JOURNAL OF CHEMICAL RESEARCH 2017 363
17β-Hydroxy-17-methylandrost-4-en-3-one (1dd): Light yellow
solid; m.p. 160–162 °C; yield 144 mg (>99%).
1- (4,6-O- (4-Fluorobenzylidene) -β-d -glucopyranosyl) -2-
propanone (2d'd'): White solid; m.p. 187–188 °C; yield 181 mg
(93%); IR (KBr) (νmax cm−1): 3501, 2984, 2906, 2831, 1710, 1607,
1512, 1376, 1082, 1020, 829; 1H NMR (400 MHz, CDCl3): δ 7.54–7.43
(m, 2H), 7.07 (t, J = 8.5 Hz, 2H), 5.50 (s, 1H), 4.30 (d, J = 10.3 Hz,
1H), 3.93–3.82 (m, 1H), 3.80–3.70 (m, 1H), 3.65 (t, J = 8.0 Hz, 1H),
3.53–3.32 (m, 3H), 3.10 (bs, 2H), 2.91 (d, J = 16.3 Hz, 1H), 2.68 (dd,
J = 16.1, 7.2 Hz, 1H), 2.22 (s, 3H); 13C NMR (101 MHz, DMSO):
δ 207.0, 163.9–161.5 (d, JCF = 244.7 Hz), 134.70–134.67 (d, JCF = 3.0
Hz), 129.0–128.9 (d, JCF = 8.4 Hz), 115.4–115.2 (d, JCF = 21.5 Hz),
100.4, 81.5, 77.1, 74.7, 74.4, 70.5, 68.4, 46.7, 30.7; 19F NMR (376 MHz,
DMSO): δ −113.1. HRMS (ESI) found: m/z 349.1060 [M + Na]+; calcd
for C16H19FO6Na+: 349.1063.
Phenyl 4,6-O-(4-fluorobenzylidene)-β-d-glucopyranoside (2hh):
White solid; m.p. 155–157 °C; yield 162 mg (83%); IR (KBr) (νmax
cm−1): 3559, 3388, 2883, 1602, 1502, 1230, 1087, 1019, 830; 1H NMR
(400 MHz, DMSO): δ 7.51 (dd, J = 8.6, 5.7 Hz, 2H), 7.31 (t, J = 8.0 Hz,
2H), 7.22 (t, J = 8.9 Hz, 2H), 7.10–6.98 (m, 3H), 5.63 (s, 1H), 5.62 (s,
1H), 5.47 (d, J = 5.1 Hz, 1H), 5.12 (d, J = 7.7 Hz, 1H), 4.22 (dd, J = 9.4,
4.2 Hz, 1H), 3.74–3.53 (m, 3H), 3.47 (t, J = 9.0 Hz, 1H), 3.41–3.34 (m,
1H); 13C NMR (101 MHz, DMSO): δ 164.0–161.5 (d, JCF = 244.7 Hz),
157.6, 134.63–134.60 (d, JCF = 2.9 Hz), 129.9, 129.1–129.0 (d,
JCF = 8.5 Hz), 122.6, 116.8, 115.5–115.3 (d, JCF = 21.5 Hz), 101.0, 100.4,
80.8, 74.6, 73.3, 68.3, 66.2; 19F NMR (376 MHz, DMSO): δ −113.0.
HRMS (ESI) found: m/z 385.1061 [M + Na]+; calcd for C19H19FO6Na+:
385.1063.
Methyl α-d-glucopyranoside (1ee): White solid; m.p. 162–164 °C
(lit.49 165–166 °C); yield 120 mg (95%).
5-Methyluridine (1ff): White solid; m.p. 182–184 °C (lit.50
181–182 °C); yield 129 mg (93%).
4-Iodo-butanol (1gg): Yellow oil; yield 106 mg (83%).
