The Journal of Organic Chemistry
Article
H-4 and H-5), 4.05 (t, J = 8.3 Hz, 1H, H-2), 3.63 (s, 3H, OCH3); 13
C
C5D5N) δ 195.6, 153.9, 129.9 (2C), 126.8, 122.3 (2C), 87.0, 79.8,
78.4, 74.9, 74.2, 71.1 24.3, 15.4; IR (solid) 3347, 2926, 1489, 1283,
1198, 1101, 1072, 1018 cm−1; MS (FAB) m/z (rel intensity) 361 (M +
H+, 5), 307 (30), 289 (15), 154 (100), 136 (70), 107 (20), 77 (15);
HRMS (FAB) calcd for C15H21O6S2 (M + H+) 361.0774, found
361.0812. Anal. Calcd for C15H20O6S2: C, 49.98; H, 5.59. Found: C,
49.68; H, 5.87.
NMR (100 MHz, C5D5N) δ 195.6, 153.9, 129.9 (2C), 126.8, 122.3
(2C), 105.6, 78.1, 74.8, 74.6, 71.1, 56.8; IR (solid) 3424, 2920, 1489,
1263, 1207, 1159, 1098, 1016 cm−1; MS (FAB) m/z (rel intensity)
331 (M + H+, 30), 307 (20), 289 (15), 177 (5), 154 (100), 136 (70),
107 (20), 77 (25); HRMS (FAB) calcd for C14H19O7S (M + H+)
331.0846, found 331.0845. Anal. Calcd for C14H18O7S: C, 50.90; H,
5.49. Found: C, 50.83; H, 5.37.
Methyl 6-O-(4-Tolyloxy)thiocarbonyl-β-D-glucopyranoside (6b,
Entry 5, Table 3). Major product 6b: 315.3 mg, 91% yield. Minor
Octyl 6-O-Phenoxythiocarbonyl-β-D-glucopyranoside (2b, Entry
1, Table 3). Major product 2b: 364.4 mg, 85% yield. Minor product
product 6a: 20.1 mg, 6% yield. White solid: Rf = 0.35 (MeOH/CHCl3,
1
10:90); mp 64−66 °C; [α]25 = −14.8 (c 1.05, CH3OH); H NMR
2a: 49.7 mg, 12% yield. White solid: Rf = 0.40 (MeOH/CHCl3,
D
1
10:90); mp 85−86 °C; [α]24 = −12.3 (c 1.03, CH3OH); H NMR
(400 MHz, C5D5N) δ 7.69 (br s, 1H, OH), 7.47 (br s, 1H, OH), 7.12
(d, J = 8.5 Hz, 2H, PhH), 7.07 (d, J = 8.5 Hz, 2H, PhH), 5.42 (d, J =
11.5 Hz, 1H, H-6a), 5.22 (dd, J = 11.5, 5.2 Hz, 1H, H-6b), 5.01 (br s,
1H, OH), 4.76 (d, J = 7.8 Hz, 1H, H-1), 4.30−4.15 (m, 2H, H-3, H-4
and H-5), 4.05 (t, J = 8.3 Hz, 1H, H-2), 3.64 (s, 3H, OCH3), 2.15 (s,
3H, 4-CH3-Ph); 13C NMR (100 MHz, C5D5N) δ 195.9, 151.9, 136.4,
130.4 (2C), 122.0 (2C), 105.7, 78.2, 74.9, 74.7, 74.6, 71.2, 56.8, 20.6;
IR (solid) 3368, 2918, 1506, 1285, 1219, 1190, 1034, 1015 cm−1; MS
(FAB) m/z (rel intensity) 345 (M + H+, 5), 307 (35), 289 (20), 165
(5), 154 (100), 136 (70), 107 (20), 77 (20); HRMS (FAB) calcd for
C15H21O7S (M + H+) 345.1014, found 345.1017. Anal. Calcd for
C15H20O7S: C, 52.31; H, 5.85. Found: C, 52.22; H, 5.98.
