3270
A. V. Pukin, H. Zuilhof
LETTER
Gilbert, M.; Pieters, R. J.; Zuilhof, H.; Visser, G. M.;
Turnbull, W. B. ChemBioChem 2009, 10, 329. (b) Pukin,
A. V.; Branderhorst, H. M.; Sisu, C.; Weijers, C.; Gilbert,
M.; Liskamp, R. M. J.; Visser, G. M.; Zuilhof, H.; Pieters,
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Carbohydr. Res. 2005, 340, 1547. (b) Milkereit, G.; Gerber,
S.; Brandenburg, K.; Morr, M.; Vill, V. Chem. Phys. Lipids
2005, 135, 1. (c) Katsuraya, K.; Ikushima, N.; Takahashi,
N.; Shoji, T.; Nakashima, H.; Yamamoto, N.; Yoshida, T.;
Uryu, T. Carbohydr. Res. 1994, 260, 51. (d) Dahmen, J.;
Frejd, T.; Gronberg, G.; Lave, T.; Magnusson, G.; Noori, G.
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(21) Barrientos, A. G.; de la Fuente, J. M.; Rojas, T. C.;
Fernandez, A.; Penades, S. Chem. Eur. J. 2003, 9, 1909.
(22) Data for 2b: 1H NMR (400 MHz, C6D6): d = 6.52 (d, J = 3.8
Hz, 1 H), 5.82 (t, J = 9.8 Hz, 1 H), 5.28 (t, J = 9.9 Hz, 1 H),
5.23 (dd, J = 10.0, 3.8 Hz, 1 H), 4.21–4.28 (m, 2 H), 4.08–
4.14 (m, 1 H), 1.16 (s, 9 H), 1.12 (s, 9 H), 1.12 (s, 9 H), 1.09
(s, 9 H), 1.08 (s, 9 H); 13C NMR (100 MHz, C6D6): d = 177.8,
177.2, 176.9, 176.8, 175.9, 89.5, 71.4, 70.5, 70.3, 68.5, 62.4,
39.4, 39.3, 39.2 (2 C, peaks overlap), 39.1, 27.7, 27.6, 27.5,
27.5, 27.4.
(15) (a) Seebacher, W.; Haslinger, E.; Weis, R. Monatsh. Chem.
2001, 132, 839. (b) Magnus, V.; Vikictopic, D.; Iskric, S.;
Kveder, S. Carbohydr. Res. 1983, 114, 209. (c) Wulff, G.;
Schmidt, W. Carbohydr. Res. 1977, 53, 33.
(23) Typical glycosylation procedure: To a solution of lactose
octapivalate 1 (1 g, 0.99 mmol) and 8-chlorooctan-1-ol (4b;
243 mL, 1.48 mmol) in anhydrous toluene (10 mL), was
added ZnCl2 (0.2 g, 1.48 mmol, which was dried in vacuo at
120 °C for at least 1 h prior to use) and the resulting
suspension was stirred at 70 °C for 5 h. After cooling, the
reaction mixture was diluted with EtOAc (10 mL), and solid
NaHCO3 (2 g) and H2O (0.5 mL) were added portion-wise
with stirring. After the formation of gas stopped (~20 min),
the solution was filtered over Hyflo. The precipitate was
washed thoroughly with EtOAc. The combined organic
phase was evaporated in vacuo and the residue was purified
by silica gel column chromatography (EtOAc–petroleum
ether, 1:7) to give 8-chlorooctyl lactoside 5b (0.97 g, 0.9
mmol, 91%) as a white foam. 1H NMR (400 MHz, CDCl3):
d = 5.36 (d, J = 2.3 Hz, 1 H), 5.18 (t, J = 9.5 Hz, 1 H), 5.09
(dd, J = 10.5, 8.0 Hz, 1 H), 4.96 (dd, J = 10.5, 3.5 Hz, 1 H),
4.79 (dd, J = 9.7, 7.9 Hz, 1 H), 4.50 (d, J = 7.8 Hz, 1 H),
4.47–4.56 (m, 1 H), 4.44 (d, J = 8.0 Hz, 1 H), 4.18 (dd,
J = 12.0, 5.0 Hz, 1 H), 4.04–4.11 (m, 1 H), 3.95–4.03 (m, 1
H), 3.88–3.94 (m, 1 H), 3.85 (t, J = 9.5 Hz, 1 H), 3.67–3.75
(m, 1 H), 3.47 (t, J = 6.8 Hz, 2 H), 3.44–3.53 (m, 1 H), 3.33–
3.41 (m, 1 H), 1.65–1.75 (m, 2 H), 1.48 (t, J = 6.4 Hz, 2 H),
1.32–1.42 (m, 2 H), 1.22–1.28 (m, 6 H), 1.21 (s, 9 H), 1.19
(s, 9 H), 1.17 (s, 9 H), 1.15 (s, 9 H), 1.11 (s, 9 H), 1.11 (s, 9
H), 1.05 (s, 9 H); 13C NMR (101 MHz, CDCl3): d = 177.7,
177.5, 177.2, 177.0, 176.7, 176.5, 175.9, 100.7, 100.0, 73.7,
73.3, 71.7, 71.6, 71.4, 71.3, 69.6, 68.8, 66.8, 61.7, 61.3, 44.9,
38.9–38.6 (7 C, peaks overlap), 32.5, 29.4, 29.0, 28.7, 27.3,
27.2, 27.1, 27.0 (3 C, peaks overlap), 26.9, 26.7, 25.8.
