G. Wang et al. / Carbohydrate Research 346 (2011) 2368–2373
2371
126.2, 120.4, 101.7, 98.3, 79.3, 78.9, 73.3, 68.5, 62.8, 50.1, 45.7,
22.8. HRMS (ESI) m/z calcd for C16H20O7Na [M+Na]+ 347.1107,
found 347.1122.
68.5, 63.0, 51.6, 44.7, 20.9. HRMS (ESI) m/z calcd for C18H21O8ClNa
[M+Na]+ 423.0823, found 423.0815.
exo-Type: Yield: 93%. A colorless solid. Mp 131.5–132.2 °C.
½
a 2D0 = +50.6 (c 0.30, CHCl3). 1H NMR (600 MHz, CDCl3): d 7.47–
ꢀ
4.5. 4,6-O-Benzylidene-
a-
D-glucopyranose 1,2-(phenyl methoxyl
7.35 (m, 5H, ArH), 5.86 (d, 1H, J = 5.48 Hz, H-1), 5.52 (s, 1H, PhCH),
5.38 (dd, 1H, J = 8.7, 3.66 Hz, H-3), 4.43–4.40 (m, 2H, J = 2H, H-2, H-
6a), 4.09–4.05 (m, 1H, H-5), 3.83 (d, 1H, J = 12.84 Hz, ClCH2), 3.80
(d, 1H, J = 12.42 Hz, ClCH2), 3.74 (t like, 1H, J = 9.18, 8.82 Hz, H-4),
3.71 (t like, 1H, J = 10.56, 10.08 Hz, H-6), 3.34 (s, 3H, CH3O), 2.13
(s, 3H, CH3CO). 13C NMR (150 MHz, CDCl3): d 169.7, 136.7, 129.1,
128.2, 126.1, 118.7, 101.5, 98.5, 77.7, 76.9, 73.1, 68.5, 62.7, 50.7,
43.8, 20.9. HRMS (ESI) m/z calcd for C18H21O8ClNa [M+Na]+
423.0823, found 423.0821.
orthoacetate) (3b)
endo-Type: ½a 2D0
ꢀ
= +72.0 (c 0.38, CHCl3). 1H NMR (600 MHz,
CDCl3): d 7.59–7.38 (m, 10H), 5.69 (d, 1H, J = 6.0 Hz, H-1), 5.59 (s,
1H, PhCH), 4.53 (dd, 1H, J = 10.08, 5.94 Hz, H-3), 4.44 (dd, 1H,
J = 10.5, 5.46 Hz, H-6a), 4.29 (t like, 1H, J = 6.0, 5.46 Hz, H-2), 4.11–
4.07 (m, 1H, H-5), 3.75 (t like, 1H, J = 10.56, 10.02 Hz, H-6b), 3.57
(t, 1H, J = 9.6 Hz, H-4), 3.25 (s, 3H, OCH3); 13C NMR (150 MHz,
CDCl3): d 136.9, 129.3, 128.4, 128.3, 126.2, 126.0, 120.5, 101.8,
99.3, 79.2, 78.6, 73.3, 68.6, 63.0, 53.4, 51.6, 45.9. HRMS (ESI) m/z
calcd for C21H22O7Na [M+Na]+ 409.1263, found 409.1273.
4.8. 3-O-Benzyl-4,6-O-benzylidene-a-D-glucopyranose 1,2-
(chloromethyl methoxyl orthoacetate) (4k)
exo-Type: ½a 2D0
ꢀ
= +67.4 (c 0.30, CHCl3). 1H NMR (600 MHz, CDCl3):
d 7.63–7.33 (m, 10H), 5.94 (d, 1H, J = 5.52 Hz, H-1), 5.51 (s, 1H,
PhCH), 4.39 (t like, 1H, J = 5.52, 5.46 Hz, H-2), 4.36 (dd, 1H,
J = 10.08, 5.04 Hz, H-6a), 3.82 (dd, 1H, J = 9.60, 5.52 Hz, H-3), 3.79–
3.75 (m, 1H, H-5), 3.70 (t like, 1H, J = 10.50, 10.08 Hz, H-6b), 3.51
(t, 1H, J = 9.6 Hz, H-4), 3.24 (s, 3H, OCH3); 13C NMR (150 MHz,
CDCl3): d 137.1, 136.7, 129.3, 129.3, 128.4, 128.3, 126.1, 125.9,
119.6, 101.7, 98.7, 79.1, 78.7, 72.5, 68.5, 63.2, 50.8, 45.9. HRMS
(ESI) m/z calcd for C21H22O7Na [M+Na]+ 409.1263, found 409.1282.
Following the same procedure as for compound 5e.
endo-Type: Yield: 92%. A white solid. ½a D20
ꢀ
= +58.2 (c 0.30, CHCl3).
