3826
S. Noguchi et al. / Bioorg. Med. Chem. 19 (2011) 3812–3830
4.79 (1H, d, J = 10.5 Hz, ArCHHO), 5.31 (1H, d, J = 2.9 Hz, C40H), 6.76
(2H, br d, J = 8.6 Hz, aromatic protons), 6.81–6.89 (10H, aromatic
protons), 7.12 (2H, br d, J = 8.6 Hz, aromatic protons), 7.15 (2H, br
d, J = 8.6 Hz, aromatic protons), 7.21-7.30 (8H, aromatic protons)
114.23 (aromatic carbons), 129.19 (C500a), 129.46, 129.48, 129.48,
129.48, 129.64, 129.77, 129.81, 129.85, 130.01, 130.03, 130.04,
130.08, 130.12, 130.74, 131.12, 131.22, 131.27, 131.37, 131.44,
131.48, 131.57, 131.77, 131.89, 131.90, 132.18, 132.46 (aromatic
carbons), 134.65 (C500), 159.49, 159.49, 159.56, 159.56, 159.60,
159.60, 159.62, 159.67, 159.67, 159.70, 159.77, 159.80, 159.80
(aromatic carbons), ESIMS (%, rel int.) m/z: 2253.9740 (6, calcd for
4.24. Methyl [2,3,4-6-tetrakis-O-(4-methoxyphenylmethyl)-b-
D-
glucopyranosyl-(1?4)-b-(2,3,6-tris-O-(4-methoxy
phenylmethyl)-1-thio-
D
5,5acarbaglucopyranosyl)-(1?4)-b-
C
130H148O32
S
[M+H]+: 2253.9753), 2271.0003 (9, calcd for
(2,3,6-tris-O-(4-methoxyphenylmethyl)-b-
D
-glucopyrano syl)-
C
130H152NO32S [M+NH4]+: 2271.0018).
(1?4)-b-(2,3,6-tris-O-(4-methoxyphenylmethyl)-b-D-
glucopyranoside] (21)
4.25. Methyl [b-
carbaglucopyranosyl)-(1?4)-b-(b-
D
-glucopyranosyl-(1?4)-b-(1-thio-D5,5a
-glucopyranosyl)-(1?4)-b-
D
A crude 15 prepared from thioacetate 14 (60 mg, 48
similar manner as described in Section 4.19 and the triflate 20
(51.9 mg, 90 mol) in THF (0.5 mL) was stirred with NaH (2.3 mg,
96 mol) at 0 °C for 40 min. The mixture was poured into H2O
l
mol) in a
(b-D-glucopyranoside)] (2)
l
In a similar manner as described in Section 4.21, 21 (103 mg,
46 lmol) was treated employing DDQ (275 mg, 1.19 mmol),
l
(50 mL) and extracted with EtOAc (25 mL ꢂ 3). The combined or-
ganic layer was washed with brine (25 mL), dried over MgSO4
and then concentrated in vacuo. Silica gel column chromatography
of the residue (35% EtOAc/hexane) gave 21 (76.5 mg, 70%) as an oil.
CH2Cl2 (3.0 mL), and H2O (0.3 mL). The work-up that then followed
gave 2 (20 mg 62%) as white amorphous powder. ½a D28
ꢃ ꢀ37.9
(c 1.24, H2O); 1H NMR (500 MHz, D2O) d 2.59 (1H, t, J = 10.6 Hz,
C40H), 3.14 (1H, dd, J = 8.0, 9.3 Hz, C2H), 3.17 (1H, dd, J = 8.0,
9.3 Hz, C20H), 3.18 (1H, dd, J = 8.0, 9.3 Hz, C2000H), 3.25 (1H, dd,
J = 9.2, 9.7 Hz, C4000H), 3.35 (1H, ddd, J = 2.2, 5.6, 12.2 Hz, C5000H),
3.36 (1H, t, J = 9.2 Hz, C3000H), 3.37 (1H, dd, J = 9.3, 10.6 Hz, C30H),
3.39 (1H, br d, J = 9.0 Hz, C100H), 3.41 (3H, s, C1OCH3), 3.42–3.48
(4H, C3H, C4H, C5H, C50H), 3.48 (1H, dd, J = 9.0, 10.0 Hz, C200H),
3.56 (1H, dd, J = 7.5, 10.0 Hz, C300H), 3.57 (1H, dd, J = 5.6, 12.3 Hz,
C6000HH), 3.65 (1H, dd, J = 4.6, 12.2 Hz, C6HH), 3.76 (1H, dd,
J = 2.2, 12.3 Hz, C6000HH), 3.80 (1H, dd, J = 5.4, 12.2 Hz, C60HH),
3.82 (1H, dd, J = 2.0, 12.2 Hz, C6HH), 3.97 (1H, dd, J = 1.5, 12.2 Hz,
C60HH), 3.97 (1H, br d, J = 13.6 Hz, C600HH), 4.13 (1H, br d,
J = 13.6 Hz, C600HH), 4.24(1H, br d, J = 7.5 Hz, C400H), 4.24 (1H, d,
J = 8.0 Hz, C1H), 4.32 (1H, d, J = 8.0 Hz, C10H), 4.48 (1H, d,
J = 8.0 Hz, C1000H), 5.68 (1H, br s, C500aH); 13C NMR (125 MHz,
D2O) d 55.73 (C40), 56.38 (C100), 65.02 (C1OCH3), 67.81 (C6), 68.42
(C6000), 69.14, 69.16 (C60 or C600), 77.28 (C4000), 80.64 (C2), 81.19
(C2000), 81.26 (C200), 81.96 (C20), 82.02 (C30), 82.13 (C3), 82.53 (C5),
82.63 (C300), 83.48 (C3000), 83.86 (C5000), 84.23 (C50), 86.46 (C4),
89.91 (C400), 110.15 (C10), 110.86 (C1 or C1000), 110.89 (C1 or C1000),
134.31 (C500a), 144.13 (C500); ESIMS (%, rel int.) m/z: 693.2275 (58,
calcd for C26H45O19S [M+H]+: 693.2276), 715.2094 (100, calcd for
C26H44O19NaS [M+Na]+: 715.2095).
