Q. Li et al. / Carbohydrate Research 340 (2005) 1601–1604
1603
mixture was stirred for 10 h and then MeOH (40 mL)
3.4. 2-(4-Allyloxyphenyl)ethyl 2,3-di-O-allyl-6-O-allyl-
oylcarbonyl-b-D-glucopyranoside (5)
was added and the mixture was poured into ice water
(200 mL), and extracted by CH2Cl2 (50 mL · 3). The or-
ganic layer was washed with water (50 mL · 3), dried
with anhydrous Na2SO4, and concentrated. The residue
was subjected to column chromatography, eluting with
5:1 petroleum ether (60–90 ꢁC)–EtOAc to give 3
To a solution of 4 (7.67 g, 4.29 mmol) and AocOBt16
(1.13 g, 5.14 mmol) in anhydrous CH2Cl2 (20 mL) was
added 3.0 mL triethylamine, and then the mixture was
stirred for 3 h. The mixture was evaporated and the res-
idue purified by column chromatography (4:1 petroleum
ether (60–90 ꢁC)–EtOAc) to give 5 (1.16 g, syrup,
92.2%); [a]D ꢀ35.3 (c 3.4, CHCl3); IR(cm ꢀ1): 3488,
(6.67 g, 81.4%); [a]D ꢀ33.3 (c 3.60, CHCl3); IR(cm ꢀ1):
1
1642; H NMR(CDCl ): d 7.49–7.26 (m, 5H, Ar–H),
3
7.13, 6.84 (dd, 4H, Ar–H), 5.95 (m, 3H, 3 · CH2–
CH@CH2), 5.52 (s, 1H, benzylidene–OCHO–), 5.43–
5.12 (m, 6H, 3 · CH2–CH@CH2), 4.52 (dd, 1H, H-2),
4.50 (t, 1H, H-3), 4.37 (d, 1H, J1,2 7.8 Hz, H-1), 4.32
(dd, 1H, H-6a), 4.16 (t, 2H, OCH2CH2Ar), 4.29 and
3.60 (2m, 6H, 3 · CH2–CH@CH2), 4.11 (m, 1H, H-5),
3.75 (dd, 1H, H-6b), 3.72 (t, 1H, H-4), 2.89 (m, 2H,
OCH2CH2Ar); 13C NMR(CDCl 3): d 157.1, 137.4,
130.7, 129.8, 128.9, 128.2, 125.9, and 114.7 (Ar), 135.4,
135.2, and 133.4 (3 · –OCH2–CH@CH2), 117.6, 116.8,
and 116.7 (3 · –OCH2–CH@CH2), 103.9 (C-1), 101.1
(benzylidene–OCHO–), 80.4 (C-3), 74.0 (C-4), 73.9
(C-2), 71.3 (–OCH2CH2Ar), 69.7, 68.8, and 68.6
(3 · –OCH2–CH@CH2), 68.8 (C-6), 66.0 (C-5), 35.3
(–OCH2CH2Ar); MS(FAB), m/z: 509 (M+1)+. Anal.
Calcd for C30H36O7: C, 70.84; H, 7.14. Found: C,
70.85; H, 7.13.
1
1742, 1642; H NMR(CDCl 3): d 7.11 and 6.82 (dd,
4H, Ar–H), 6.06–5.85 (m, 4H, 4 · –OCH2–CH@CH2),
5.43–5.10 (m, 8H, 4 · –OCH2–CH@CH2), 4.63 (dd,
1H, H-2), 4.61 (t, 1H, H-3), 4.50 (m, 1H, H-5), 4.33
(d, 1H, J1,2 7.8 Hz, H-1), 4.32 (dd, 1H, H-6a), 4.16 (t,
1H, H-4), 4.07 and 3.69 (2m, 8H, 4 · –OCH2
–CH@CH2), 3.84 (dd, 1H, H-6b), 3.69 (t, 2H, –OCH2-
CH2Ar), 2.87 (t, 2H, –OCH2CH2Ar); 13C NMR
(CDCl3): d 157.1(Ar), 155.1 (allyloylcarbonyl, C@O),
130.8, 129.8 and 114.6 (Ar), 135.1, 134.9, 133.4, and
131.4 (4 · –OCH2–CH@CH2), 119.0, 117.5, 117.2, and
116.8 (4 · –OCH2–CH@CH2), 103.5 (C-1), 81.3 (C-3),
74.1 (C-4), 73.4 (C-2), 73.2 (C-6), 73.2, 69.7, 68.8, and
68.6 (4 · –OCH2–CH@CH2), 70.9 (–OCH2CH2Ar),
66.8 (C-5), 35.2 (–OCH2CH2Ar); MS(FAB), m/z: 543
(M+K)+. Anal. Calcd for C27H36O9: C, 64.27; H, 7.19.
Found: C, 64.35; H, 7.34.