4-Iodobutyl (3β)-3-hydroxyurs-12-en-28-oate (1hh): Colourless
syrup; yield 148 mg (87%); IR (KBr) (νmax cm−1): 3449, 2926, 2870,
1721, 1455, 1382, 1228; 1H NMR (400 MHz, CDCl3): δ 5.25 (t,
J = 3.2 Hz, 1H), 4.08–3.95 (m, 2H), 3.26–3.17 (m, 3H), 2.22 (d, J = 11.3
Hz, 1H), 2.02–1.87 (m, 5H), 1.75–1.46 (m, 14H), 1.37–1.25 (m, 9H),
1.08 (s, 3H), 0.99 (s, 3H), 0.95–0.90 (m, 6H), 0.86 (d, J = 6.4 Hz, 3H),
0.78 (s, 3H), 0.75 (s, 3H); 13C NMR (101 MHz, CDCl3): δ 177.5, 138.2,
125.6, 78.9, 63.0, 55.2, 52.8, 48.1, 47.5, 42.0, 39.5, 39.1, 38.9, 38.7, 38.6,
37.0, 36.8, 33.0, 30.7, 30.3, 29.7, 29.6, 28.2, 28.0, 27.2, 24.2, 23.6, 23.3,
21.2, 18.3, 17.2, 17.1, 15.7, 15.5, 6.0. HRMS (ESI) found: m/z 661.3087
[M + Na]+; calcd for C34H55IO3Na+: 661.3088.
Methyl 4,6-O-benzylidene-α-d-glucopyranoside (2aa): White solid;
m.p. 163–165 °C (lit.9 168–169 °C); yield 159 mg (87%).
3,9-Diphenyl-2,4,8,10-tetraoxaspiro[5,5]undecane (2bb): White
solid; m.p. 161–163 °C (lit.9 160–162 °C); yield 156 mg (91%).
Methyl 4,6-O-benzylidene-α-d-galactopyranoside (2cc): White
solid; m.p. 169–170 °C (lit.9 202–204 °C); yield 156 mg (95%).
1-(4,6-O-Benzylidene-β-d-glucopyranosyl)-2-propanone
(2dd):
White solid; m.p. 150–151 °C (lit.52 152–154 °C); yield 151 mg (82%).
4-Methylphenyl
4,6-O-(4-fluorobenzylidene)-1-thio-β-d-gluco-
1,2,3,6,2',3'-Hexa-O-acetyl-4',6'-benzylidene-β-d-lactose
White solid, m.p. 212–215 °C; yield 187 mg (97%).
2-(4-Flurophenyl)-4-phenyl-1,3-dioxolane (2ff): Colourless oil;
yield 139 mg (72%), a mixture of two diastereomers.
(2ee):
pyranoside (2ii): White solid; m.p. 150–151 °C; yield 164 mg (84%);
IR (KBr) (νmax cm−1): 3442, 2973, 2870, 1607, 1511, 1459, 1377, 1104,
1006, 830, 807; 1H NMR (400 MHz, CDCl3): δ 7.50–7.39 (m, 4H), 7.15
(d, J = 7.9 Hz, 2H), 7.04 (t, J = 8.7 Hz, 2H), 5.50 (s, 1H), 4.74 (bs, 2H),
4.56 (d, J = 9.7 Hz, 1H), 4.36 (dd, J = 10.5, 4.2 Hz, 1H), 3.86–3.71 (m,
2H), 3.52–3.38 (m, 3H), 2.36 (s, 3H); 13C NMR (101 MHz, CDCl3): δ
3,9-Di(4-fluorophenyl)-2,4,8,10-tetraoxaspiro[5,5]undecane
(2b'b'): White solid; m.p. 162–164 °C; yield 195 mg (>99%).
