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U. Westerlind et al. / Carbohydrate Research 340 (2005) 221–233
(d, 1H, J = 2.9 Hz, H-40), 3.64 (m, H-20), 3.51 (m,
H-2), 3.32 (dd, 1H, J = 2.9, 9.1 Hz, H-30). HRMS:
Calcd for C21H34O11N: 476.2132. Found: 476.2123
(M+NH4+).
4.41 (d, 1H, J = 11.6 Hz, CH2Ph), 4.30 (d, 1H,
J = 11.6 Hz, CH2Ph), 4.03 (dd, 1H, J = 9.7 Hz, H-4),
3.86 (br d, 1H, J = 2.4 Hz, H-40), 3.70 (m, 2H, H-2, H-
3), 2.19 (d, 1H, J = 5.5 Hz, OH-30). HRMS: Calcd for
C60H66O11N: 976.4636. Found: 976.4617 (M+NH4+).
3.15. Phenyl 4-O-(3-O-allyl-2,4,6-tri-O-benzyl-b-D-
galactopyranosyl)-2,3,6-tri-O-benzyl-b-D-glucopyranoside
(26)
3.17. Phenyl 4-O-(2,4,6-tri-O-benzyl-3-keto-b-D-xylo-
hexopyranosyl)-2,3,6-tri-O-benzyl-b-D-glucopyranoside
(28)
A solution of 25 (2.30 g, 5.02 mmol) in N,N-dimethyl-
formamide (80 mL) was stirred with NaH (3.3 g, 80%
dispersion) and benzyl bromide (13 mL) overnight.
MeOH (40 mL) and then water (53 mL) were added,
the mixture was extracted with CHCl3 and the extract
was dried (Na2SO4) and concentrated. Column chroma-
tography (hexane/EtOAc, 5:1) of the residue gave 26
(3.15 g, 3.15 mmol, 63%) as a white solid, [a]D ꢀ15 (c
A solution of DMSO (426 lL, 6.00 mmol) in dry
CH2Cl2 (15 mL) was cooled to ꢀ78 °C, then oxalyl chlo-
ride (230 lL, 2.64 mmol) was added, followed by, after
15 min, a solution of 27 (2.30 g, 2.40 mmol) in dry
CH2Cl2 (35 mL). The mixture was stirred for 15 min
and then Et3N (1.66 mL, 11.99 mmol) was added. After
20 min, the cooling bath was removed, and when the
mixture had reached rt water was added (100 mL).
The mixture was then extracted with CH2Cl2
(100 mL), dried (MgSO4) and concentrated. Column
chromatography (toluene/EtOAc, 10:1) of the residue
gave 28 (2.13 g, 2.23 mmol, 93%) as a white solid, [a]D
ꢀ38 (c 0.7, CHCl3); 1H NMR data (CDCl3): d 5.01
(m, 3H, H-1, CH2Ph), 4.83 (dd, 2H, J = 11.0, 10.7 Hz,
CH2Ph), 4.69 (d, 1H, J = 11.4 Hz, CH2Ph), 4.67 (d,
1H, J = 7.5 Hz, H-10), 4.52 (d, 1H, J = 11.4 Hz, CH2Ph),
4.47 (d, 1H, J = 11.8 Hz, CH2Ph), 4.41 (m, 3H, CH2Ph),
4.36 (m, 2H, H-20, CH2Ph), 4.24 (d, 1H, J = 12.1 Hz,
CH2Ph), 3.99 (dd, 1H, J = 9.2 Hz, H-4), 3.86 (m, 2H,
H-40, H-6a), 3.77 (dd, 1H, J = 5.0, 11.0 Hz, H-6b),
3.72–3.63 (m, 3H, H-2, H-3, H-6a0), 3.59 (ddd, 1H,
J = 1.5, 5.0, 9.2 Hz, H-5), 3.45 (ddd, 1H, J = 1.1,
5.3 Hz, H-50), 3.40 (dd, 1H, J = 5.3, 8.8 Hz, H-6b0).
HRMS: Calcd for C60H64O11N: 974.4480. Found:
974.4496 (M+NH4+).