1H NMR (600 MHz, CDCl3): d 7.52–7.28 (m, 10H), 5.82 (d, 1H,
J = 6.0 Hz), 5.60 (s, 1H), 4.86 (d, 1H, J = 11.88 Hz), 4.84 (d, 1H,
J = 11.88 Hz), 4.42 (dd, 1H, J = 5.94, 5.04 Hz), 4.40 (dd, 1H, J = 10.56,
5.52 Hz), 4.10 (dd, 1H, J = 9.18, 4.56 Hz), 3.99–3.95 (m, 1H), 3.75–
3.66 (m, 4H), 3.33 (s, 3H); 13C NMR (150 MHz, CDCl3): d 137.8,
137.1, 129.0, 128.3, 128.2, 127.9, 127.8, 126.0, 119.5, 101.1, 99.7,
79.4, 79.1, 79.0, 73.0, 68.6, 62.9, 51.0, 44.8. HRMS (ESI) m/z calcd
for C23H25O7ClNa [M+Na]+ 471.1187, found 471.1198.
4.6. 4,6-O-Benzylidene-
a-D-glucopyranose 1,2-(chloromethyl
methoxyl orthoacetate) (3c)
exo-Type: Yield: 91%. A white solid. ½a D20
ꢀ
= +43.8 (c 0.32, CHCl3).
1H NMR (600 MHz, CDCl3): d 7.51–7.29 (m, 10H), 5.86 (d, 1H,
J = 5.46 Hz), 5.59 (s, 1H), 4.83 (s, 2H), 4.50 (dd, 1H, J = 5.52,
4.14 Hz), 4.40 (dd, 1H, J = 10.50, 5.04 Hz), 4.05 (dd, 1H, J = 8.7,
4.14 Hz), 4.00–3.95 (m, 1H), 3.74–3.69 (m, 4H), 3.35 (s, 3H); 13C
NMR (150 MHz, CDCl3): d 137.6, 137.0, 129.0, 128.5, 128.4, 128.2,
128.0, 127.8, 126.9, 126.0, 118.7, 101.2, 99.0, 79.4, 79.2, 79.0,
73.0, 68.6, 62.8, 50.5, 44.2. HRMS (ESI) m/z calcd for C23H25O7ClNa
[M+Na]+ 471.1187, found 471.1164.
endo-Type: ½a 2D0
ꢀ
= +69.9 (c 0.31, CHCl3). 1H NMR (600 MHz,
CDCl3): d 7.51–7.37 (m, 5H), 5.80 (d, 1H, J = 5.52 Hz), 5.56 (s, 1H),
4.39 (dd, 1H, J = 10.5, 5.46 Hz), 4.31–4.28 (m, 2H), 3.95–3.92 (m,
1H), 3.74–3.67 (m, 3H), 3.54 (t like, 1H, J = 9.66, 9.60 Hz), 3.47 (s,
3H). 13C NMR (150 MHz, CDCl3): d 129.4, 128.4, 126.2, 119.4,
101.8, 99.9, 78.9, 78.6, 73.2, 68.5, 63.1, 51.3, 44.6. HRMS (ESI) m/
z calcd for C16H19O7ClNa [M+Na]+ 381.0717, found 381.0727.
exo-Type: ½a 2D0
ꢀ
= +60.1 (c 0.28, CHCl3). 1H NMR (600 MHz,
CDCl3): d 7.50–7.37 (m, 5H), 5.85 (d, 1H, J = 5.52 Hz), 5.55 (s, 1H),
4.40 (t like, 1H, J = 5.46, 5.04 Hz), 4.37 (t like, 1H, J = 5.52,
5.46 Hz), 4.21 (dd, 1H, J = 8.7, 5.46 Hz), 3.99–3.95 (m, 1H), 3.78
(d, 1H, J = 12.36 Hz), 3.74 (d, 1H, J = 11.94 Hz), 3.69 (t like, 1H,
J = 10.56, 10.50 Hz), 3.54 (t, 1H, J = 9.6 Hz), 3.34 (s, 3H).13C NMR
(150 MHz, CDCl3): d 129.4, 128.4, 126.2, 118.6, 101.8, 98.9, 79.4,
78.8, 73.5, 68.4, 63.1, 50.6, 44.3. HRMS (ESI) m/z calcd for
4.9. 3-O-tert-Butyldimethylsiloxy-4,6-O-benzylidene-a-D-
glucopyranose 1,2-(chloromethyl methoxyl orthoacetate) (4l)
Following the same procedure as for compound 5f.
