N. Ding et al. / Carbohydrate Research 341 (2006) 2769–2776
2773
and then filtered and concentrated. The residue was
3.6. p-Methoxyphenyl 2,3,4-tri-O-acetyl-a-L-rhamno-
pyranosyl-(1!3)-2-deoxy-2-phthalimido-b-D-galacto-
pyranoside (9)
purified by column chromatography (3:1 petroleum
ether–EtOAc) to afford 5 (110.0 mg, 82.9%) as an
amorphous solid: Rf 0.12 (3:1 petroleum ether–EtOAc);
22
1
½aꢁD +116.0 (c 0.2, CHCl3); H NMR (CDCl3): d 7.51–
Compound 8 (250.0 mg) was added to 80% HOAc–H2O
(10 mL), and the mixture was heated at 90 °C for 8 h,
then concentrated and co-evaporated with toluene
(5 mL) three times. The residue was purified by column
chromatography (20:1 CHCl3–CH3OH) to give com-
pound 9 (188.6 mg, 85.1%) as a white solid: Rf 0.5
7.26 (m, 25H, PhCH and 4Ph), 5.87 (m, 1H,
OCH2CH@CH2), 5.26 (dd, 1H,
J 17.2, 1.5 Hz,
OCH2CH@CHH), 5.13 (d, 1H, J 3.2 Hz, H-1), 5.13
(dd, 1H, J 12.0, 1.5 Hz, OCH2CH@CHH), 5.04 (d,
1H, J 3.7 Hz, H-10), 4.92–4.56 (m, 8H, 4PhCH2), 4.35
(dd, 1H, J 10.3, 3.3 Hz, H-2), 4.23 (m, 2H, H-6a, H-
4), 4.16 (m, 1H, OCHHCH@CH2), 4.07–4.01 (m, 5H,
H-3, H-20, OCHHCH@CH2, H-50, H-6b), 3.97 (dd,
1H, J 9.9, 2.9 Hz, H-30), 3.71 (d, 1H, J 1.8 Hz, H-40),
3.66 (s, 1H, H-5), 3.50 (m, 1H, H-60a), 3.26 (m, 1H,
H-60b), 1.72 (s, 1H, 60-OH); 13C NMR (CDCl3): d
138.7, 138.6, 138.4, 138.3, 137.7, 133.8, 128.9, 128.4–
127.5, 126.3, 126.1, 118.3, 100.8 (PhCH), 95.6 (C1),
95.3 (C10), 79.1 (C30), 75.9, 75.1 (C5), 74.7, 74.4, 73.9
(C4), 73.0, 72.9, 71.6, 70.9 (C2), 70.4, 69.3 (C6), 68.8
(OCH2), 62.7, 62.4. HRMS: calcd for C50H54O11Na+
853.3564; found 853.3528.
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1
(20:1 CHCl3–CH3OH); ½aꢁD +36.6 (c 0.2, CHCl3); H
NMR (CDCl3): d 7.93–6.71 (m, 8H, Ph), 5.66 (d, 1H,
J 8.8 Hz, H-1), 5.20 (dd, 1H, J 9.9, 3.3 Hz, H-30), 4.97
(dd, 1H, J 9.9, 9.5 Hz, H-40), 4.84 (dd, 1H, J 11.0,
8.4 Hz, H-2), 4.79 (m, 1H, H-20), 4.77 (d, 1H, J
1.8 Hz, H-10), 4.63 (dd, 1H, J 11.0, 3.3 Hz, H-3), 4.23
(br s, 1H, H-4), 4.12 (m, 1H, H-50), 4.04 (dd, 1H, J
11.7, 5.9 Hz, H-6a), 3.94 (dm, 1H, J 12.1 Hz, H-6a),
3.81 (dd, 1H, J 5.5, 5.2 Hz, H-5), 3.71 (s, 3H, OCH3),
3.09 (br s, 1H, OH-4), 2.37 (br s, 1H, OH-6), 2.03 (s,
3H, COCH3), 1.94 (s, 3H, COCH3), 1.89 (s, 3H,
COCH3), 1.20 (d, 3H, J 6.2 Hz, CH3-60); 13C NMR
(CDCl3): d 170.0, 169.6, 169.5, 155.4, 150.6, 134.2,
131.4, 118.3, 114.5, 98.7 (C10), 97.8 (C1), 77.0 (C3),
74.3 (C5), 70.9 (C40), 69.7 (C20), 69.2 (C4), 68.5 (C30),
67.4 (C50), 62.6 (C6), 55.6 (OCH3), 51.7 (C2), 20.8
(COCH3), 20.6 (COCH3), 20.6 (COCH3), 17.4 (CH3-
60). HRMS calcd for C33H37NO15K+ 726.1800; found
726.1801.