D
(400 MHz, C5D5N) δ 7.67 (br s, 1H, OH), 7.55−7.30 (m, 2H, PhH),
7.41 (br s, 1H, OH), 7.30−7.15 (m, 3H, PhH), 5.44 (d, J = 11.2 Hz,
1H, H-6a), 5.22 (dd, J = 11.2, 5.0 Hz, 1H, H-6b), 4.99 (br s, 1H, OH),
4.88 (d, J = 7.8 Hz, 1H, H-1), 4.30−4.00 (m, 5H, H-2, H-3, H-4, H-5
and OCH2(CH2)6CH3), 3.71 (dt, J = 16.1, 6.8 Hz, 1H,
OCH2(CH2)6CH3), 1.75−1.60 (m, 2H, OCH2CH2(CH2)5CH3),
1.40−1.25 (m, 2H, OCH2CH2CH2(CH2)4CH3), 1.25−1.05 (m, 8H,
OCH2CH2CH2(CH2)4CH3), 0.82 (t,
J = 7.0 Hz, 3H,
OCH2(CH2)6CH3); 13C NMR (100 MHz, C5D5N) δ 195.7, 154.0,
129.9 (2C), 126.8, 122.4 (2C), 104.8, 78.2, 75.0, 74.8, 74.7, 71.3, 70.0,
31.9, 30.2, 29.6, 29.4, 26.3, 22.8, 14.2; IR (solid) 3414, 2924, 1491,
1375, 1290, 1200, 1082, 1020 cm−1; MS (FAB) m/z (rel intensity)
429 (M + H+, 20), 299 (90), 281 (25), 154 (40), 145 (100), 127 (65),
85 (95), 57 (65); HRMS (FAB) calcd for C21H33O7S (M + H+)
429.1942, found 429.1960. Anal. Calcd for C21H32O7S: C, 58.86; H,
7.53. Found: C, 58.86; H, 7.78.
Methyl 6-O-(2-Naphthoxy)thiocarbonyl-β-D-glucopyranoside
(7b, Entry 6, Table 3). Major product 7b: 302.8 mg, 80% yield.
Minor product 7a: 12.6 mg, 3% yield. White solid: Rf = 0.35 (MeOH/
CHCl3, 10:90); mp 114−116 °C; [α]27 = −14.8 (c 1.22, CH3OH);
D
1H NMR (400 MHz, C5D5N) δ 7.89 (d, J = 8.8 Hz, 1H, NaphH),
Phenyl 6-O-Phenoxythiocarbonyl-β-D-glucopyranoside (3b, Entry
2, Table 3). Major product 3b: 266.7 mg, 68% yield. Minor product
3a: 54.6 mg, 14% yield. White solid: Rf = 0.35 (MeOH/CHCl3,
10:90); mp 140−141 °C; [α]26D = −65.5 (c 1.06, CH3OH); 1H NMR
(400 MHz, C5D5N) δ 8.00−7.80 (m, 2H, PhH and OH), 7.65 (br s,
1H, OH), 7.50−7.30 (m, 5H, PhH), 7.30−7.10 (m, 3H, PhH), 7.04 (t,
J = 7.1 Hz, 1H, PhH), 6.60 (d, J = 7.1 Hz, 1H, H-1), 5.39 (d, J = 11.5
Hz, 1H, H-6a), 5.25 (dd, J = 11.5, 5.9 Hz, 1H, H-6b), 5.02 (br s, 1H,
OH), 4.50−4.20 (m, 4H, H-2, H-3, H-4 and H-5); 13C NMR (100
MHz, C5D5N) δ 195.6, 158.6, 154.0, 129.9 (4C), 126.8, 122.5, 122.4
(2C), 117.0 (2), 102.2, 78.1, 74.8, 74.7, 74.4, 71.0; IR (solid) 3389,
2887, 1489, 1279, 1221, 1196, 1070, 1016 cm−1; MS (FAB) m/z (rel
intensity) 393 (M + H+, 10), 307 (20), 299 (10), 289 (15), 154 (100),
136 (70), 107 (20), 77 (20); HRMS (FAB) Calcd for C19H21O7S (M
+ H+) 393.1003, found 393.1015. Anal. Calcd for C19H20O7S: C,
58.15; H, 5.14. Found: C, 57.89; H, 5.31.
