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8a The
C-glucoside 1 was synthesized according
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Meldal M.
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8b Mp 66-67 °C(pentane), [α]
D²0 = +17.3
(c 2.0, CHCl3); lit.
[9]
mp 58 °C, [α]D
20 = +17.4
(c 1.6, CHCl3)
9
Alzeer J.
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10 Compound 3:
mp 178-180 °C (AcOEt-cyclohexane); [α]D
20 = +7.4
(c 1.0, CHCl3); 1H
NMR selected data (C6D6): δ = 3.96
(dd, 1 H, J
1,3 = 2.2
Hz, J
3,4 = 9.7 Hz,
H-3), 3.76 (dd, 1 H, J
4,5 = 8.8
Hz, J
5,6 = 9.7 Hz,
H-5), 1.99 (d, 1 H, H-1).
11a
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13 Compound 5:
mp 150-151 °C(cyclohexane); [α]D
20 =-54.6 (c 1.0, CHCl3); 1H
NMR (CDCl3): δ 7.40-7.25 and 7.17-7.12
(2 m, 44 H, Ar), 5.05 and 4.87 (2 d, 4 H, J = 10.7
Hz, PhCH
2), 4.96 and 4.87
(2 d, 4 H, J = 11.1 Hz, PhCH
2), 4.85 and 4.55 (2 d, 4
H, J = 11.0 Hz, PhCH
2), 4.66 and 4.57 (2 d, 4
H, J = 12.4 Hz, PhCH
2), 4.33-4.27 (m,
2 H, 2 H-3), 3.81-3.66 (m, 10 H), 3.55-3.49 (m,
2 H); MALDI-TOF MS: 1196.1 (M + Na + 2
H), 1212.4 (M + K + 2 H). Compound 6:
mp 180-181 °C (AcOEt-MeOH); [α]20
D = -33.1
(c 0.8, CH3OH); 1H
NMR (D2O): δ 7.12 (s, 4 H, Ar), 3.77 (dd, 2
H, J
7,8a = 0.8 Hz, J
8a,8b = 12.2 Hz,
2 H-8a), 3.58-3.51 (m, 2 H, 2 H-8b), 3.28-3.16
(m, 6 H), 3.11-3.02 (m, 4 H), 2.77-2.52, 2.03-1.90,
and 1.65-1.52 (3 m, 8 H, 4 H-1, 4 H-2). Compound 7: mp 279-280 °C (CHCl3-Et2O); [α]D
20 =-58.5 (c 1.1, CHCl3); 1H
NMR (C6D6): δ 7.12 (s, 4 H, Ar),
5.50 (dd, 2 H, J
3,4 = 9.9
Hz, J
4,5 = 9.1 Hz,
2 H-4), 5.32 (dd, 2 H, J
5,6 = 9.3
Hz, 2 H-5), 5.24 (dd, 2 H, J
6,7 = 9.6
Hz, 2 H-6), 4.22 (dd, 1 H, J
7,8a = 4.6
Hz, J
8a,8b = 12.6
Hz, 2 H-8a), 4.07 (d, 2 H, 2 H-3), 4.02 (dd, 2 H, J
7,8b = 2.0
Hz, 2 H-8b), 3.13 (ddd, 2 H, 2 H-7), 1.69, 1.68, 1.66, and 1.64
(4 s, 24 H, 8 Ac); MALDI-TOF MS: 810.2 (M + Na),
826.8 (M + K). Compound 8: mp 254-255 °C
(MeOH-AcOEt); [α]D
20 = 0
(c 0.3, CH3OH); [α]43620 = -9.0
(c 0.3, CH3OH); 1H
NMR (CD3OD): δ 7.45 (s, 4 H, Ar), 4.21-4.15
(m, 2 H, 2 H-3), 3.90 (dd, 2 H, J
7,8a = 0.8 Hz, J
8a,8b = 12.0 Hz,
2 H-8a), 3.72-3.64 (m, 2 H, 2 H-8b), 3.43-3.27 (m, 8 H).
14
Godt A.
Franzen C.
Veit S.
Enkelmann V.
Pannier M.
Jeschke G.
