S. Yan et al. / Carbohydrate Research 354 (2012) 6–20
15
(20 mL) at room temperature under Ar atmosphere, and the mix-
ture was then stirred at the same temperature followed by TLC.
After the completion of the reaction, BzCl (0.70 mL, 6.0 mmol)
was added dropwise to the reaction mixture, and then catalytic
DMAP added. The reaction was monitored by TLC, after comple-
tion, methanol (2 mL) added and the mixture concentrated under
vacuum, then the residue diluted with CH2Cl2 (50 mL). The organic
layer was washed sequentially with 1 M HCl (10 mL ꢀ 2) and then
brine (20 mL ꢀ 2) and dried over anhydrous Na2SO4. The solvent
was removed under vacuum, and the residue was purified by flash
½
a 2D5 +91.3 (c 0.5 CHCl3); 1H NMR (400 MHz, CDCl3) d: 7.97–7.70
ꢁ
(m, 12H, Ar-H), 7.68–7.28 (m, 24H, Ar-H), 7.25–7.13 (m, 5H, Ar-
H), 6.96 (t, J = 7.6 Hz, 2H, Ar-H), 6.87–6.79 (m, 3H, Ar-H), 6.72–
6.65 (m, 4H, Ar-H), 6.00 (d, J = 2.6 Hz, 1H, H-4’), 5.68 (t, J = 9.6 Hz,
1H, H-3), 5.61–5.51 (m, 3H), 5.18 (d, J = 7.6 Hz, 1H, H-1), 5.01 (d,
J = 7.8 Hz, 1H, H-1’), 4.52 (t, J = 9.6 Hz, 1H), 3.97–3.90 (m, 3H),
3.73 (s, 3H, –OCH3), 3.52 (dd, J = 9.7, 5.3 Hz, 1H), 3.41 (d,
J = 9.5 Hz, 1H), 3.10 (t, J = 9.7 Hz, 1H), 1.19 (s, 9H, –C(CH3)3), 0.94
(s, 9H, –C(CH3)3); 13C NMR (100 MHz, CDCl3) d: 165.50 (COPh),
165.45 (COPh), 165.28 (COPh), 165.18 (COPh), 164.57 (COPh),
155.60, 151.22, 136.00, 135.95, 135.65, 135.55, 135.50, 135.46,
133.52, 133.15, 133.07, 132.75, 132.57, 132.34, 132.05, 130.40,
130.06, 129.99, 129.94, 129.87, 129.84, 129.65, 129.59, 129.51,
129.45, 129.43, 129.10, 128.98, 128.48, 128.43, 128.37, 128.26,
128.22, 128.14, 127.99, 127.83, 127.79, 127.58, 119.17, 114.41
(Ar-C), 100.87 (C-1), 100.20 (C-1’), 75.33, 73.39, 73.16, 72.75,
72.06, 71.94, 70.23, 67.18, 60.96, 59.70, 55.64, 27.02 (3)
(–C(CH3)3), 26.57 (3) (–C(CH3)3), 19.55, 18.87; HRMS calcd for
C86H84O17Si2Na (M+Na)+: 1467.5139, found: 1467.5128.
column chromatography to afford 27 (1.06 g, 82%): ½a D25
ꢁ
+18.8 (c
0.5 CHCl3);1H NMR (400 MHz, CDCl3) d: 7.91–7.79 (m, 6H, Ar-H),
7.70 (dd, J = 12.4, 5.7 Hz, 4H, Ar-H), 7.63–7.59 (m, 2H, Ar-H), 7.54
(t, J = 7.5 Hz, 1H, Ar-H), 7.46 (t, J = 7.4 Hz, 1H, Ar-H), 7.42–7.19
(m, 10H, Ar-H), 7.01–6.96 (m, 2H, Mp-Ar-H), 6.78–6.72 (m, 2H,
Mp-Ar-H), 6.32 (dd, J = 10.7, 9.3 Hz, 1H, H-3), 6.05 (d, J = 8.4 Hz,
1H, H-1), 5.72 (t, J = 9.7 Hz, 1H, H-4), 4.84 (dd, J = 10.7, 8.5 Hz,
1H, H-2), 4.10 (ddd, J = 10.0, 5.1, 2.1 Hz, 1H, H-5), 3.94–3.85
(m,2H, H-6), 3.74 (s, 3H, –OCH3), 1.07 (s, 9H, –C(CH3)3); 13C NMR
(100 MHz, CDCl3) d: 165.83 (COPh), 165.04 (COPh), 155.59,
150.84, 135.64 (2), 135.50 (2), 134.24 (2), 133.25 (2), 133.01,
132.77, 131.44, 129.86 (2), 129.79 (2), 129.64, 129.60, 129.13,
128.68, 128.37 (2), 128.32 (2), 127.80, 127.66 (2), 127.63 (2),
123.68 (2), 118.95 (2), 114.47 (2) (Ar-C), 97.65 (C-1), 75.37,
71.47, 69.60, 62.66, 55.63, 55.01, 26.62 (3) (–C(CH3)3), 19.17;
4.34. p-Methoxyphenyl 2,3,4-tri-O-benzoyl-b-
-galactopyranosyl (1?4)-2,3-di-O-benzoyl-b-D-glucopyranoside
(30)
D
Product 30 was obtained from 29 (722 mg, 0.5 mmol) following
the procedure C. The pure product 30 was obtained by column
chromatography on silica gel as a white foam (339 mg, 70%):
½
HRMS calcd for
884.2850.