½
a 2D7
ꢃ
+0.5 (c 1.67, CHCl3); IR (film) 2910, 1610, 1510, 1465, 1250,
1070, 815 cmꢀ1 1H NMR (500 MHz, C6D6) d 3.21 (1H, m, C40H),
;
3.22, 3.280, 3.288, 3.289, 3.291, 3.291, 3.298, 3.301, 3.305, 3.312
(each 3H, ArOCH3), 3.318 (1H, m, C30H), 3.330, 3.331 (each 3H, Ar-
OCH3), 3.35 (1H, m, C50H), 3.36, 3.40 (each 3H, ArOCH3), 3.40 (1H,
ddd, J = 1.7, 3.5, 9.3 Hz, C5H), 3.44 (1H, ddd, J = 1.9, 4.6, 9.2 Hz,
C5000H), 3.50 (1H, dd, J = 8.0, 8.6 Hz, C20H), 3.60 (1H, dd, J = 7.9,
8.9 Hz, C2000H), 3.66 (1H, dd, J = 7.6, 8.9 Hz, C2H), 3.678 (1H, dd,
J = 4.6, 11.0 Hz, C6000HH), 3.684 (1H, dd, J = 8.9, 9.2 Hz, C3000H),
3.718 (1H, t, J = 8.2 Hz, C200H), 3.721 (1H, br d, J = 11.3 Hz, C600HH),
3.747 (1H, dd, J = 1.9, 11.0 Hz, C6000HH), 3.750 (1H, t, J = 9.2 Hz,
C4000H), 3.787 (1H, dd, J = 8.9, 9.3 Hz, C3H), 3.788 (1H, dd, J = 1.7,
10.7 Hz, C6HH), 3.94 (1H, dd, J = 1.0, 10.5 Hz, C60HH), 4.01 (1H,
dd, J = 1.8, 8.2 Hz, C100H), 4.09 (1H, dd, J = 3.5, 10.7 Hz, C6HH),
4.12 (1H, dd, J = 96.1, 8.2 Hz, C300H), 4.22 (1H, dd, J = 3.5, 10.5 Hz,
C60HH), 4.24 (1H, d, J = 11.2 Hz, ArCHHO), 4.32 (1H, dd, J = 7.6
Hz, C1H), 4.33 (1H, d, J = 11.6 Hz, ArCHHO), 4.37 (1H, t, J = 9.3 Hz,
C4H), 4.41 (1H, d, J = 11.5 Hz, ArCHHO), 4.41 (1H, d, J = 11.5 Hz,
ArCHHO), 4.47 (1H, d, J = 11.2 Hz, ArCHHO), 4.48 (1H, d, J =
11.5 Hz, ArCHHO), 4.50 (1H, d, J = 11.5 Hz, ArCHHO), 4.56 (1H, d,
J = 11.0 Hz, ArCHHO), 4.58 (1H, d, J = 11.6 Hz, ArCHHO), 4.67 (1H,
br d, J = 11.3 Hz, C600HH), 4.68 (1H, d, J = 8.0 Hz, C10H), 4.70 (1H,
d, J = 10.6 Hz, ArCHHO), 4.76 (1H, d, J = 11.0 Hz, ArCHHO), 4.79
(1H, d, J = 10.5 Hz, ArCHHO), 4.81 (1H, d, J = 11.1 Hz, ArCHHO),
4.87 (1H, d, J = 11.0 Hz, ArCHHO), 4.89 (1H, d, J = 10.8 Hz, ArCHHO),
4.90 (1H, d, J = 11.0 Hz, ArCHHO), 4.91 (1H, br d, J = 6.1 Hz, C400H),
4.955 (1H, d, J = 11.4 Hz, ArCHHO), 4.959 (1H, d, J = 11.3 Hz, ArCH-
HO), 4.965 (1H, d, J = 10.6 Hz, ArCHHO), 4.971 (1H, d, J = 10.5 Hz,
ArCHHO), 4.99 (1H, d, J = 11.1 Hz, ArCHHO), 5.03 (1H, d,
J = 7.9 Hz, C1000H), 5.06 (1H, d, J = 10.8 Hz, ArCHHO), 5.07 (1H, d,
J = 10.8 Hz, ArCHHO), 5.14 (1H, d, J = 10.8 Hz, ArCHHO), 5.26 (1H,
d, J = 11.3 Hz, ArCHHO), 5.41 (1H, d, J = 11.4 Hz, ArCHHO), 6.23
(1H, br d, J = 1.8 Hz, C500aH), 6.75-6.91 (26H, aromatic protons),
7.24-7.36 (18H, aromatic protons), 7.40 (2H, br d, J = 8.7 Hz, aro-
