 (C-2i/-3i/-5i), 74.2 (C-3n-PBA),
73.7 (C-4n-PBA), 67.6 (C-5n-PBA), 63.3 (C-6n-PBA), 60.9–60.2 (C-6i).
Acknowledgments
This work was financially supported by ‘Fachagentur
Nachwachsende Rohstoffe e.V.’ (project 22021905). We would like
to thank Dr. Wolfgang Poppitz (Institute of Inorganic and Analyti-
cal Chemistry, Friedrich Schiller University of Jena) for MS mea-
surements. The authors also thank Anja Baumgaertel (Laboratory
of Organic and Macromolecular Chemistry, Friedrich-Schiller-
University Jena) for carrying out the MALDI-TOF MS measurements.
4.4. Synthesis of Me-b-D-clb phenylboronate sample (3)
1
(150 mg, 0.42 mmol) and triphenylboroxole (255 mg,
Supplementary data
0.82 mmol) were dissolved in a mixture of N,N-dimethylformam-
ide (15 cm3) and toluene (35 cm3), and it was proceeded similarly
to preparation of 2 (Soxhlet apparatus filled with molecular sieve
3 Å). Removal of solvents under diminished pressure and drying
under vacuum yielded sample 3 (330 mg, 95%). Compound 3a:
1H NMR (400 MHz, DMSO-d6): d 7.93–7.89 (o-HPBA), 7.42–7.33
(m-, p-HPBA), 5.07 (H-10), 4.87 (OH-6), 4.59 (H-1), 4.35 (H-3),
4.27–3.93 (H-4/-6/-2 + H-30/-60/-40/-20), 3.79 (H-50), 3.61 (H-5),
3.60 (OMe); 13C NMR (100.6 MHz, DMSO-d6): d 133.5–133.0
(o-C), 129.0 (p-C), 127.3–126.9 (m-C), 102.5 (C-1), 102.0 (C-10),
78.6 (C-3), 78.0 (C-30), 77.0 (C-20), 76.7 (C-2), 76.0 (C-4), 74.6
(C-5), 73.9 (C-40), 66.9 (C-50), 63.4 (C-60), 59.1 (C-6), 56.2 (OMe).
Compound 3b: 1H NMR (400 MHz, DMSO-d6): d 7.93–7.89 (o-HPBA),
7.42–7.33 (m-, p-HPBA), 5.12 (H-10), 4.73–4.55 (H-6), 4.62 (H-1),
4.39 (H-3), 4.27–3.93 (H-4/-2 + H-30/-60/-40/-20), 3.84 (H-5), 3.69
(H-50), 3.54 (OMe); 13C NMR (100.6 MHz, DMSO-d6): d 133.5–
133.0 (o-C), 129.0 (p-C), 127.3–126.9 (m-C), 102.5 (C-1), 102.0
(C-10), 78.6 (C-3), 78.0 (C-30), 77.0 (C-20), 76.7 (C-2), 76.0 (C-4), 73.9
(C-40), 73.6 (C-5), 66.9 (C-50), 63.4 (C-60), 60.6 (C-6), 56.0 (OMe).
Supplementary data associated with this article can be found, in
References
1. Lehmann, J.; Redlich, H. G. Kohlenhydrate: Chemie und Biologie, 2nd ed.; Thieme:
Stuttgart and New York, 1996.
2. (a) Majewicz, T. G. U.S. Patent 4,306,061, 1981; Chem. Abstr., 1982, 96, 54146.;
(b) Huybrechts, S.; Detemmerman, A.; De Pooter, J.; Blyweertt, R. E. WO Patent
88 07059, 1988; Chem. Abstr., 1989, 110, 2927.
3. Bishop, M.; Shahid, N.; Yang, J.; Barron, A. R. J. Chem. Soc., Dalton Trans. 2004, 17,
2621–2634.
4. James, T. D.; Phillips, M. D.; Shinkai, S. Boronic Acids in Saccharide Recognition;
RSC: Cambridge, 2006.
5. (a) Norrild, J. C.; Eggert, H. J. Am. Chem. Soc. 1995, 117, 1479–1484; (b) Bielecki,
M.; Eggert, H.; Norrild, J. C. J. Chem. Soc., Perkin Trans. 2 1999, 3, 449–455.
6. Meiland, M.; Heinze, T.; Guenther, W.; Liebert, T. Tetrahedron Lett. 2009, 50,
469–473.
7. Nicholls, M. P.; Paul, P. K. C. Org. Biomol. Chem. 2004, 2, 1334–1441.
8. Kuzuhara, H.; Emoto, S. Agric. Biol. Chem. 1966, 30, 122–125.
9. (a) Hunsen, M.; Long, D. A.; D’Ardenne, C. R.; Smith, A. L. Carbohydr. Res. 2005,
340, 2670–2674; (b) Fairweather, J. K.; McDonough, M. J.; Stick, R. V.; Tilbrook,
D. M. G. Aust. J. Chem. 2004, 57, 197–205.
10. Leeflang, B. R.; Vliegenthart, J. F. G.; Kroon-Batenburg, L. M. J.; van Eijck, B. P.;
Kroon, J. Carbohydr. Res. 1992, 230, 41–61.
11. Robinson, D. S.; Eagles, J.; Self, R. Carbohydr. Res. 1973, 26, 204–207.
12. Ferrier, R. J. Adv. Carbohydr. Chem. Biochem. 1978, 35, 31–80.
13. Liebert, T.; Seifert, M.; Heinze, Th. Macromol. Symp. 2008, 262, 140–149.
4.5. Synthesis of cellodextrin phenylboronate sample (4)
Cellodextrin (100 mg, 0.62 mmol; DPn = 8, DPw = 12) was dis-
solved in dimethylsulfoxide (10 cm3). After heating to 80 °C
triphenylboroxole (35 mg, 0.32 mmol) in toluene (15 cm3) was