C
51H47O10NSiNa (M+Na)+: 884.2861, found:
a 2D5 +61.3 (c 0.5 CHCl3); 1H NMR (400 MHz, CDCl3) d: 8.04 (t,
ꢁ
4.32. p-Methoxyphenyl 3,4-Di-O-benzoyl-2-deoxy-2-
phthalimdo-b- -glucopyranoside (28)
J = 8.0 Hz, 4H, Ar-H), 7.96 (d, J = 7.9 Hz, 2H, Ar-H), 7.85 (d,
J = 7.0 Hz, 2H, Ar-H), 7.79 (d, J = 7.4 Hz, 2H, Ar-H), 7.69 (t,
J = 7.4 Hz, 1H, Ar-H), 7.60–7.50 (m, 4H, Ar-H), 7.45–7.36 (m, 6H,
Ar-H), 7.25 (t, J = 7.8 Hz, 2H, Ar-H), 7.10 (t, J = 7.8 Hz, 2H, Ar-H),
6.87 (d, J = 8.9 Hz, 2H, Mp-Ar-H), 6.75 (d, J = 9.1 Hz, 2H, Mp-Ar-
H), 5.83–5.71 (m, 2H), 5.70–5.59 (m, 2H), 5.54–5.43 (m, 1H), 5.16
(d, J = 7.7 Hz, 1H, H-1), 5.01 (t, J = 8.7 Hz, 1H), 4.35 (t, J = 9.4 Hz,
1H), 3.91–3.78 (m, 3H), 3.73 (s, 3H, –OCH3), 3.61 (d, J = 9.7 Hz,
1H), 2.99–2.88 (m, 1H), 2.74 (dd, J = 12.0, 6.8 Hz, 1H); 13C NMR
(100 MHz, CDCl3) d: 166.41 (COPh), 165.46 (COPh), 165.28 (COPh),
165.27 (COPh), 164.92 (COPh), 155.68, 150.97, 133.84, 133.48,
133.33, 133.31, 133.04, 130.16, 129.89, 129.80, 129.76, 129.73,
129.49, 129.16, 129.02, 128.69, 128.58, 128.42, 128.33, 128.25,
118.56, 114.57 (Ar-C), 100.85 (C-1), 100.63 (C-1’), 75.27, 74.70,
73.89, 73.21, 71.90, 71.53, 70.35, 68.53, 60.35, 59.83, 55.61; HRMS
calcd for C54H48O17Na (M+Na)+: 991.2784, found: 991.2768.
D
Product 28 was obtained from 27 (862 mg, 1.0 mmol) following
the procedure C. The pure product 28 was obtained by column
chromatography on silica gel as a white foam (548 mg, 88%):
½
a 2D5 +11.7 (c 0.5 CHCl3); 1H NMR (400 MHz, CDCl3) d: 7.95 (d,
ꢁ
J = 7.8 Hz, 2H, Ar-H), 7.79 (m, 4H, Ar-H), 7.67 (m, 2H, Ar-H), 7.51
(t, J = 7.4 Hz, 1H, Ar-H), 7.44–7.33 (m, 3H, Ar-H), 7.27 (m, 2H, Ar-
H), 6.91 (d, J = 9.0 Hz, 2H, Mp-Ar-H), 6.76 (d, J = 9.0 Hz, 2H, Mp-
Ar-H), 6.40 (t, J = 10.0 Hz, 1H, H-3), 6.08 (d, J = 8.5 Hz, 1H, H-1),
5.60 (t, J = 9.6 Hz, 1H,H-4), 4.81 (dd, J = 10.6, 8.6 Hz, 1H, H-2),
4.03–3.95 (m, 1H), 3.92–3.83 (m, 1H), 3.76 (d, J = 12.7 Hz, 1H),
3.72 (s, 3H, –OCH3), 2.68 (br, 1H, –OH); 13C NMR (100 MHz, CDCl3)
d: 165.96 (COPh), 165.65 (COPh), 155.67, 150.45, 134.28 (2),
133.66, 133.34, 131.29, 129.91 (2), 129.74 (2), 128.51, 128.47 (2),
128.33 (2), 123.65 (2), 118.77 (2), 114.53 (2) (Ar-C), 97.52 (C-1),
74.64, 70.84, 69.88, 61.31, 55.56, 54.76; HRMS calcd for
35H29O10NNa (M+Na)+: 646.1684, found: 646.1690.
