Med Chem Res
added dropwise and the resulting clear solution was con-
centrated under reduced pressure. The solution was trans-
ferred to silica gel chromatography (ethyl acetate/hexane,
2:8) to give the corresponding sulfide 14.
7.48–7.00 (m, 17H, Ar), 5.50 (d, J = 3.2 Hz, 1H, H-1), 4.89
(d, J = 11.2 Hz, 1H, –OCHAHBPh), 4.77 (d, J = 10.8 Hz,
1H, –OCHAHBPh), 4.69–4.45 (m, 4H, the remaining
–OCH2Ph), 4.13–4.00 (m, 1H, H-3), 3.80–3.48 (m, 5H, H-
4, H-5, H-6a, H-6b, and H-7a), 3.34 (dd, J = 3.0 and 13.0
1-O-Acetyl-3,4,6-tri-O-benzyl-2-deoxy-2-C-(4-pro-
pylbenzene)thiomethyl-α and -β-D-glucopyranosyl (14a):
Hz,
1H,
H-7b),
2.54
(t,
J = 7.8 Hz,
2H,
colorless oil, 94% (2.58 g), IR (neat cm−1): 1750, 1491,
–SArCH2(CH2)4CH3), 2.15–2.00 (m, 1H, H-2), 1.98 (s, 3H,
OAc), 1.64–1.50 (m, 2H, –SArCH2CH2(CH2)3CH3),
1.40–1.20 (m, 6H, –SArCH2CH2(CH2)3CH3), 0.98–0.75
(m, 3H, –SArCH2(CH2)4CH3); 13C NMR (100 MHz,
CDCl3) δ: α-anomer 160.3 (C=O), 140.8, 138.3, 138.1,
137.8, 132.6, 129.9, 129.1, 128.5, 128.4, 128.0, 127.8,
127.7 (Ar), 92.5 (C-1), 80.2 (C-3), 79.8 (C-4), 75.3 (C-5),
74.8 (–OCH2Ph), 73.5 (–OCH2Ph), 70.8 (–OCH2Ph), 68.9
(C-6), 45.7 (C-2), 35.5 (–SArCH2(CH2)4CH3), 31.7 (C-7),
31.4, 28.9, 22.6 (–SArCH2(CH2)4CH3), 20.1 (OAc), 14.1
(–SArCH2(CH2)4CH3). HRMS (ESI): m/z [M + Na+] calcd
for C42H50NaO6S: 705.3220; found: 705.3218.
1-O-Acetyl-3,4,6-tri-O-benzyl-2-deoxy-2-C-(4-octylben-
zene)thiomethyl-α and -β-D-glucopyranosyl (14d): a color-
less oil, 83% (1.64 g), IR (neat cm−1): 1750, 1500, 1460,
1131, 610; 1H NMR (400 MHz, CDCl3) δ: α-anomer
7.50–7.02 (m, 19H, Ar), 6.40 (bs, 1H, H-1), 4.98 (d, J =
11.2 Hz, 1H, –OCHAHBPh), 4.79 (d, J = 10.4 Hz, 1H,
–OCHAHBPh), 4.75–4.42 (m, 4H, the remaining
–OCH2Ph), 3.95–3.62 (m, 5H, H-3, H-4, H-5, H-6a, and H-
6b), 3.38 (d, J = 13.2 Hz, 1H, H-7a), 2.56 (t, J = 12.4 Hz,
1H, H-7b), 2.51 (t, J = 7.8 Hz, 2H, –SArCH2(CH2)6CH3),
2.95–2.18 (m, 1H, H-2), 2.05 (s, 3H, OAc), 1.63–1.30 (m,
12H, –SArCH2(CH2)6CH3), 0.91 (t, J = 6.4 Hz, 3H,
–SArCH2(CH2)6CH3); δ: β-anomer 5.68 (d, J = 8.8 Hz, 1H,
H-1), 3.27 (d, J = 11.6 Hz, 1H, H-7a), 3.15 (d, J = 12.8 Hz,
1H, H-7b), 2.0 (s, 3H, OAc); 13C NMR (100 MHz, CDCl3)
δ: α-anomer 169.0 (C=O), 138.3, 137.9, 137.5, 136.2,
132.0, 130.6, 130.0, 128.4, 128.3, 128.0, 127.8, 127.8 (Ar),
92.1 (C-1), 78.9 (C-4), 78.8 (C-3), 75.4 (C-5), 75.0
(–OCH2Ph), 73.5 (–OCH2Ph), 73.0 (–OCH2Ph), 68.1 (C-6),
44.3 (C-2), 35.6 (–SArCH2(CH2)6CH3), 31.8 (–SArCH2
CH2CH2(CH2)4CH3), 32.0 (–SAr(CH2)3CH2CH2(CH2)2
CH3), 31.4 (C-7), 28.9 (–SAr(CH2)5CH2CH2CH3), 22.6
(–SAr(CH2)6CH2CH3), 20.9 (OAc), 14.1 (–SAr(CH2)7
CH3). HRMS (ESI): m/z [M + Na+] calcd for C44H54NaO6
S: 733.3533; found: 733.3530.