Methyl 4,6-O-(4-fluorobenzylidene)-α-d-glucopyranoside (2a'a'):
White solid; m.p. 184–185 °C; yield 162 mg (83%); IR (KBr) (νmax cm−1):
3400, 3005 2938, 2882, 1609, 1515, 1460, 1379, 1128, 1072, 839; 1H NMR
(400 MHz, CDCl3): δ 7.49 (dd, J = 8.6, 5.5 Hz, 2H), 7.06 (t, J = 8.7 Hz,
2H), 5.51 (s, 1H), 4.78 (d, J = 3.9 Hz, 1H), 4.29 (dd, J = 9.4, 4.0 Hz, 1H ),
3.91 (t, J = 9.3 Hz, 1H), 3.83–3.70 (m, 2H), 3.61 (dd, J = 9.1, 3.9 Hz, 1 H),
164.4–162.0 (d, JCF = 247.6 Hz), 138.8, 133.6, 132.96–132.93 (d, JCF
=
3.2 Hz), 129.9, 128.3–128.2 (d, JCF = 8.4 Hz), 127.4, 115.4–115.2 (d, JCF
= 21.7 Hz), 101.2, 88.8, 80.2, 74.4, 72.6, 70.4, 68.6, 21.2;19F NMR (376
MHz, CDCl3): δ −112.3. HRMS (ESI) found: m/z 415.0985 [M + Na]+;
calcd for C20H21FO5SNa+: 415.0991.
Allyl 4,6-O-(4-fluorobenzylidene)-β-d-glucopyranoside (2jj):
White solid; m.p. 155–157 °C; yield 170 mg (87%).
3.51–3.44 (m, 4H); 13C NMR (101 MHz, CDCl3): δ 164.4–161.9 (d, JCF
=
247.4 Hz), 133.14–133.11 (d, JCF = 3.1 Hz), 128.33–128.25 (d, JCF = 8.4 Hz),
115.3–115.1 (d, JCF = 21.6 Hz), 101.2, 99.9, 80.9, 72.8, 71.3, 68.9, 62.3, 55.5;
19F NMR (376 MHz, CDCl3): δ −112.4. HRMS (ESI) found: m/z 323.0916
[M + Na]+; calcd for C14H17FO6Na+: 323.0907.
Methyl 2,3-di-O-acetyl-4,6-O-(4-fluorobenzylidene)-α-d-gluco-
pyraniside (2kk): White solid; m.p. 107–109 °C; yield 158 mg (81%);
IR (KBr) (νmax cm−1): 3476, 3070, 2932, 2859, 1749, 1610, 1514, 1433,
1374, 1234, 1055, 994, 836; 1H NMR (400 MHz, CDCl3): δ 7.45–7.39
(m, 2H), 7.03 (t, J = 8.7 Hz, 2H), 5.57 (t, J = 9.7 Hz, 1H), 5.48 (s, 1H),
4.96–4.88 (m, 2H), 4.29 (dd, J = 10.3, 4.8 Hz, 1H), 3.95–3.87 (m, 1H),
3.76 (t, J = 10.3 Hz, 1H), 3.64 (t, J = 9.6 Hz, 1H), 3.41 (s, 3H), 2.09
(s, 3H), 2.06 (s, 3H); 13C NMR (101 MHz, CDCl3): δ 170.4, 169.8,
164.3–161.9 (d, JCF = 247.4 Hz), 132.98–132.94 (d, JCF = 3.1 Hz),
128.14–128.05 (d, JCF = 8.4 Hz), 115.2–115.0 (d, JCF = 21.6 Hz), 100.9,
97.6, 79.2, 71.6, 69.0, 68.8, 62.3, 55.4, 20.8, 20.7; 19F NMR (376 MHz,
CDCl3): δ −112.7. HRMS (ESI) found: m/z 407.1121 [M + Na]+; calcd
for C18H21FO8Na+: 407.1118.
