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4.32 (m, 1 H), 4.24–4.21 (m, 1 H), 4.15–4.12 (m, 1 H), 2.07 (s, 3 H),
1.98 (s, 3 H), 1.94 (s, 3 H), 0.85 (s, 9 H), 0.02 (s, 3 H), 0.00 (s, 3 H).
HRMS (ESI): m/z [M + Na]+ calcd for C26H35BrNaO17: 721.0955;
found: 721.0957.
13C NMR (100 MHz, CDCl3): δ = 170.3, 170.2, 169.7, 91.9, 71.2,
70.3, 69.1, 66.6, 62.6, 25.8, 20.8, 20.7, 18.4, –5.4, –5.5.
HRMS (ESI): m/z [M + Na]+ calcd for C18H31BrNaO8Si: 505.0869;
2,3,6,2′,3′,4′,6′-Hepta-O-acetyl-α-D-cellobiosyl Bromide (2i)18
20
White solid; yield: 628 mg (90%); mp 186 °C; [α]D +96 (c 1.0,
CHCl3); Rf = 0.33 (PE–EtOAc, 1:1).
IR (KBr): 3469, 1745, 1434, 1372, 1229, 1047, 908 cm–1.
found: 505.0865.
1H NMR (400 MHz, CDCl3): δ = 6.53 (d, J = 4.0 Hz, 1 H), 5.53 (dd,
J = 9.6, 10.0 Hz, 1 H), 5.13 (dd, J = 9.2, 10.0 Hz, 1 H), 5.08 (dd,
J = 9.6, 10.0 Hz, 1 H), 4.94 (dd, J = 8.8, 10.0 Hz, 1 H), 4.77 (dd,
J = 4.0, 10.0 Hz, 1 H), 4.56–4.52 (m, 2 H), 4.38 (dd, J = 4.4, 12.0
Hz, 1 H), 4.21–4.15 (m, 2 H), 4.04 (dd, J = 2.0, 12.0 Hz, 1 H), 3.84
(t, J = 9.6 Hz, 1 H), 3.68 (ddd, J = 2.0, 4.0, 9.6 Hz, 1 H), 2.15 (s, 6
H), 2.10 (s, 3 H), 2.05 (s, 3 H), 2.02 (s, 6 H), 1.99 (s, 3 H).
13C NMR (100 MHz, CDCl3): δ = 170.4, 170.2, 170.0, 169.9, 169.2,
168.9, 100.5, 86.4, 75.1, 72.9, 72.8, 72.6, 71.9, 71.5, 70.7, 69.3,
67.7, 61.5, 60.8, 20.7, 20.6, 20.5.
2,4,6-Tri-O-acetyl-3-O-benzyl-α-D-glucopyranosyl Bromide
(2e)
20
Colorless oil; yield: 403 mg (88%); [α]D +132 (c 0.5, CHCl3);
Rf = 0.46 (PE– EtOAc, 3:1).
IR (thin film): 3379, 2907, 2859, 1728, 892 cm–1.
1H NMR (400 MHz, CDCl3): δ = 7.36–7.25 (m, 5 H), 6.64 (d, J =
3.6 Hz, 1 H), 5.18 (t, J = 10.0 Hz, 1 H), 4.78–4.73 (m, 2 H), 4.63 (m,
1 H), 4.26 (dd, J = 4.4, 12.8 Hz, 1 H), 4.19–4.16 (m, 1 H), 4.10–4.04
(m, 2 H), 2.08 (s, 6 H), 1.96 (s, 3 H).
13C NMR (100 MHz, CDCl3): δ = 170.4, 169.6, 169.1, 137.7, 128.3,
127.8, 127.5, 87.9, 75.0, 72.9, 72.5, 68.0, 61.1, 20.1, 20.0.
HRMS (ESI): m/z [M + Na]+ calcd for C19H23BrO8Na: 481.0474;
HRMS (ESI): m/z [M + Na]+ calcd for C26H35BrNaO17: 721.0955;
found: 721.0955.
found: 481.0477.