matic protons), 7.47 (2H, br d, J = 8.7 Hz, aromatic protons), 7.56
(2H, br d, J = 8.7 Hz, aromatic protons), 7.59 (2H, br d, J = 8.7 Hz, aro-
matic protons); 13C NMR (125 MHz, C6D6) d 48.96 (C100) 50.07 (C40)
54.62, 54.67, 54.70, 54.70, 54.70, 54.70, 54.73, 54.73, 54.73, 54.73,
54.77, 54.80 (each 3H, ArOCH3), 56.52 (C1OCH3), 68.30 (C6), 69.19
(C6000), 69.73 (C60), 71.12 (C600), 71.74, 73.00, 73.13, 73.29, 74.40,
74.47, 74.70, 74.78, 74.85, 74.91, 75.28 (each ArCH2O), 75.56
(C5000), 75.71 (C5), 76.13 (ArCH2O), 76.51 (C400), 77.12 (C4), 77.53
(C50), 78.25 (C4000), 80.57 (C200), 81.98 (C2) 82.64 (C300), 82.77 (C3),
83.05 (C2000), 83.53 (C30), 83.95 (C20), 85.06 (C3000), 102.76 (C10),
103.87 (C1000), 105.27 (C1), 113.86, 113.86, 113.90, 113.93,
113.94, 113.99, 114.01, 114.01, 114.05, 114.05, 114.07, 114.20,
4.26. Methyl [2,3,4-6-tetra-O-acetyl-b-
b-(2,3,6-O-triacetyl-1-thio-
5,5acarbaglucopyranosyl)-(1?4)-b-
(2,3,6-tri-O-acetyl-b- -glucopyranoside)] (22)
D-glucopyranosyl-(1?4)-
D
D
A mixture of 1b (5.2 mg, 9.8
idine (200 g, 1.6 mol) in a mixture of pyridine (1.0 mL) and ace-
tic anhydride (200 L) at 60 °C for 2 h. After concentration in
lmol) and 4-(dimethylamino)pyr-
l
l
l
vacuo, silica gel column chromatography of the residue with
EtOAc/hexane = 80:20 gave 22 (7.8 mg, 87%). ½a D23
ꢃ ꢀ52 (c 0.56,
CDCl3),IR (film) 2940, 1750, 1225, 1040 cmꢀ1 1H NMR (500 MHz,
,
C6D6) d 1.66, 1.67, 1.69, 1.77, 1.79, 1.82, 1.84, 1.89, 1.93, 1.97 (each
3H, s, OCOCH3), 2.84 (1H, dd, J = 10.0, 11.0 Hz, C4H), 2.92 (1H, ddd,
J = 1.9, 4.5, 11.0 Hz, C5H), 3.21 (3H, s, C1OCH3), 3.46 (1H, ddd,
J = 2.1, 4.6, 10.1 Hz, C500H), 3.54 (1H, br dd, J = 3.7, 10.0 Hz, C10H),
4.04 (1H, d, J = 7.6 Hz, C1H), 4.05 (1H, br d, J = 4.4 Hz, C40H), 4.09
(1H, dd, J = 2.1, 12.4 Hz, C600HH), 4.31 (1H, dd, J = 4.5, 12.0 C6HH),
4.37 (1H, dd, J = 4.6, 12.4, C600HH), 4.54 (1H, d, J = 8.1 Hz, C100H),
4.58 (2H, br d, J = 7.8 Hz, C60H2), 4.63 (1H, dd, J = 1.9, 12.4 Hz,
C6HH), 5.21 (1H, dd, J = 8.1, 9.4 Hz, C200H), 5.21 (1H, dd, J = 7.6,
9.4 Hz, C2H), 5.23 (1H, dd, J = 9.4, 10.1 Hz, C400H), 5.25 (1H, dd,
J = 9.4, 10.0 Hz, C3H)5.37 (1H, t, J = 9.4 Hz, C300H), 5.40 (1H, dd,
J = 5.0, 6.6 Hz, C20H), 5.77 (1H, dd, J = 4.4, 6.6 Hz, C30H), 5.92 (1H,
br d, J = 3.7 Hz, C5aH), 13C NMR (125 MHz, C6D6) d 20.08, 20.13,
20.28, 20.32, 20.35, 20.36, 20.41, 20.45 (each COCH3), 20.54