2046
K. YAMAMOTO et al.
J ¼ 3:3, 10.2 Hz, C300H), 3.74, 3.75, 3.76, 3.76, 3.76,
3.79 (each s, 3H, OCH3), 3.83 (dd, 1H, J ¼ 3:3, 10.3 Hz,
C20H), 3.86 (dd, 1H, J ¼ 3:2, 10.2 Hz, C200H), 3.89 (brd,
1H, J ¼ 3:3 Hz, C400H), 4.01 (dd, 1H, J ¼ 2:3, 10.3 Hz,
C30H), 4.37 (brd, 1H, J ¼ 2:3 Hz, C40H), 4.50 (d, 1H,
J ¼ 12:0 Hz, ArCHHO), 4.51 (d, 1H, J ¼ 12:4 Hz,
ArCHHO), 4.52 (s, 2H, ArCH2O), 4.56 (d, 1H, J ¼
12:0 Hz, ArCHHO), 4.61 (brs, 1H, C50H), 4.63, 4.67
(each d, 1H, J ¼ 11:4 Hz, ArCH2O), 4.69 (brs, 1H,
C5H), 4.75 (d, 1H, J ¼ 12:4 Hz, ArCHHO), 4.90 (d, 1H,
J ¼ 3:2 Hz, C100H), 4.94 (brd, 1H, J ¼ 2:4 Hz, C4H),
5.13 (d, 1H, J ¼ 3:3 Hz, C10H), 5.24 (s, 1H, ArCH), 5.34
(d, 1H, J ¼ 2:9 Hz, C1H), 5.67 (dd, 1H, J ¼ 2:9,
11.0 Hz, C2H), 5.71 (dd, 1H, J ¼ 2:4, 11.0 Hz, C3H),
6.76–6.88 (m, 10H, aromatic protons), 7.18 (brd, 2H,
J ¼ 8:7 Hz, aromatic protons), 7.25–7.37 (m, 12H,
aromatic protons), 7.48 (m, 2H, aromatic protons),
7.88 (brdd, 2H, J ¼ 1:3, 8.3 Hz, aromatic protons), 7.94
(brdd, 2H, J ¼ 1:4, 8.6 Hz, aromatic protons); 13C-
NMR (CDCl3) ꢃ: 51.52, 52.52, 55.13, 55.18, 55.18,
55.21, 55.23, 56.16 (each OCH3), 62.85 (C500), 68.35
(C3), 69.12 (C600), 69.57 (C5), 70.16 (C2), 71.23, 71.33,
72.30 (each ArCH2O), 72.63 (C50), 72.78 (ArCH2O),
73.00 (C200), 74.11 (C20), 74.48 (C400), 75.74 (C300),
76.14 (C4), 76.20 (C30), 76.33 (C40), 97.80 (C1), 98.82
(C10), 99.78 (C100), 100.59 (ArC(OR)2), 113.30, 113.45,
113.51, 113.53, 113.72, 127.61, 128.37, 128.49, 128.96,
129.00, 129.16, 129.16, 129.61, 129.72, 129.80, 129.90,
130.39, 130.40, 130.70, 130.83, 131.05, 133.24, 133.30,
158.86, 159.95, 159.07, 159.09, 159.84 (aromatic
carbons), 165.87, 165.87 (each ArC=O), 167.88,
168.06 (each C=O); FABMS (%, rel. int.) m=z: 1403
(4.2, ½M þ Naꢄþ), 121 (100, [CH3OPhCH2]þ), 105
(82, [PhCO]þ); FAB-HRMS: calcd. for C75H80O25Na
½M þ Naꢄþ, 1403.4886; found, m=z 1403.4907.
(d, 1H, J ¼ 12:1 Hz, ArCHHO), 4.65 (d, 1H, J ¼
0:9 Hz, C50H), 4.65, 4.68 (each d, 1H, J ¼ 12:1 Hz,
ArCH2O), 4.68 (brs, 1H, C5H), 4.70 (d, 1H, J ¼ 12:1
Hz, ArCHHO), 4.81 (brs, 1H, C100H), 4.91 (brd, 1H,
J ¼ 2:1 Hz, C4H), 5.06 (d, 1H, J ¼ 3:3 Hz, C10H),
5.35 (d, 1H, J ¼ 2:8 Hz, C1H), 5.66 (dd, 1H, J ¼ 2:8,
10.9 Hz, C2H), 5.70 (dd, 1H, J ¼ 2:1, 10.9 Hz, C3H),
6.78–6.81 (m, 4H, aromatic protons), 6.81–6.89 (m, 4H,
aromatic protons), 7.18–7.21 (m, 4H, aromatic protons),
7.26–7.36 (m, 8H, aromatic protons), 7.48 (m, 2H,
aromatic protons), 7.88 (brdd, 2H, J ¼ 1:3, 8.3 Hz,
aromatic protons), 7.95 (brdd, 2H, J ¼ 1:3, 8.3 Hz,
aromatic protons); 13C-NMR (CDCl3) ꢃ: 51.68, 52.54,
55.12, 55.21, 55.21, 55.25, 56.19 (each OCH3),
62.96 (C600), 68.39 (C3), 69.09 (C400), 69.61 (C5),
69.70 (C500), 70.23 (C2), 71.37 (C50), 72.20, 72.57,
72.63, 73.01 (each ArCH2O) 73.79 (C20), 74.82 (C200 or
300), 76.18 (C30), 76.53 (C4), 77.20 (C200 or 300), 77.81
(C40), 97.82 (C1), 99.21 (C100), 99.25 (C10), 113.61,
113.61, 113.79, 113.82, 128.38, 128.46, 129.00, 129.20,
129.36, 129.56, 129.69, 129.69, 129.74, 129.88, 130.13,
130.28, 130.56, 130.59, 133.22, 133.31, 159.07, 159.09,
159.25, 159.28 (aromatic carbons), 165.86, 165.94
(each ArC=O), 167.99, 168.02 (each C=O); FABMS
(%, rel. int.) m=z: 1285 (0.6, ½M þ Naꢄþ), 121 (100,
[CH3OPhCH2]þ); FAB-HRMS: calcd. for C67H74O24Na
½M þ Naꢄþ, 1285.4468; found, m=z 1285.4490.
