ꢀ ꢀ
L. Lazar et al. / Tetrahedron 68 (2012) 7386e7399
7397
H-2, H-4, H-5), 3.08, 2.85 (2s, 2H, 2ꢂOH) ppm; 13C NMR (CDCl3,
3.83 (d, 1H, J 10.5 Hz), 3.63e3.57 (m, 5H), 3.49e3.35 (m, 9H), 3.17
(dd, 1H, J 9.6, 9.4 Hz), 3.07 (dd, 1H, J 3.5, 9.8 Hz), 2.07, 2.01 (2s, 6H,
90 MHz):
d
¼134.1, 133.7, 132.8, 131.3 (4ꢂCq arom), 133.0e123.6
(12C, arom),102.0 (PhCH), 88.6 (C-1), 80.2, 74.5, 72.6, 70.5 (skeleton
carbons), 68.6 (C-6) ppm. Anal. Calcd for C23H22O5S (410.48): C,
67.30; H, 5.40; S, 7.81. Found: C, 67.57; H, 5.44; S, 7.89.
2ꢂCH3) ppm; 13C NMR (CDCl3, 90 MHz):
¼169.7, 169.5 (2ꢂCO),
d
137.9, 135.7, 133.1, 132.8, 131.8 (5ꢂCq arom), 132.8e125.6 (17C,
arom), 97.8 (C-10), 85.1 (C-1), 83.0, 81.6, 79.1, 79.0, 75.7, 74.2, 71.1,
70.4 (skeleton carbons), 73.3, 73.1 (2ꢂCH2Ph), 68.6, 68.2 (C-6, C-60),
60.6, 60.3, 59.2 (3ꢂOCH3), 20.9, 20.7 (2ꢂCH3) ppm. Anal. Calcd for
C43H50O12S (790.91): C, 65.30; H, 6.37; S, 4.05. Found: C, 65.27; H,
6.54; S, 3.88.
4.40. Phenyl 2,3-di-O-acetyl-4,6-O-(20-naphthyl)methylene-1-
thio-b-D-glucopyranoside (42)
Compound 41 (3.00 g, 7.31 mmol) was converted to 42 accord-
ing to general method A to give 3.29 g (91%) of 42 as a white
4.43. Methyl (6-O-benzyl-2,3,4-tri-O-methyl-a- -
powder. The product was recrystallized from EtOAc; mp
glucopyranosyl)-(1/4)-[2,3-di-O-acetyl-6-O-(20D-naphthyl)
25
199e202 ꢁC; [
a
]
D
ꢀ57.2 (c 0.20, CHCl3); Rf 0.35 (8:2 n-hexane/
methyl-b-
D-glucopyranosyl]-(1/4)-2,6-di-O-benzyl-3-deoxy-
EtOAc); IR nmax (KBr): 3437, 3060, 2943, 2871, 1747, 1480, 1440,
3-C-(methyl sulfonatomethyl)-a-D-glucopyranoside (45)
1373, 1236, 1098, 1076, 1035, 902, 826, 748, 690, 613, 484 cmꢀ1; 1H
NMR (CDCl3, 360 MHz):
d
¼7.89e7.33 (m, 12H, arom), 5.63 (s, 1H,
Compound 7 (200 mg, 0.423 mmol) was glycosylated with 44
(402 mg, 0.508 mmol) according to general method B. The crude
product was purified by silica gel chromatography (95:5 CH2Cl2/
PhCH), 5.37 (dd, 1H, J2,3 9.0 Hz, J3,4 8.7 Hz, H-3), 5.03 (dd, 1H, J1,2
9.8 Hz, J2,3 9.0 Hz, H-2), 4.82 (d, 1H, J1,2 9.8 Hz, H-1), 4.45e4.39 (m,
1H, H-6a), 3.83 (dd, 1H, J 9.1, 9.8 Hz, H-6b), 3.71 (dd, 1H, J3,4 8.7 Hz,
J4,5 9.1 Hz, H-4), 3.64e3.58 (m, 1H, H-5), 2.10, 2.03 (2s, 6H, 2ꢂCH3)
acetone) to give 45 (354 mg, 73%) as a colourless syrup; [
a]
25 þ62.1
D
(c 0.38, CHCl3); Rf 0.50 (6:4 n-hexane/acetone); IR nmax (KBr): 3445,
ppm; 13C NMR (CDCl3, 90 MHz):
d¼170.0, 169.4 (2ꢂCO), 134.0,
2933, 2359, 2342, 1756, 1455, 1361, 1240, 1218, 1162, 1101, 1042,
133.6, 132.7, 131.7 (4ꢂCq arom), 132.9e123.6 (12C, arom), 101.6
(PhCH), 86.5 (C-1), 78.1, 72.8, 70.7, 70.6 (skeleton carbons), 68.6 (C-
6), 20.7, 20.7 (2ꢂCH3) ppm. Anal. Calcd for C27H26O7S (494.56): C,
65.57; H, 5.30; S, 6.48. Found: C, 65.26; H, 5.48; S, 6.51.