1
1449, 1091, 680; H NMR (400 MHz, CDCl3) δ: β-anomer
7.43–7.12 (m, 19 H, Ar), 5.67 (d, J = 8.8 Hz, 1H, H-1), 4.91
(d, J = 10.8 Hz, 1H, –OCHAHBPh), 4.78 (d, J = 10.8 Hz,
1H, –OCHAHBPh), 4.66 (d, J = 9.4 Hz, 1H, –OCHAHBPh),
4.63 (d, J = 9.4 Hz, 1H, –OCHAHBPh), 4.60–4.42 (m, 2H,
–OCH2Ph), 3.92–3.54 (m, 5 H, H-3, H-4, H-5, H-6a, and H-
6b), 3.26 (dd, J = 4.2 and 13.4 Hz, 1H, H-7a), 3.14 (dd, J =
3.2 and 13.2 Hz, 1H, H-7b), 2.53 (t, J = 7.6 Hz, 2H,
–SArCH2CH2CH3), 2.32–2.17 (m, 1H, H-2), 1.96 (s, 3H,
OAc), 1.70–1.51 (m, 2H, –SArCH2CH2CH3), 0.92 (t, J =
7.2 Hz, 3H, –SArCH2CH2CH3); δ: α-anomer 6.41 (d, J =
3.2 Hz, 1H, H-1), 4.95 (d, J = 11.6 Hz, 1H, –OCHAHBPh),
3.41 (dd, J = 3.4 and 13.8 Hz, 1H, H-7a), 2.03 (s, 3H, OAc);
13C NMR (100 MHz, CDCl3) δ: β-anomer 168.8 (C=O),
141.4, 138.1, 137.9, 133.3, 129.5, 129.2, 128.5, 128.4, 128.3,
128.0, 127.8, 127.7, 127.6 (Ar), 93.2 (C-1), 80.3 (C-3),
79.0 (C-4), 75.4 (C-5), 75.2 (–OCH2Ph), 74.6 (–OCH2Ph),
73.5 (–OCH2Ph), 68.2 (C-6), 46.2 (C-2), 37.5 (–SArCH2CH2
CH3), 32.1 (C-7), 24.4 (–SArCH2CH2CH3), 20.9 (OAc),
13.8 (ArCH2CH2CH3); δ: α-anomer 160.0 (C=O), 137.8,
130.4, 128.4, 128.3, 128.0, 127.8, 127.6 (Ar), 92.0 (C-1),
78.8 (C-3), 75.3 (–OCH2Ph), 74.9 (–OCH2Ph), 44.4 (C-2),
31.3 (C-7). HRMS (ESI): m/z [M + Na+] calcd for
C39H44NaO6S: 663.2751; found: 663.2750.
1-O-Acetyl-3,4,6-tri-O-benzyl-2-deoxy-2-C-[4-(2-
methylbutyl)benzene]thiomethyl-α and -β-D-glucopyranosyl
(14b): colorless oil, 87% (2.20 g), IR (neat cm−1): 1752,
1
1496, 1455, 1130, 698; H NMR (400 MHz, CDCl3) δ: α-
anomer 7.48–7.00 (m, 19H, Ar), 6.39 (d, J = 2.8 Hz, 1H, H-
1), 4.93 (d, J = 11.2 Hz, 1H, –OCHAHBPh), 4.76 (d, J =
10.6 Hz, 1H, –OCHAHBPh), 4.67 (d, J = 11.2 Hz, 1H,
–OCHAHBPh), 4.61 (d, J = 12.0 Hz, 1H, –OCHAHBPh),
4.51 (d, J = 10.6 Hz, 1H, –OCHAHBPh), 4.46 (d, J = 12.0
Hz, 1H, –OCHAHBPh), 3.83–3.50 (m, 6H, H-3, H-4, H-5,
H-6a, H-6b, and H-7a), 3.39 (dd, J = 2.8 and 13.6 Hz, 1H,
H-7b), 2.65–2.42 (m, 1H, –SArCHAHBCHCH3CH2CH3),
2.38–2.17 (m, 2H, H-2, and –SArCHAHBCHCH3CH2CH3),
2.03 (s, 3H, OAc), 1.70–1.51 (m, 1H, –SArCH2CHCH3
CH2CH3), 1.47–1.10 (m, 2H, –SArCH2CHCH3CH2CH3),
0.94–0.70 (m, 6H, –SArCH2CHCH3CH2CH3). HRMS
(ESI): m/z [M + Na+] calcd for C41H48NaO6S: 691.3064;
found: 691.3061.
1-O-Acetyl-3,4,6-tri-O-benzyl-2-deoxy-2-C-(4-octade-
cylbenzene)thiomethyl-α and -β-D-glucopyranosyl (14e):
colorless oil, 89% (0.53 g), IR (neat cm−1): 1753, 1650,
1
1501, 1460, 1131, 1030, 1009, 689; H NMR (400 MHz,
CDCl3) δ: β-anomer 7.48–7.00 (m, 19 H, Ar), 6.39 (d, J =
3.2 Hz, 1H, H-1), 4.93 (d, J = 11.2 Hz, 1H, –OCHAHBPh),
4.76 (d, J = 10.8 Hz, 1H –OCHAHBPh), 4.66 (d, J = 11.2
Hz, 1H, –OCHAHBPh), 4.61 (d, J = 12.0 Hz, 1H,
–OCHAHBPh), 4.52 (d, J = 10.8 Hz, 1H, –OCHAHBPh),
4.46 (d, J = 12.0 Hz, 1H, –OCHAHBPh), 3.82–3.56 (m, 6H,
1-O-Acetyl-3,4,6-tri-O-benzyl-2-deoxy-2-C-(4-hex-
ylbenzene)thiomethyl-α and -β-D-glucopyranosyl (14c):
colorless oil, 86% (1.91 g), IR (neat cm−1): 1753, 1501,
1460, 1131, 699; 1H NMR (400 MHz, CDCl3) δ: α-anomer