4.35. Phenyl 2,3,4-tri-O-benzoyl-b-
2,3-di-O-benzoyl-1-thio-b- -glucopyranoside (32)
D-galactopyranosyl (1?4)-
C
D
4.33. p-Methoxyphenyl 2,3,4-tri-O-benzoyl-6-O-tert-
butyldiphenylsiyl-b- -galactopyranosyl (1?4)-2,3-di-O-
benzoyl-6-O-tert-butyldiphenylsiyl-b- -gluco pyranoside (29)
Product 32 was obtained from 31 (715 mg, 0.5 mmol) following
the procedure C. The pure product 32 was obtained by column
chromatography on silica gel as a white foam (372 mg, 78%):
D
D
½
a 2D5 +68.9 (c 0.5 CHCl3);1H NMR (400 MHz, CDCl3) d: 7.98 (t,
ꢁ
TBDPSCl (0.55 mL, 2.2 mmol) was added to a stirred mixture of
p-Methoxyphenyl b- -galactopyranosyl (1?4)-b- -glucopyrano-
J = 8.1 Hz, 4H, Ar-H), 7.84 (t, J = 8.8 Hz, 4H, Ar-H), 7.65 (t,
J = 7.5 Hz, 1H, Ar-H), 7.55–7.45 (m, 7H, Ar-H), 7.42–7.24 (m, 12H,
Ar-H), 7.15 (t, J = 7.8 Hz, 2H, Ar-H), 5.74 (t, J = 9.5 Hz, 1H, H-3),
5.47 (d, J = 3.2 Hz, 1H, H-4’), 5.43 (t, J = 9.8 Hz, 1H, H-2), 5.24 (dd,
J = 10.1, 3.3 Hz, 1H, H-3’), 4.99 (d, J = 10.0 Hz, 1H, H-1’), 4.67 (d,
J = 7.6 Hz, 1H, H-1), 4.27 (t, J = 9.6 Hz, 1H, H-2’), 4.10–4.01 (m,
3H), 3.74 (d, J = 9.8 Hz, 1H), 3.52 (t, J = 6.8 Hz, 1H), 3.30 (br, 1H,
–OH), 2.89 (s, 1H), 2.84 (s, 1H), 2.50 (br, 1H, –OH); 13C NMR
(100 MHz, CDCl3) d: 166.31 (COPh), 166.00 (COPh), 165.53 (COPh),
165.16 (COPh), 133.74, 133.35, 133.31, 133.21, 132.88 (2), 131.88,
129.96 (2), 129.83 (2), 129.73 (2), 129.47 (2), 129.44 (2), 129.10,
129.03 (2), 128.99, 128.79, 128.54 (2), 128.37 (3), 128.31 (3) (Ar-
C), 103.46 (C-1’), 86.28 (C-1), 79.29, 75.55, 74.99, 73.83, 73.28,
D
D
side (448 mg, 1.0 mmol) and imidazole (306 mg, 4.5 mmol) in
dry Py (20 mL) at room temperature under Ar atmosphere, and
the mixture was then stirred at the same temperature followed
by TLC. After the completion of the reaction, BzCl (1.41 mL,
12.0 mmol) was added dropwise to the reaction mixture, and then
catalytic DMAP added. The reaction was monitored by TLC, after
completion, methanol (2 mL) added and the mixture concentrated
under vacuum, then the residue diluted with CH2Cl2 (50 mL). The
organic layer was washed sequentially with 1 M HCl (10 mL ꢀ 2)
and then brine (20 mL ꢀ 2) and dried over anhydrous Na2SO4.
The solvent was removed under vacuum, and the residue was puri-
fied by flash column chromatography to afford 29 (910 mg, 63%):