996, 900, 856, 819, 784, 741, 699, 590, 477 cmꢀ1 1H NMR (CDCl3,
;
360 MHz):
d
¼7.83e7.79 (m, 4H, arom), 7.47e7.21 (18H, arom),
5.13e5.09 (m, 2H, H-100, H-30), 4.84 (dd, 1H, J1 ,2 8.1 Hz, J2 ,3 9.5 Hz,
0
0
0
0
H-20), 4.76e4.64 (m, 4H, H-1, CH2NAP, PhCH2), 4.54 (s, 2H, PhCH2),
0
0
4.45, 4.44 (2d, 2ꢂ1H, J 12.2, 12.2 Hz, PhCH2), 4.36 (d, 1H, J1 ,2
4.41. Phenyl 2,3-di-O-acetyl-6-O-(20-naphthyl)methyl-1-thio-
b-D-glucopyranoside (43)
8.1 Hz, H-10), 4.28 (d, 1H, J 12.1 Hz, PhCH2), 4.10 (dd, 1H, J 10.0,
10.3 Hz), 4.03e3.88 (m, 3H), 3.78e3.57 (m, 13H), 3.48e3.29 (m,
13H), 3.18 (t, 1H, J 9.5, 9.5 Hz), 3.06 (dd, 1H, J 3.3, 9.7 Hz), 2.55e2.47
(m, 1H, H-3), 2.00, 1.93 (2s, 6H, 2ꢂCH3) ppm; 13C NMR (CDCl3,
To a solution of 42 (1.57 g, 3.17 mmol) in dry CH2Cl2 (23 mL) at
0 ꢁC, Et3SiH (6.07 mL, 38.0 mmol) and BF3$Et2O (782
L,
m
90 MHz):
d¼169.7, 169.1 (2ꢂCO), 137.8, 137.8, 137.4, 135.8, 133.1,
6.34 mmol) was added. The reaction mixture was stirred at room
temperature for 4 h. The mixture was diluted with CH2Cl2 (150 mL),
washed with satd NaHCO3 (2ꢂ50 mL) and H2O (50 mL), then dried
and concentrated. The crude product was purified by silica gel
132.7 (6ꢂCq arom), 128.5e125.6 (22C, arom), 100.0 (C-10), 97.5 (C-
1), 95.9 (C-100), 82.9, 81.7, 79.0, 75.8, 74.6, 74.6, 74.6, 73.8, 71.9, 71.0,
70.4 (skeleton carbons), 73.4, 73.0, 73.0, 71.7 (4ꢂCH2Ph), 68.3, 68.1,
67.3 (C-6, C-60, C-600), 60.5, 60.1, 58.8, 55.3, 54.9 (5ꢂOCH3), 46.1
(CH2SO3), 38.4 (C-3), 20.8, 20.5 (2ꢂCH3) ppm. Anal. Calcd for
C60H74O20S (1147.28): C, 62.81; H, 6.50; S, 2.79. Found: C, 62.69; H,
6.33; S, 2.66.
chromatography (96:4 CH2Cl2/acetone) to give 43 as a colourless
25
syrup (1.29 g, 82%); [
a
]
D
ꢀ29.3 (c 1.26, CHCl3); Rf 0.22 (7:3 n-hex-
ane/acetone); IR nmax (KBr): 3453, 3057, 2868, 1751, 1631, 1479,
1440, 1372, 1240, 1050, 907, 820, 750, 691, 608, 475 cmꢀ1; 1H NMR
(CDCl3, 360 MHz):
d
¼7.82e7.75 (m, 4H, arom), 7.50e7.41 (m, 5H,
4.44. Methyl (6-O-benzyl-2,3,4-tri-O-methyl-
glucopyranosyl)-(1/4)-(2,3-di-O-acetyl- -glucopyranosyl)-
(1/4)-2,6-di-O-benzyl-3-deoxy-3-C-(methyl
sulfonatomethyl)- -glucopyranoside (46)
a-D-
arom), 7.25e7.23 (m, 3H, arom), 5.08 (t, 1H, J2,3 9.2 Hz, J3,4 9.2 Hz,
H-3), 4.94 (dd, 1H, J 9.8, 9.4 Hz, H-2), 4.75e4.67 (m, 3H, H-1,
CH2NAP), 3.81 (d, 2H, J 4.5 Hz, H-6a,b), 3.73 (ddd, 1H, J4,OH 4.1 Hz, J
9.5, 9.3 Hz, H-4), 3.59e3.54 (m, 1H, H-5), 3.12 (d, 1H, J4,OH 4.2 Hz,
OH), 2.07, 2.05 (2s, 6H, 2ꢂCH3) ppm; 13C NMR (CDCl3, 90 MHz):
b-D
a-D
To a vigorously stirred solution of 45 (150 mg, 0.131 mmol) in
CH2Cl2 (1.8 mL) and H2O (0.2 mL) was added DDQ (45.0 mg,
0.197 mmol). After 30 min the mixture was diluted with CH2Cl2
(50 mL) and extracted with satd aq NaHCO3 (2ꢂ10 mL), H2O
d
¼171.2, 169.5 (2ꢂCO), 135.0, 133.1, 132.9, 132.2 (4ꢂCq arom),
132.4e125.5 (12C, arom), 85.6 (C-1), 78.5, 76.6, 70.0, 69.9 (skeleton
carbons), 73.7 (CH2Ph), 69.8 (C-6), 20.7, 20.7 (2ꢂCH3) ppm. Anal.