2,3,6,2′,3′,4′,6′-Hepta-O-acetyl-α-D-melibiosyl Bromide (2j)
White solid; yield: 607 mg (87%); mp 133 °C; [α]D20 +105.3 (c 0.5,
CHCl3); Rf = 0.35 (PE–EtOAc, 1:1).
IR (KBr): 3411, 2896, 1737, 1427, 1364, 1219, 1169, 1038 cm–1.
2,3,4,6-Tetra-O-acetyl-α-D-galactopyranosyl Bromide (2f)15
White solid; yield: 353 mg (86%); mp 86 °C; [α]D +216 (c 1.0,
CHCl3); Rf = 0.70 (PE– EtOAc, 1:1).
20
1H NMR (400 MHz, CDCl3): δ = 6.60 (d, J = 4.0 Hz, 1 H), 5.56 (t,
J = 9.6 Hz, 1 H), 5.47 (m, 1 H), 5.35 (m, 1 H), 5.32 (dd, J = 5.2, 11.2
Hz, 1 H), 5.20–5.17 (m, 1 H), 5.10 (dd, J = 10.0, 11.2 Hz, 1 H), 4.80
(dd, J = 4.0, 9.6 Hz, 1 H), 4.20 (m, 1 H), 4.16–4.08 (m, 1 H), 4.07–
4.05 (m, 2 H), 3.79–3.75 (m, 1 H), 3.65–3.62 (m, 1 H), 2.14 (s, 3 H),
2.13 (s, 3 H), 2.11 (s, 3 H), 2.07 (s, 3 H), 2.05 (s, 3 H), 2.04 (s, 3 H),
1.99 (s, 3 H).
13C NMR (100 MHz, CDCl3): δ = 170.4, 170.2, 169.7, 169.2, 96.1,
86.4, 72.8, 70.5, 70.1, 67.9, 66.3, 65.3, 61.5, 20.7, 20.5.
HRMS (ESI): m/z [M + Na]+ calcd for C26H35Br O17Na: 721.0955;
found: 721.0954.
IR (thin film): 3422, 1745, 1378, 1249, 1053, 901 cm–1.
1H NMR (400 MHz, CDCl3): δ = 6.71 (d, J = 4.0 Hz, 1 H), 5.52–
5.46 (m, 1 H), 5.40 (dd, J = 3.2, 10.8 Hz, 1 H), 5.05 (dd, J = 4.0,
10.8 Hz, 1 H), 4.51–4.48 (m, 1 H), 4.19 (dd, J = 6.4, 11.8 Hz, 1 H),
4.11 (dd, J = 6.4, 11.2 Hz, 1 H), 2.16 (s, 3 H), 2.12 (s, 3 H), 2.07 (s,
3 H), 2.01 (s, 3 H).
13C NMR (100 MHz, CDCl3): δ = 170.1, 169.8, 169.7, 169.5, 88.0,
70.9, 67.8, 67.6, 66.8, 60.6, 20.5, 20.4, 20.3, 20.0.
HRMS (ESI): m/z [M + Na]+ calcd for C14H19BrNaO9: 433.0110;
found: 433.0112.
2,3,6,2′,3′,4′,6′-Hepta-O-acetyl-α-D-maltosyl bromide (2g)16
20
White solid; yield: 642 mg (92%); mp 83 °C; [α]D +107 (c 1.0,
CHCl3); Rf = 0.32 (PE–EtOAc, 1:1).
Acknowledgment
IR (KBr): 3426, 2971, 1749, 1376, 1230 cm–1.
This work was financially supported by the Fundamental Research
Funds for Lanzhou University (lzujbky-2013-74).
1H NMR (400 MHz, CDCl3): δ = 6.53 (d, J = 4.0 Hz, 1 H), 5.61 (dd,
J = 8.8, 9.6 Hz, 1 H), 5.41 (d, J = 3.6 Hz, 1 H), 5.54–5.51 (m, 1 H),
5.35 (t, J = 10.0 Hz, 1 H), 5.08 (dd, J = 9.6, 10.0 Hz, 1 H), 4.87 (dd,
J = 3.6, 10.0 Hz, 1 H), 4.72 (dd, J = 10.0, 12.5 Hz, 1 H), 4.29–4.24
(m, 3 H), 4.14–4.03 (m, 3 H), 2.15 (s, 3 H), 2.10 (s, 3 H), 2.08 (s, 3
H), 2.05 (s, 3 H), 2.04 (s, 3 H), 2.03 (s, 3 H), 2.01 (s, 3 H).