Methyl 2,3-di-O-allyl-4,6-O-(4-fluorobenzylidene)-α-d-gluco-pyraniside
(2ll): White solid; m.p. 83–85 °C; yield 166 mg (85%); IR (KBr) (νmax
cm−1): 3425, 3080, 2919, 2865, 1607, 1511, 1461, 1374, 1153, 1003, 827;
1H NMR (400 MHz, CDCl3): δ 7.50–7.43 (m, 2H), 7.08–7.02 (m, 2H),
5.99–5.88 (m, 2H), 5.51 (s, 1H), 5.33–5.29 (m, 1H), 5.29–5.25 (m, 1H),
5.23–5.18 (m, 1H), 5.17–5.12 (m, 1H), 4.77 (d, J = 3.7 Hz, 1H), 4.37–4.31
(m, 1H), 4.31–4.23 (m, 3H), 4.21–4.15 (m, 1H), 3.88–3.76 (m, 2H),
3.74–3.68 (m, 1H), 3.53 (t, J = 9.3 Hz, 1H), 3.48–3.41 (m, 4H); 13C NMR
(101 MHz, CDCl3): δ 164.3–161.8 (d, JCF = 247.0 Hz), 135.2, 134.8,
133.46–133.43 (d, JCF = 3.0 Hz), 128.0–127.9 (d, JCF = 8.4 Hz), 117.7,
116.7, 115.2–115.0 (d, JCF = 21.6 Hz), 100.7, 99.3, 82.0, 79.1, 77.9, 74.0,
73.1, 69.1, 62.3, 55.3;19F NMR (376 MHz, CDCl3): δ −113.0. HRMS (ESI)
found: m/z 403.1530 [M + Na]+; calcd for C20H25FO6Na+: 403.1533.
1,2,3,6,2',3'-Hexa-O-acetyl-4',6'-(4-fluorobenzylidene)-β-d-lactose
(2e'e'): Colourless syrup; yield 182 mg (92%); IR (KBr) (νmax cm−1):
Methyl
4,6-O-(4-fluorobenzylidene)-α-d-galactopyranoside
(2c'c'): White solid; m.p. 161–162 °C; yield 156 mg (80%); IR (KBr)
(νmax cm−1): 3441, 2913, 2859, 1609, 1514, 1453, 1398, 1089, 1043, 832;
1H NMR (400 MHz, CDCl3): δ 7.50–7.46 (m, 2H), 7.05 (t, J = 8.7 Hz,
2H), 5.53 (s, 1H), 4.92 (d, J = 2.7 Hz, 1H), 4.71 (bs, 1H), 4.30–4.24
(m, 2H), 4.07 (dd, J = 12.6, 1.6 Hz, 1H), 3.93–3.86 (m, 2H), 3.70 (bs,
1H), 3.46 (s, 3H); 13C NMR (101 MHz, CDCl3): δ 164.4–161.9 (d,
JCF = 247.5 Hz), 133.66–133.63 (d, JCF = 3.1 Hz), 128.3–128.2 (d, JCF
= 8.4 Hz), 115.2–115.0 (d, JCF = 21.6 Hz), 100.5, 100.2, 76.0, 69.5, 69.4,
69.3, 62.7, 55.7; 19F NMR (376 MHz, CDCl3): δ −112.4. HRMS (ESI)
found: m/z 323.0906 [M + Na]+; calcd for C14H17FO6Na+: 323.0907.
Phenyl 4,6-O-(4-fluorobenzylidene)-α-d-glucopyranoside
(2gg): White solid; m.p. 217–218 °C; yield 145 mg (74%); IR
(KBr) (νmax cm−1): 3381, 2931, 2871, 1602, 1508, 1227, 1082,
1
1030, 835; H NMR (400 MHz, DMSO): δ 7.53–7.47 (m, 2H),
7.36–7.30 (m, 2H), 7.21 (t, J = 8.9 Hz, 2H), 7.10 (d, J = 7.8 Hz,
2H), 7.03 (t, J = 7.3 Hz, 1H), 5.62 (s, 1H), 5.55 (d, J = 3.7 Hz,
1H), 4.09–4.01 (m, 1H), 3.82 (t, J = 9.3 Hz, 1H), 3.76–3.68 (m,
2H), 3.56–3.47 (m, 2H); 13C NMR (101 MHz, DMSO): δ 164.0–
161.5 (d, JCF = 244.7 Hz), 157.2, 134.59–134.57 (d, JCF = 2.9 Hz),
130.0, 129.1–129.0 (d, JCF = 8.5 Hz), 122.6, 117.3, 115.5–115.3
(d, JCF = 21.5 Hz), 100.6, 98.4, 81.5, 72.5, 70.2, 68.5, 63.9; 19F
NMR (376 MHz, CDCl3): δ −112.3. HRMS (ESI) found: m/z
385.1062 [M + Na]+; calcd for C19H19FO6Na+: 385.1063.