(24) (a) Lemieux, R. U. Can. J. Chem.-Rev. Can. Chim. 1951, 29,
1079. (b) Lemieux, R. U.; Brice, C. Can. J. Chem.-Rev. Can.
Chim. 1955, 33, 109.
(16) (a) Murakami, T.; Sato, Y.; Shibakami, M. Carbohydr. Res.
2008, 343, 1297. (b) Yao, Q. J.; Song, J.; Xia, C. F.; Zhang,
W. P.; Wang, P. G. Org. Lett. 2006, 8, 911. (c) Rai, A. N.;
Basu, A. J. Org. Chem. 2005, 70, 8228. (d) Takeda, Y.;
Horito, S. Carbohydr. Res. 2005, 340, 211. (e) Yamamura,
T.; Hada, N.; Kaburaki, A.; Yamano, K.; Takeda, T.
Carbohydr. Res. 2004, 339, 2749. (f) Compostella, F.;
Franchini, L.; De Libero, G.; Palmisano, G.; Ronchetti, F.;
Panza, L. Tetrahedron 2002, 58, 8703. (g) Lindberg, J.;
Svensson, S. C. T.; Pahlsson, P.; Konradsson, P.
Tetrahedron 2002, 58, 5109. (h) Gege, C.; Geyer, A.;
Schmidt, R. R. Chem. Eur. J. 2002, 8, 2454. (i) Castro-
Palomino, J. C.; Simon, B.; Speer, O.; Leist, M.; Schmidt,
R. R. Chem. Eur. J. 2001, 7, 2178. (j) Nicolaou, K. C.; Li,
J.; Zenke, G. Helv. Chim. Acta 2000, 83, 1977.
(17) Presser, A.; Kunert, O.; Potschger, I. Monatsh. Chem. 2006,
137, 365.
(18) (a) Pukin, A. V.; Weijers, C.; van Lagen, B.; Wechselberger,
R.; Sun, B.; Gilbert, M.; Karwaski, M. F.; Florack, D. E. A.;
Jacobs, B. C.; Tio-Gillen, A. P.; van Belkum, A.; Endtz,
H. P.; Visser, G. M.; Zuilhof, H. Carbohydr. Res. 2008, 343,
636. (b) Sun, B.; Pukin, A. V.; Visser, G. M.; Zuilhof, H.
Tetrahedron Lett. 2006, 47, 7371. (c) de Smet, L.; Pukin,
A. V.; Stork, G. A.; de Vos, C. H. R.; Visser, G. M.; Zuilhof,
H.; Sudholter, E. J. R. Carbohydr. Res. 2004, 339, 2599.
(19) (a) de Smet, L.; Pukin, A. V.; Sun, Q. Y.; Eves, B. J.;
Lopinski, G. P.; Visser, G. M.; Zuilhof, H.; Sudholter, E. J.
R. Appl. Surf. Sci. 2005, 252, 24. (b) de Smet, L. C. P. M.;
Stork, G. A.; Hurenkarnp, G. H. F.; Sun, Q. Y.; Topal, H.;
Vronen, P. J. E.; Sieval, A. B.; Wright, A.; Visser, G. M.;
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(20) (a) Sisu, C.; Baron, A. J.; Branderhorst, H. M.; Connel,
S. D.; Weijers, C.; de Vries, R.; Hayes, E. D.; Pukin, A. V.;
Synlett 2009, No. 20, 3267–3270 © Thieme Stuttgart · New York