3.3. 2-(4-Allyloxyphenyl)ethyl 2,3-di-O-allyl-b-D-gluco-
pyranoside (4)
3.5. 2-(4-Allyloxyphenyl)ethyl 2,3-di-O-allyl-4-O-[(E)-(4-
O-allyl)feruloyl]-6-O-allyloylcarbonyl-b-D-glucopyrano-
side (6)
A mixture of 3 (4.60 g, 9.05 mmol) and 80% HOAc
(100 mL) was stirred at 80 ꢁC for 4 h and then toluene
(50 mL) was added, and the solvent was evaporated in
vacuo. he residue was dissolved in CHCl3 (50 mL) and
the organic layer was washed with ice water, aqueous
NaHCO3 (5%), and water, and then dried and evapo-
rated. The resulting residue was purified by column
chromatography (2:1 petroleum ether (60–90 ꢁC)
–EtOAc) to give 4 (3.41 g) as a syrup; yield 74.1%;
A mixture of 5 (0.66 g, 1.31 mmol), 4-O-allylferulic acid7
(0.46 g, 1.96 mmol), DCC (270 mg, 1.31 mmol), DMAP
˚
(10 mg), powdered 4 A molecular sieves (200 mg), and
anhydrous CH2Cl2 (20 mL) was stirred for 16 h, during
which time the mixture was allowed to warm to room
temperature. The reaction mixture was filtered and the
filtrate evaporated to dryness. The residue was purified
by preparative TLC (40:1 benzene–EtOAc) to give 6
(0.87 g, 92.3%); [a]D ꢀ8.7 (c 4.6, CHCl3); IR(cm ꢀ1):
1742, 1710; 1H NMR(CDCl 3): d 7.65 (d, 1H, J
15.2 Hz, trans-CH@CH–C@O), 7.26 (s, 1H), 7.14 and
6.85 (dd, 4H), 7.06 and 6.88 (AB, 2H) [Ar–H], 6.29 (d,
1H, J 15.2 Hz, trans-CH@CH–C@O), 6.03, and 5.83
(2m, 5H, 5 · –OCH2–CH@CH2), 5.43–5.00 (m, 10H,
5 · –OCH2–CH@CH2), 4.65 (dd, 1H, H-2), 4.58 (dd,
1H, H-3), 4.50 (m, 1H, H-6a), 4.37 (d, 1H, J1,2 7.5 Hz,
H-1), 4.25 (dd, 1H, H-4), 4.23, and 4.09 (2m, 10H,
5 · –OCH2–CH@CH2), 3.92 (s, 3H, OCH3), 3.90 (t,
1H, H-6b), 3.70 (t, 1H, H-5), 3.68 (m, 2H, –OCH2-
CH2Ar), 2.89 (m, 2H, –OCH2CH2Ar); 13C NMR
(CDCl3): d 165.8 (CH@CH–C@O), 157.1 (Ar), 154.7
(allyloylcarbonyl C@O), 150.3 and 149.5 (Ar), 146.0
(CH@CH–C@O), 134.9, 133.4, 132.6, 131.4, and 131.3
(5 · –OCH2–CH@CH2), 130.8, 129.8, 127.3, and 120.7
1
[a]D ꢀ22.5 (c 8.9, CHCl3); IR(cm ꢀ1): 3410, 1642; H
NMR(CDCl ): d 7.12, 6.83 (dd, 4H, Ar–H), 5.94 (m,
3
3H, 3 · –OCH2–CH@CH2), 5.42–5.10 (m, 6H, 3 ·
–OCH2–CH@CH2), 4.50 (dd, 1H, H-2), 4.47 (t, 1H,
H-3), 4.35 (d, 1H, J1,2 7.8 Hz, H-1), 4.30 (dd, 1H,
H-6a), 4.17 (t, 1H, H-4), 4.12 (m, 2H, H-5), 4.09
and 3.67 (2m, 6H, 3 · –OCH2–CH@CH2), 3.74 (dd,
1H, H-6b), 3.70 (t, 2H, –OCH2CH2Ar), 2.87 (m, 2H,
–OCH2CH2Ar), 2.35 (br s, 2H, 2 · –OH); 13C NMR
(CDCl3): d 157.2 (Ar), 134.9, 133.4 and 131.4 (3 ·
–OCH2–CH@CH2), 130.7, 129.8 and 114.7 (Ar), 117.5,
117.2, and 116.8 (3 · –OCH2CH@CH2), 103.6 (C-1),
81.5 (C-3), 74.1 (C-4), 73.4 (C-2), 73.4, 70.2 and 68.8
(3 · –OCH2–CH@CH2), 71.1 (–CH2CH2Ar), 70.2 (C-
6), 62.6 (C-5), 35.3 (–CH2CH2Ar); MS(FAB), m/z: 459
(M+1)+. Anal. Calcd for C23H32O7: C, 65.55; H, 7.77.
Found: C, 65.70; H, 7.67.