K. Parkan et al. / Carbohydrate Research 345 (2010) 352–362
361
00
00
did not contain the starting compound and the reaction was
quenched by the addition of a NaHCO3 solution to pH 8. After par-
titioning between dichloromethane and aqueous NaHCO3, the or-
ganic phase was dried, the solvent evaporated, and the residue
chromatographed on a short silica gel column in light petroleum/
ethyl acetate (2:1) affording 0.20 g of 2,3-dideoxy-3-C-[(2,3,4,6-
J = 2.8 Hz, H-100b), 2.04 (dt, 1H, J1b ,1a = 14.2 Hz, J = 2.8 Hz, H-100a),
2.39 (dt, 1H, J = 11.00 Hz, J = 1.9 Hz, H-3), 3.48 (dd, 1H,
J3,4 = J4,5 = 9.2 Hz, H-4), 3.54 (m, 1H, H-30), 3.56–3.63 (m, 2H, H-40,
H-50), 3.75–3.87 (m, 3H, H-5, H-6a, H-6b), 3.92 (m, 1H, H-20),
4.11 (ddd, 1H, J = 13.3 Hz, J = 7.8 Hz, J = 3.2 Hz, H-10), 4.47–4.86
(m, 11H, 5 ꢂ CH2Ph, H-2), 6.32 (dd, 1H, J = 2.3 Hz, J = 5.9 Hz, H-1),
13
tetra-O-benzyl-b-
D
-glucopyranosyl)methyl]-4,6-di-O-benzyl-
L
-ara-
7.1–7.45 (m, 25H, 5 ꢂ C6H5). C NMR (CDCl3): 16.0 (C-60), 29.6
bino-hexopyranose (Rf 0.3, light petroleum/ethyl acetate (2:1), m/z
865.7 [M+H]+). The obtained compound (0.23 mmol) was dissolved
in dichloromethane (5 ml) and the solution was treated in an inert
atmosphere at 0 °C with s-collidine (0.415 g, 3.43 mmol) and mesyl
anhydride (0.08 g, 0.458 mmol). The reaction mixture was stirred
at 0 °C and its course was monitored by TLC (light petroleum/ethyl
acetate 3:1). After 4 h, the reaction mixture was partitioned be-
tween dichloromethane and aqueous NaHCO3. The organic phase
was dried, the solvent evaporated, and the residue chromato-
graphed on silica gel in light petroleum/ethyl acetate (7:1?4:1),
affording 0.145 g (64%) of compound 9, Rf = 0.65 (light petro-
(C-100), 35.1 (C-3), 67.4 (C-50), 68.6 (C-6), 69.0 (C-10), 72.8, 73.0,
73.8, 73.5, 74.3 (5 ꢂ PhCH2), 76.7 (C-40), 76.7 (C-20), 76.9 (C-4),
77.8 (C-5), 78.2 (C-30), 101.7 (C-2), 127.3–128.3 (5 ꢂ C6H5), 138.2,
138.3, 138.4, 138.5, 138.8 (5 ꢂ ipso C6H5), 142.4 (C-1). ESIMS m/z:
calcd for (C48H52O7): 740.9. Found, 758.1 [M+NH4]+. Anal. Calcd
for C48H52O7: C, 77.81; H, 7.07. Found: C, 77.95; H, 7.68.
Acknowledgments
This work was supported by the Grant Agency of the Czech
Republic (Grant No. 203/08/1124) and by the Ministry of Education,
Youth and Sport of the Czech Republic (Grant No. 6046137305).