3.5. p-Methoxyphenyl O-(2,3,4-tri-O-acetyl-a-L-rhamno-
pyranosyl)-(1!3)-4,6-O-benzylidene-2-deoxy-2-phthal-
imido-b-D-galactopyranoside (8)
To a mixture of 6 (336.1 mg, 0.67 mmol), 7 (376.0 mg,
˚
0.87 mmol), and 4 A molecular sieves (400 mg) in dried
CH2Cl2 (10 mL) was added TMSOTf (15.6 mg,
0.07 mmol) at ꢀ40 °C under Ar protection. The mixture
was stirred under these conditions for 1 h, then neutral-
ized with Et3N. The solid was filtered off, and the filtrate
was concentrated under vacuum to give a yellow syrup,
which was purified by column chromatography (2:1
3.7. p-Methoxyphenyl 2,3,4-tri-O-acetyl-a-L-rhamnopyr-
anosyl-(1!3)-4,6-di-O-acetyl-2-deoxy-2-phthalimido-b-
D-galactopyranoside (10)
Compound 9 (120.0 mg, 0.18 mmol) was dissolved in
pyridine (2 mL) and Ac2O (1 mL), and the mixture
was stirred overnight. Excess Ac2O was destroyed by
addition of CH3OH (5 mL). The mixture was concen-
trated and purified by chromatography (1:1 petroleum
ether–EtOAc) to afford compound 10 (122.3 mg,
90.8%) as a foamy solid: Rf 0.4 (3:2 petroleum ether–
petroleum ether–EtOAc) to give compound
8
(517.5 mg, 100%) as a white solid: Rf 0.20 (1:1 petro-
22
leum ether–EtOAc); ½aꢁD +43.6 (c 0.2, CHCl3); 1H
NMR (CDCl3): d 7.96–6.71 (m, 13H, Ph), 5.68 (d, 1H,
J 8.3 Hz, H-1), 5.59 (s, 1H, PhCH), 5.10 (dd, 1H, J
10.1, 3.2 Hz, H-30), 5.01 (dd, 1H, J 11.5, 8.7 Hz, H-2),
4.91 (dd, 1H, J 10.1, 9.6 Hz, H-40), 4.86 (d, 1H, J
1.9 Hz, H-10), 4.79 (dd, 1H, J 3.7, 1.9 Hz, H-20), 4.75
(dd, 1H, J 11.5, 3.7 Hz, H-3), 4.48 (d, 1H, J 3.2 Hz,
H-4), 4.40 (d, 1H, J 12.4 Hz, H-6a), 4.13 (m, 2H, H-
50, H-6b), 3.72 (s, 3H, OCH3), 3.68 (s, 1H, H-5), 1.98
(s, 3H, COCH3), 1.96 (s, 3H, COCH3), 1.84 (s, 3H,
COCH3), 0.98 (d, 3H, J 6.4 Hz, CH3-60); 13C NMR
(CDCl3): d 170.0, 169.7, 169.2, 167.4, 155.5, 150.8,
137.3, 134.3, 134.1, 131.6, 131.3, 129.1, 128.2, 126.3,
124.1, 123.2, 119.1, 114.3, 101.1 (PhCH), 98.9 (C10),
98.4 (C1), 76.5 (C3), 74.9 (C4), 70.7 (C40), 69.6 (C20),
69.2 (C6), 68.8 (C30), 67.0 (C50), 66.5 (C5), 55.5
(OCH3), 51.4 (C2), 20.7 (2COCH3), 20.5 (COCH3),
17.3 (CH3-60). HRMS: calcd for C40H41NO15Na+
798.2374; found 798.2363.
22
1
EtOAc); ½aꢁD +42.6 (c 0.2, CHCl3); H NMR (CDCl3):
d 7.93–6.71 (m, 8H, Ph), 5.61 (d, 1H, J 8.5 Hz,
H-1), 5.51 (br s, 1H, H-4), 5.07 (dd, 1H, J 9.9, 3.7 Hz,
H-30), 4.95 (dd, 1H, J 9.9, 9.8 Hz, H-40), 4.81
(m, 2H, H-2, H-3), 4.70 (dd, 1H, J 3.3, 1.9 Hz, H-20),
4.67 (d, 1H, J 1.9 Hz, H-10), 4.20 (m, 2H, H-6), 4.12
(dd, 1H, J 6.6, 6.2 Hz, H-5), 3.92 (dq, 1H, J 9.5,
6.2 Hz, H-50), 3.72 (s, 3H, OCH3), 2.30 (s, 3H, Ac),
2.08 (s, 3H, COCH3), 2.04 (s, 3H, COCH3), 1.89 (s,
3H, COCH3), 1.86 (s, 3H, COCH3), 1.94 (d, 3H,
J 6.2 Hz, CH3-60); 13C NMR (CDCl3): d 170.6, 170.5,
170.1, 169.5, 169.4, 155.6, 150.6, 134.2, 118.6, 114.4,
98.8 (C10), 98.0 (C1), 73.6 (C3), 71.5 (C5), 70.7 (C40),
70.0 (C20), 68.5 (C4), 68.1 (C30), 67.5 (C50), 62.0
(C6), 55.6 (OCH3), 52.8 (C2), 20.9 (COCH3), 20.8