Calcd for C27H28O7S (496.57): C, 65.31; H, 5.68; S, 6.46. Found: C,
65.17; H, 5.60; S, 6.31.
(10 mL), dried, and concentrated. Column chromatography (91:9
25
CH2Cl2/acetone) gave 46 (111 mg, 84%) as a colourless oil; [a]
D
þ45.8 (c 0.04, CHCl3); Rf 0.48 (9:1 CH2Cl2/acetone); IR nmax (KBr):
4.42. Phenyl (6-O-benzyl-2,3,4-tri-O-methyl-
glucopyranosyl)-(1/4)-2,3-di-O-acetyl-6-O-(20-naphthyl)
methyl-1-thio- -glucopyranoside (44)
a
-
D
-
3454, 2938, 1755, 1633, 1455, 1371, 1242, 1160, 1102, 1038, 993, 899,
742, 699 cmꢀ1
;
1H NMR (CDCl3, 360 MHz):
d
¼7.42e7.28 (m, 15H,
b
-D
arom), 5.14e5.09 (m, 2H, H-100, H-30), 4.79 (dd, 1H, J 8.4, 7.3 Hz,
H-20), 4.73 (d, 1H, J 11.9 Hz, PhCH2), 4.69 (d, 1H, J1,2 3.1 Hz, H-1), 4.65
(d, 1H, J 12.1 Hz, PhCH2), 4.59 (s, 2H, PhCH2), 4.500, 4.46 (2d, 2ꢂ1H, J
Compound 43 (600 mg, 1.21 mmol) was glycosylated with 14
(587 mg, 1.45 mmol) according to general method B. The crude
product was purified twice by silica gel chromatography using first
0
0
12.3,11.7 Hz, PhCH2), 4.43 (d,1H, J1 ,2 7.6 Hz, H-1 ), 4.35 (t,1H, J 10.4,
10.4 Hz), 3.98e3.52 (m, 18H), 3.45e3.37 (m, 7H), 3.28e3.10 (m, 7H),
2.46e2.39 (m, 1H, H-3), 2.00, 1.91 (2s, 6H, 2ꢂCH3) ppm; 13C NMR
n-hexane/EtOAc (7:3), and then CH2Cl2/acetone (95:5) as eluents to
25
give 44 (678 mg, 71%) as a colourless oil; [
a]
þ30.9 (c 0.37,
(CDCl3, 90 MHz):
d¼169.7, 169.3 (2ꢂCO), 138.0, 137.9, 137.4 (3ꢂCq
D
CHCl3); Rf 0.39 (95:5 CH2Cl2/acetone); IR nmax (KBr): 3444, 1634,
1219, 772, 685, 674 cmꢀ1; 1H NMR (CDCl3, 360 MHz):
¼7.85e7.75
(m, 4H, arom), 7.52e7.42 (m, 5H, arom), 7.30e7.21 (m, 8H, arom),
arom), 128.6e127.5 (15C, arom), 99.5 (C-10), 97.8 (C-1), 96.1 (C-100),
83.2, 81.4, 79.2, 75.8, 75.2, 75.1, 73.6, 72.5, 71.5, 71.2, 70.7 (skeleton
carbons), 73.5, 73.4, 71.8 (3ꢂCH2Ph), 68.4, 67.4 (C-6, C-600), 60.3 (C-
60), 60.6, 60.3, 59.3, 55.3, 55.0 (5ꢂOCH3), 45.2 (CH2SO3), 39.3 (C-3),
20.9, 20.6 (2ꢂCH3) ppm. Anal. Calcd for C49H66O20S (1007.10): C,
58.44; H, 6.61; S, 3.18. Found: C, 58.27; H, 6.58; S, 3.12.
d
0
0
0
5.32 (t, 1H, J2,3 9.2 Hz, J3,4 9.2 Hz, H-3), 5.11 (d, 1H, J1 ,2 3.5 Hz, H-1 ),
4.92 (dd, 1H, J 9.7, 9.5 Hz, H-2), 4.72e4.65 (m, 3H, H-1, CH2NAP),
4.44, 4.27 (2d, 2ꢂ1H, J 12.1, 12.1 Hz, CH2Ph), 3.98e3.90 (m, 2H),