Supporting Information for this article is available online at
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13C NMR (100 MHz, CDCl3): δ = 170.3, 170.1, 169.9, 169.4, 169.2,
169.0, 95.4, 85.9, 72.2, 72.0, 71.3, 70.6, 69.7, 68.8, 68.3, 67.5, 61.5,
61.0, 20.7, 20.5, 20.4, 20.3, 20.2.
HRMS (ESI): m/z [M + Na]+ calcd for C26H35BrNaO17: 721.0955;
found: 721.0957.
References
(1) (a) Fujimaki, I.; Ichikawa, Y.; Kuzuhara, H. Carbohydr.
Res. 1982, 101, 148. (b) Boons, G.-J.; Isles, S.; Setälä, P.
Synlett 1995, 755.
(2) Tropper, F. D.; Andersson, F. O.; Braun, S.; Roy, R.
Synthesis 1992, 618.
(3) (a) Tropper, F. D.; Andersson, F. O.; Grand-Maître, C.; Roy,
R. Synthesis 1991, 734. (b) Tsvetkov, Y. E.; Byramova, N.
É.; Backinowsky, L. V. Carbohydr. Res. 1983, 115, 254.
(4) (a) Roth, W.; Pigman, W. Methods Carbohydr. Chem. 1963,
2, 405. (b) Spencer, R. P.; Cavallaro, C. L.; Schwartz, J. J.
Org. Chem. 1999, 64, 3987. (c) Cavallaro, C. L.; Schwartz,
J. J. Org. Chem. 1995, 60, 7055. (d) Hansen, T.; Daasbjerg,
K.; Skrydstrup, T. Tetrahedron Lett. 2000, 41, 8645.
(e) Forbes, C. L.; Franck, R. W. J. Org. Chem. 1999, 64,
1424. (f) Zhao, J.; Wei, S.; Ma, X.; Shao, H. Carbohydr.
Res. 2010, 345, 168.
2,3,6,2′,3′,4′,6′-Hepta-O-acetyl-α-D-lactosyl Bromide (2h)17
20
White solid; yield: 649 mg (93%); mp 140 °C; [α]D +112 (c 1.0,
CHCl3); Rf = 0.30 (PE–EtOAc, 1:1).
IR (KBr): 3432, 2935, 1751, 1641, 1371, 1223, 1048 cm–1.
1H NMR (400 MHz, CDCl3): δ = 6.53 (d, J = 4.0 Hz, 1 H), 5.55 (t,
J = 9.6 Hz, 1 H), 5.35 (dd, J = 9.6, 10.0 Hz, 1 H), 4.97 (dd, J = 3.6,
10.4 Hz, 1 H), 4.76 (dd, J = 4.0, 10.0 Hz, 1 H), 4.53–4.49 (m, 2 H),
4.22–4.03 (m, 4 H), 3.92–3.85 (m, 2 H), 2.17 (s, 3 H), 2.14 (s, 3 H),
2.10 (s, 3 H), 2.07 (s, 3 H), 2.06 (s, 3 H), 2.05 (s, 3 H), 1.97 (s, 3 H).
13C NMR (100 MHz, CDCl3): δ = 170.2, 170.0, 169.8, 100.6, 86.3,
74.8, 72.8, 70.6, 69.5, 68.9, 66.5, 60.9, 60.8, 20.6, 20.5, 20.3.
(5) (a) Matta, K. L.; Girotra, R. N.; Barlow, J. J. Carbohydr.
Res. 1975, 43, 101. (b) Fulton, D. A.; Stoddart, J. F. J. Org.
Synthesis 2013, 45, 331–335
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