endo-Type: Yield: 85%. A white solid. ½a D20
ꢀ
= +43.1 (c 0.30,
CHCl3). 1H NMR (600 MHz, CDCl3): d 7.50–7.35 (m, 5H), 5.79 (d,
1H, J = 6.0 Hz), 5.55 (s, 1H), 4.37 (dd, 1H, J = 10.56, 5.52 Hz), 4.26–
4.21 (m, 2H), 3.94–3.90 (m, 1H), 3.72–3.66 (m, 3H), 3.51 (t like,
1H, J = 9.66, 9.12 Hz), 3.46 (s, 3H), 0.90 (s, 9H), 0.13, 0.05 (s, 3H
each). 13C NMR (150 MHz, CDCl3): d 137.1, 128.9, 128.1, 126.0,
119.3, 101.3, 99.8, 81.0, 79.7, 74.1, 68.6, 63.1, 51.1, 44.8, 25.7,
18.1, ꢁ4.5, ꢁ4.9. MS (ESI) m/z calcd for C22H34O7ClSi [M+H]+
473.1762, found 473.1248.
C
16H19O7ClNa [M+Na]+ 381.0717, found 381.0712.
4.7. 3-O-Acetyl-4,6-O-benzylidene- -glucopyranose 1,2-
a-D
(chloromethyl methoxyl orthoacetate) (4j)
Compound 3c (1.0 mmol), DMAP (12 mg, 0.1 mmol) and pyridine
(322
lL, 4.0 mmol) were dissolved in CH2Cl2 (10 mL) and cooled to
exo-Type: Yield: 86%. A white solid. ½a D20
ꢀ
= +30.4 (c 0.39, CHCl3).
0 °C, Ac2O (151
lL, 1.5 mmol) was added dropwise. The reaction was
1H NMR (600 MHz, CDCl3): d 7.50–7.35 (m, 5H), 5.85 (d, 1H,
J = 5.46 Hz), 5.55 (s, 1H), 4.38 (dd, 1H, J = 10.56, 5.04 Hz), 4.33 (t like,
1H, J = 5.46, 4.62 Hz), 4.18 (dd, 1H, J = 9.12, 4.14 Hz), 3.97–3.93 (m,
1H), 3.78 (d, 1H, J = 12.36 Hz), 3.75 (d, 1H, J = 12.36 Hz), 3.68 (t like,
1H, J = 10.56, 10.08 Hz), 3.53 (t, 1H, J = 9.18 Hz), 3.35 (s, 3H), 0.90 (s,
9H), 0.14, 0.08 (s, 3H each); 13C NMR (150 MHz, CDCl3): d 137.1,
128.9, 128.1, 126.0, 118.5, 101.3, 99.1, 81.4, 79.6, 74.2, 68.5, 63.2,
50.5, 44.2, 25.7, 18.1, ꢁ4.5, ꢁ4.9. HRMS (ESI) m/z calcd for
stirred for 1 h at rt, CH3OH (1.5 mmol) was added and was stirred for
30 min, the solution was diluted with CH2Cl2 (50 mL) and was washed
with aqueous 2 N HCl, saturated aqueous NaHCO3 and brine, and dried
over Na2SO4, concentrated and purified by column chromatography on
silica gel (EtOAc/petroleum ether = 1:3) to afford 4j. Recrystallized by
EtOAc/hexane = 1:10 to afford 5j as a colorless solid.
endo-Type: Yield: 93%. A colorless solid. Mp 138.5–139.4 °C.
½
a 2D0
ꢀ
= +58.2 (c 0.30, CHCl3). 1H NMR (600 MHz, CDCl3): d 7.46–
C
22H34O7SiCl [M+H]+ 473.1762, found 473.1776.
7.35 (m, 5H, ArH), 5.84 (d, 1H, J = 5.94 Hz, H-1), 5.58 (dd, 1H,
J = 9.60, 5.04 Hz, H-3), 5.52 (s, 1H, PhCH), 4.40 (dd, 1H, J = 10.56,
5.04 Hz, H-6a), 4.35 (t like, 1H, J = 5.52, 5.46 Hz, H-2), 4.11–4.07
(m, 1H, H-5), 3.74–3.66 (m, 4H, H-4, H-6b, ClCH2), 3.54 (s, 3H,
CH3O), 2.13 (s, 3H, CH3CO). 13C NMR (150 MHz, CDCl3): d 169.7,
136.7, 129.1, 128.2, 126.1, 119.6, 101.3, 99.6, 77.3, 76.6, 73.3,
4.10. 1-O-Acetyl-3-O-benzoyl-4,6-O-benzylidene-a-D-
glucopyranose (5d)
Compound 3a (324 mg, 1.0 mmol), DMAP (12 mg, 0.1 mmol)
and pyridine (2.0 mmol) were dissolved in CH2Cl2 (10 mL) and