7.90−7.80 (m, 2H, NaphH), 7.63 (d, J = 2.4 Hz, 1H, NaphH), 7.60−
7.40 (m, 2H, NaphH), 7.37 (dd, J = 8.8, 2.4 Hz, 1H, NaphH), 5.46 (d,
J = 11.0 Hz, 1H, H-6a), 5.28 (dd, J = 11.0, 2.4 Hz, 1H, H-6b), 4.79 (d,
J = 7.8 Hz, 1H, H-1), 4.35−4.15 (m, 3H, H-3, H-4 and H-5), 4.08 (t, J
= 8.3 Hz, 1H, H-2), 3.66 (s, 3H, OCH3); 13C NMR (100 MHz,
C5D5N) δ 195.8, 151.5, 134.1, 132.1, 129.9, 128.2, 128.1, 127.1, 126.5,
121.9, 119.4, 105.7, 78.2, 74.9, 74.8, 74.7, 71.2, 56.8; IR (solid) 3352,
2913, 1510, 1448, 1290, 1103, 1080, 1034 cm−1; MS (FAB) m/z (rel
intensity) 381 (M + H+, 20), 307 (25), 289 (25), 154 (100), 136 (70),
117 (25), 77 (30); HRMS (FAB) calcd for C18H21O7S (M + H+)
381.1003, found 381.1020.
Methyl 6-O-(4-Chlorophenoxy)thiocarbonyl-β-D-glucopyranoside
(8b, Entry 7, Table 3). Major product 8b: 298.5 mg, 82% yield. Minor
product 8a: 12.4 mg, 4% yield. White solid: Rf = 0.30 (MeOH/CHCl3,
10:90); mp 136−138 °C; [α]25D = −13.6 (c 1.08, CH3OH); 1H NMR
(400 MHz, C5D5N) δ 7.71 (br s, 1H, OH), 7.50 (br s, 2H, OH), 7.40
(d, J = 9.0 Hz, 2H, 4-Cl-PhH), 7.13 (d, J = 9.0 Hz, 2H, 4-Cl-PhH),
5.39 (dd, J = 11.5 Hz, 1H, H-6a), 5.19 (d, J = 11.5, 4.5 Hz, 1H, H-6b),
4.76 (d, J = 7.6 Hz, 1H, H-1), 4.30−4.22 (m, 1H, H-3), 4.22−4.13 (m,
4-Nitrophenyl 6-O-Phenoxythiocarbonyl-β-D-glucopyranoside
(4b, Entry 3, Table 3). Major product 4b: 299.3 mg, 68% yield.
Minor product 4a: 79.5 mg, 18% yield. White solid: Rf = 0.35
(MeOH/CHCl3, 10:90); mp 66−69 °C; [α]25 = −111.4 (c 1.05,
D
2H, H-4 and H-5), 4.10−4.00 (m, 1H, H-2), 3.64 (s, 3H, OCH3); 13
C
CH3OH); 1H NMR (400 MHz, C5D5N) δ 8.24 (d, J = 9.0 Hz, 2H, 4-
NO2-PhH), 8.09 (br s, 1H, OH), 7.58 (br s, 1H, OH), 7.45−7.27 (m,
4H, 4-NO2-PhH and PhH), 7.27−7.10 (m, 3H, PhH), 5.81 (d, J = 7.3
Hz, 1H, H-1), 5.44 (dd, J = 11.5 Hz, H-6a), 5.26 (dd, J = 11.5, 5.8 Hz,
1H, H-6b), 5.03 (br s, 1H, OH), 4.60−4.47 (m, 1H, H-5), 4.47−4.20
(m, 3H, H-2, H-3 and H-4); 13C NMR (100 MHz, C5D5N) δ 195.6,
163.0, 154.0, 142.7, 130.0 (2C), 126.8, 126.1 (2C), 122.3 (2C), 116.8
(2C), 101.5, 78.0, 75.1, 74.5, 74.3, 70.8; IR (solid) 3366, 2895, 1591,
1514, 1344, 1240, 1198, 1016 cm−1; MS (FAB) m/z (rel intensity)