leum/ethyl acetate, 3:1). [
a
]
+35.1 (c 0.43, CHCl3). 1H NMR
D
(CDCl3): 1.50 (m, 1H, H-1a00), 1.76 (ddd, 1H, J1a ,1b = 13.3 Hz,
00
00
J = 10.1 Hz, J = 3.2 Hz, H-1b000), 2.65 (m, 1H, H-3), 3.19 (dd, 1H,
J3 ,4 = J4 ,5 = 8.9 Hz, H-40), 3.30–3.38 (m, 2H, H-10, H-50), 3.44 (dd,
0
0
0
0
References
1H, J3,4 = J4,5 = 8.8 Hz, H-4), 3.56–3.76 (m, 4H, H-30, H-6a , H-6b ,
H-20), 3.77–3.81 (m, 1H, H-6a), 3.82–3.86 (m, 2H, H-5, H-6b),
4.47–4.67 (m, 8H, 4 ꢂ CH2Ph), 4.69 (dd, 1H, J = 5.9 Hz, J = 2.0 Hz,
H-2), 4.75–4.92 (m, 4H, 2 ꢂ CH2Ph), 6.30 (dd, 1H, J = 5.9 Hz,
J = 1.8 Hz, H-1), 7.16–7.38 (m, 30H, 6 ꢂ C6H5). 13C (CDCl3): 34.5
(C-100), 35.3 (C-3), 68.7, 69.0 (C-60, C-6), 73.4, 73.6, 73.8, 74.9,
75.2, 75.6 (6 ꢂ CH2Ph), 76.0, 76.2 (C-40, C-4), 77.9 (C-5), 78.6 (C-
30), 79.1 (C-10), 82.4 (C-50), 87.3 (C-20), 102.1 (C-2), 127.5–128.4
(6 ꢂ C6H5), 138.0, 138.1, 138.2, 138.3, 138.4, 138.6 (6 ꢂ ipso
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848.3 [M+H]+. Anal. Calcd for C55H58O8: C, 77.99; H, 6.90. Found:
C, 78.36; H, 7. 7.06.
0
0
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4.22. 1,5-Anhydro-4,6-di-O-benzyl-2,3-dideoxy-3-C-[(2,3,4,6-
tetra-O-benzyl-b-D-glucopyranosyl)methyl]-D-arabino-hex-1-
enitol (10)
Using the same procedure as described for the preparation of
compound 9, the mixture of compounds 32a,b (1.6 g; 1.11 mmol)
was converted to compound 10 (0.63 g; 67%), Rf = 0.65 (light petro-
leum/ethyl acetate, 3:1). [
a
]
D +7.4 (c 0.99, CHCl3). 1H NMR (CDCl3):
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1.53 (m, 1H, H-100), 1.77 (m, 1H, H-100), 2.67 (m, 1H, H-3), 3.21 (dd,
1H, J3 ,4 = J4 ,5 = 9.0 Hz, H-40), 3.31–3.38 (m, 2H, H-10, H-50), 3.45
0
0
0
0
(dd, 1H, J3,4 = J4,5 = 8.9 Hz, H-4), 3.56–3.74 (m, 4H, H-30, H-6a , H-
0
0
6b , H-20), 3.76–3.82 (m, 1H, H-6a), 3.82–3.88 (m, 2H, H-5, H-6b),
4.37–4.68 (m, 8H, 4 ꢂ CH2Ph), 4.70 (dd, 1H, J = 5.9 Hz, J = 1.6 Hz,
H-2), 4.76–4.95 (m, 4H, 2 ꢂ CH2Ph), 6.32 (dd, 1H, J = 5.9 Hz,
J = 2.0 Hz, H-1), 7.05–7.45 (m, 30H, 6 ꢂ C6H5). 13C (CDCl3): 34.4
(C-100), 35.2 (C-3), 68.6, 68.9 (C-60, C-6), 73.3, 73.4, 73.5, 73.7,
74.9, 75.1, (6 ꢂ CH2Ph), 75.9, 76.1 (C-40, C-4), 77.8 (C-5), 78.5 (C-
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C6H5), 142.4 (C-1). ESIMS m/z: calcd for (C55H58O8): 847.1. Found,
848.3 [M+H]+. Anal. Calcd for C55H58O8: C, 77.99; H, 6.90. Found:
C, 78.29; H, 7.12.
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benzyl-a-L-fucopyranosyl)methyl]-D-arabino-hex-1-enitol (11)
Using the same procedure as described for the preparation of
compound 9, the mixture of compounds 33a,b (0.69 g; 0.81 mmol)
was converted to compound 11 (0.26 g; 67%), Rf = 0.75 (light petro-
leum/ethyl acetate, 3:1). [
(CDCl3): 1.13 (d, 3H, J = 6.4 Hz, CH3), 1.19 (dt, 1H, J1a ,1b = 14.2 Hz,
a
]
ꢀ43.0 (c 0.74, CHCl3). 1H NMR
D
00
00