1
0.7, CHCl3); H NMR data (CDCl3): d 5.93 (ddt, 1H,
J = 5.3, 10.5, 17.1 Hz, CH2@CHCH2), 5.32 (ddd,
1H, J = 1.8, 3.3, 17.1 Hz, CH2@CHCH2), 5.15 (ddd,
1H, J = 1.8, 3.2, 10.3 Hz, CH2@CHCH2), 5.05 (d, 1H,
J = 10.7 Hz, CH2Ph), 4.99 (m, 3H, CH2Ph, H-1), 4.82
(m, 2H, CH2Ph), 4.74 (m, 2H, CH2Ph), 4.55 (d, 1H,
J = 11.6 Hz, CH2Ph), 4.48 (d, 1H, J = 12.1 Hz, CH2Ph),
4.44 (d, 1H, J = 7.7 Hz, H-10), 4.38 (d, 1H, J = 12.1 Hz,
CH2Ph), 4.35 (d, 1H, J = 11.8 Hz, CH2Ph), 4.25 (d, 1H,
J = 11.8 Hz, CH2Ph), 4.17 (bdd, 2H, J = 1.8, 5.3 Hz,
CH2@CHCH2), 3.98 (dd, 1H, J = 8.8, 9.7 Hz, H-4),
3.88 (br d, 1H, J = 3.1 Hz, H-40), 3.34 (dd, 1H,
J = 3.1, 9.9 Hz, H-30). HRMS: Calcd for C63H70O11N:
1016.4949. Found: 1016.4932 (M+NH4+).
3.16. Phenyl 4-O-(2,4,6-tri-O-benzyl-b-D-galactopyrano-
syl)-2,3,6-tri-O-benzyl-b-D-glucopyranoside (27)
A solution of 26 (3.00 g, 3.00 mmol), tris(triphenylphos-
phine)rhodium(I) chloride (172 mg, 0.186 mmol) and
1,8-diazabicyclo[5.4.0]undec-7-ene (51 lL, 0.342 mmol)
in ethanol/toluene/water (13 mL, 30:10:5 by vol) was
heated at reflux for 24 h, then concentrated and taken
up in acetic acid/water (30 mL, 9:1 by vol). The solution
was heated at 80 °C for 1 h, then cooled and concen-
trated. The concentrate was partitioned between diethyl
ether (70 mL) and water (70 mL). The organic layer was
washed with water, dried (MgSO4) and concentrated.
Column chromatography (toluene/EtOAc, 8:1) of the
residue gave 27 (2.32 g, 2.42 mmol, 81%) as a white
3.18. Phenyl 4-O-(2,4,6-tri-O-benzyl-3-oximino-b-D-xylo-
hexopyranosyl)-2,3,6-tri-O-benzyl-b-D-glucopyranoside
(29)
A mixture of 28 (2.00 g, 2.09 mmol) and hydroxylamine
hydrochloride (800 mg, 11.5 mmol) in 1:1 pyridine/etha-
nol (40 mL) was stirred at rt overnight. The solvent was
evaporated and the residue was mixed with water and
extracted several times with diethyl ether. The ether
solution was dried (Na2SO4) and concentrated to give
29 (1.78 g, 1.83 mmol, 88%) as a white solid, [a]D ꢀ19
1
1
solid, [a]D ꢀ14 (c 0.5, CHCl3); H NMR data (CDCl3):
(c 0.5, CHCl3); H NMR data (CDCl3): d 5.08 (br d,
d 5.07 (d, 1H, J = 11.0 Hz, CH2Ph), 5.01 (d, 1H,
J = 11.0 Hz, CH2Ph), 5.00 (d, 1H, J = 7.2 Hz, H-1),
4.85 (d, 1H, J = 11.0 Hz, CH2Ph), 4.84 (d, 1H,
J = 11.4 Hz, CH2Ph), 4.78 (d, 1H, J = 11.4 Hz, CH2Ph),
4.77 (d, 1H, J = 11.0 Hz, CH2Ph), 4.71 (d, 1H,
J = 11.6 Hz, CH2Ph), 4.63 (d, 1H, J = 11.6 Hz, CH2Ph),
4.55 (d, 1H, J = 12.1 Hz, CH2Ph), 4.44 (d, 1H,
J = 7.0 Hz, H-10), 4.43 (d, 1H, J = 12.1 Hz, CH2Ph),
1H, J < 1 Hz, H-40), 4.98 (m, 3H, H-1, CH2Ph), 4.81
(d, 2H, J = 10.5 Hz, CH2Ph), 4.78 (d, 1H, J = 10.5 Hz,
CH2Ph), 4.75 (d, 1H, J = 12.3 Hz, CH2Ph), 4.63 (d,
1H, J = 12.3 Hz, CH2Ph), 4.61 (d, 1H, J = 8.1 Hz, H-
10), 4.49–4.36 (m, 5H, CH2Ph), 4.23 (d, 1H,
J = 12.7 Hz, CH2Ph), 4.21 (d, 1H, J = 8.1 Hz, H-20),
3.99 (dd, 1H, J = 9.2 Hz, H-4), 3.84 (dd, 1H, J < 1,
11.0 Hz, H-6a), 3.76 (dd, 1H, J = 5.0, 11.0 Hz, H-6b),