438 (M + H+, 5), 307 (30), 289 (15), 154 (100), 136 (75), 107 (20),
77 (15); HRMS (FAB) Calcd for C19H20NO9S (M + H+) 438.0853,
found 438.0841. Anal. Calcd for C19H19NO9S: C, 51.89; H, 4.38; N,
3.08. Found: C, 51.77; H, 4.23; N, 2.98.
NMR (100 MHz, C5D5N) δ 195.3, 152.4, 131.9, 130.0 (2C), 124.1
(2C), 105.7, 79.7, 78.1, 74.9, 74.7, 71.2, 56.9; IR (solid) 3374, 2922,
1485, 1285, 1196, 1084, 1032, 1011 cm−1; MS (FAB) m/z (rel
intensity) 365 (M + H+, 10), 307 (25), 289 (20), 221 (10), 154 (100),
136 (75), 107 (30); HRMS (FAB) calcd for C14H18ClO7S (M + H+)
365.0456, found 365.0488. Anal. Calcd for C14H17ClO7S: C, 46.09; H,
4.70. Found: C, 46.01; H, 4.38.
Methyl 6-O-(4-Fluorophenoxy)thiocarbonyl-β-D-glucopyranoside
(9b, Entry 8, Table 3). Major product 9b: 311.8 mg, 90% yield. Minor
product 9a: 19.9 mg, 6% yield. White solid: Rf = 0.30 (MeOH/CHCl3,
23
1
10:90); mp 57−59 °C; [α]D = −14.6 (c 1.04, CH3OH); H NMR
(400 MHz, C5D5N) δ 8.58 (br s, 1H, OH), 7.16 (d, J = 6.1 Hz, 4H, 4-
F-PhH), 5.40 (d, J = 11.2 Hz, 1H, H-6a), 5.20 (dd, J = 11.2, 5.3 Hz,
1H, H-6b), 4.76 (d, J = 7.6 Hz, 1H, H-1), 4.30−4.10 (m, 3H, H-3, H-4
and H-5), 4.05 (t, J = 8.3 Hz, 1H, H-2), 3.64 (s, 3H, OCH3); 13C
NMR (100 MHz, C5D5N) δ 195.7, 160.8 (d, J = 244.1 Hz), 150.1,
124.1 (d, J = 8.3 Hz, 2C), 116.5 (d, J = 24.0 Hz, 2C), 105.7, 78.1, 74.8
(2C), 74.6, 71.1, 56.8; IR (solid) 3362, 2903, 1501, 1283, 1213, 1184,
1082, 1011 cm−1; MS (FAB) m/z (rel intensity) 349 (M + H+, 25),
317 (25), 307 (15), 237 (20), 154 (100), 137 (55), 85 (35), 77 (20);
HRMS (FAB) calcd for C14H18FO7S (M + H+) 349.0752, found
Ethyl 6-O-Phenoxythiocarbonyl-β-D-thioglucopyranoside (5b,
Entry 4, Table 3). Major product 5b: 284.2 mg, 79% yield. Minor
product 5a: 18.1 mg, 5% yield. White solid: Rf = 0.32 (MeOH/CHCl3,
1
10:90); mp 89−90 °C; [α]26 = −31.3 (c 1.01, CH3OH); H NMR
D
(400 MHz, C5D5N) δ 7.38 (t, J = 7.8 Hz, 2H, PhH), 7.30−7.10 (m,
3H), 5.41 (dd, J = 11.5, 1.5 Hz, 1H, H-6a), 5.17 (dd, J = 11.5, 5.9 Hz,
1H, H-6b), 5.02 (d, J = 9.8 Hz, 1H, H-1), 4.30−4.10 (m, 3H, H-3, H-4
and H-5), 4.05 (t, J = 9.2 Hz, 1H, H-2), 3.00−2.73 (m, 2H,
SCH2CH3), 1.29 (t, J = 7.5 Hz, 3H, SCH2CH3); 13C NMR (100 MHz,
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dx.doi.org/10.1021/jo3024279 | J. Org. Chem. 2013, 78, 2336−2345