A suspension of the product (20.0 mg, 15.8 mmol) in
CH2Cl2 (1.0 ml) was stirred with PhI(OAc)2 (26.2 mg,
81.3 mmol) and TEMPO (1.2 mg, 7.7 mmol) at room
temperature for 30 min. The mixture was poured into
H2O (20 ml) and extracted with AcOEt (15 ml ꢃ 3).
The organic layers were washed with brine (15 ml),
combined, dried over MgSO4, and then concentrated
in vacuo. After diluting with a mixture of 2-methyl-2-
propanol (0.5 ml) and 2-methyl-2-butene (4.4 mg, 63.0
mmol), sodium dihydrogenphosphate dehydrate (14.8
mg, 94.9 mmol) and sodium chlorite (5.7 mg, 63.0 mmol)
were successively added at room temperature. After
stirring for 30 min, the mixture was poured into H2O
(20 ml) and extracted with AcOEt (15 ml ꢃ 3). The
organic layers were washed with brine (15 ml), com-
bined, dried over MgSO4, and then concentrated in
vacuo. After diluting with THF (1.0 ml), an ethereal
solution of diazomethane was added until the yellow
color did not disappear. After concentrating in vacuo,
silica gel column chromatography (AcOEt:hexane =
40:60) of the residue gave 14 (14.0 mg, 68%) as an oil,
Methyl {methyl 2,3-di-O-benzoyl-4-O-{20,30-bis-O-
(4-methoxyphenylmethyl)-40-O-[200,300-bis-O-(4-methoxy-
phenylmethyl)-600-methyl-ꢀ-D-galactopyranuronosyl]-60-
methyl-ꢀ-D-galactopyranuronosyl}-ꢀ-D-galactopyrano-
sid}uronate (14). A solution of 13 (21.1 mg, 15.4 mmol)
in 90% aqueous acetic acid solution (1.0 ml) was stirred
at 50 ꢀC for 20 min. After cooling, the mixture was
concentrated in vacuo. Silica gel column chromatogra-
phy of the residue (AcOEt:hexane = 70:30) gave the
23
corresponding diol (15.4 mg, 79%) as an oil, ½ꢀꢄD
+75.0 (c 0.84, CHCl3); IR (film) cmꢁ1: 3450, 2935,
1730, 1510, 1250, 1095, 1030, 710; 1H-NMR (CDCl3) ꢃ:
2.33 (brd, 1H, J ¼ 8:9 Hz, C600OH), 2.51 (brs, 1H,
C400OH), 3.04 (s, 3H, OCH3), 3.48 (m, 1H, C600HH),
3.49 (s, 3H, OCH3), 3.57–3.65 (m, 3H, C600HH, C200H,
C300H), 3.70, 3.73, 3.75, 3.76, 3.79 (each s, 3H, OCH3),
3.83 (dd, 1H, J ¼ 3:3, 10.3 Hz, C20H), 3.87–3.90
(m, 2H, C400H, C500H), 4.03 (dd, 1H, J ¼ 2:5, 10.3 Hz,
C30H), 4.27 (dd, 1H, J ¼ 0:9, 2.5 Hz, C40H), 4.43
(d, 1H, J ¼ 12:1 Hz, ArCHHO), 4.45 (d, 1H,
J ¼ 10:6 Hz, ArCHHO), 4.51 (d, 1H, J ¼ 12:1 Hz,
ArCHHO), 4.53 (d, 1H, J ¼ 10:6 Hz, ArCHHO), 4.59
23
½ꢀꢄD +67.2 (c 0.75, CHCl3); IR (film) cmꢁ1: 3450,
2935, 1730, 1510, 1250, 1100, 1030, 820, 715; 1H-NMR
(CDCl3) ꢃ: 2.92, 3.49 (each s, 3H, OCH3), 3.54 (dd, 1H,
J ¼ 3:2, 10.0 Hz, C300H), 3.59 (s, 3H, OCH3), 3.62
(d, 1H, J ¼ 3:0, 10.0 Hz, C200H), 3.70, 3.74, 3.74, 3.79,
3.80 (each s, 3H, OCH3), 3.28 (dd, 1H, J ¼ 3:3, 10.5 Hz,
C20H), 4.03 (dd, 1H, J ¼ 2:2, 10.5 Hz, C30H), 4.23 (brd,
1H, J ¼ 3:2 Hz, C400H), 4.25 (brd, 1H, J ¼ 2:2 Hz,
C40H), 4.39 (d, 1H, J ¼ 12:3 Hz, ArCH2O), 4.43 (s,
2H, ArCH2O), 4.52 (d, 1H, J ¼ 12:3 Hz, ArCH2O), 4.55