J. Org. Chem.
2000,
65:
7575
15 Compound 10:
mp 133-134 °C (AcOEt-MeOH); [α]D
20 =
-48.5
(c 1.2, CHCl3); 1H
NMR (CDCl3): δ 7.43 (s, 3 H, Ar), 7.39-7.22
and 7.18-7.13 (2 m, 60 H, 12 Ph), 4.96 and 4.82 (2 d, 6
H, J = 10.7 Hz, PhCH
2), 4.95 and 4.86 (2 d, 6
H, J = 11.0 Hz, PhCH
2), 4.85 and 4.56 (2 d, 6
H, J = 11.0 Hz, PhCH
2), 4.65 and 4.56 (2 d, 6
H, J = 12.3 Hz, PhCH
2), 4.30-4.24 (m,
3 H, 3 H-3), 3.81-3.66 (m, 15 H), 3.54-3.48 (m,
3 H); MALDI-TOF MS: 1742.0 (M + Na), 1758.4 (M + K). Compound 11: mp 234-236 °C (AcOEt); [α]D
20 = -58.4
(c 0.9, CHCl3); 1H
NMR (C6D6): δ 7.33 (s, 3 H, Ar),
5.46 (dd, 3 H, J
3,4 = 9.8
Hz, J
4,5 = 9.2 Hz,
3 H-4), 5.32 (dd, 3 H, J
5,6 = 9.1
Hz, 3 H-5), 5.24 (dd, 3 H, J
6,7 = 9.6
Hz, 3 H-6), 4.23 (dd, 3 H, J
7,8a = 4.5
Hz, J
8a,8b = 12.5
Hz, 3 H-8a), 4.03 (dd, 3 H, J
7,8b = 2.0
Hz, 3 H-8b), 4.00 (d, 3 H, 3 H-3), 3.14 (ddd, 3 H, 3 H-7), 1.79,
1.68, 1.66, and 1.65 (4 s, 36 H, 12 Ac); MALDI-TOF MS:
1164.3 (M + Na), 1180.7 (M + K). Compound 12: mp 178-180 °C, dec.
(MeOH); [α]D
20 = +5.5 (c 0.2, CH3OH); 1H
NMR (D2O): δ 7.55 (s, 3 H, Ar), 4.24-4.17
(m, 3 H, 3 H-3), 3.80 (dd, 3 H, J
7,8a = 0.9
Hz, J
8a,8b = 12.5
Hz, 3 H-8a), 3.60 (dd, 3 H, J
7,8b = 5.0
Hz, 3 H-8b), 3.45-3.28 (m, 12 H). Compound 13: [α]D
20 = -39.6
(c 0.8, CH3OH); 1H
NMR (D2O): δ 6.93 (s, 3 H, Ar), 3.80 (dd, 3
H, J
7,8a = 0.9 Hz, J
8a,8b = 12.2 Hz,
3 H-8a), 3.58 (dd, 3 H, J
7,8b = 5.0
Hz, 3 H-8b), 3.28-3.16 (m, 9 H), 3.13-2.98 (m,
6 H), 2.77-2.54, 2.05-1.91, and 1.69-1.55
(3 m, 12 H, 6 H-1, 6 H-2). Compound 14:
mp 116 °C, softening 86 °C(cyclohexane); [α]D
20 = -10.8
(c 0.5, CHCl3); 1H
NMR (CDCl3) selected data: δ 7.41 (s, 3 H, Ar),
7.35-7.15 (m, 105 H, 21 Ph), 4.23-4.18 (m, 3 H,
3 H-3), 3.71-3.59 (m, 18 H), 3.42-3.18 (m, 15
H), 2.22-2.15 and 1.55-1.46 (2 m, 12 H, 6 H-8,
6 H-9); MALDI-TOF MS: 3035.7 (M + Na + 3
H), 3051.7 (M + K + 3 H). Compound 15Ac:
mp 245-246 °C (EtOAc); [α]D
20 =-13.0
(c 0.4, CHCl3); 1H
NMR (CDCl3): δ 6.79 (s, 3 H, Ar), 5.20 (dd,
3 H, J
11,12 = J
12,13 = 9.4 Hz,
3 H-12), 5.14 (dd, 3 H, J
4,5 = J
5,6 = 9.3 Hz, 3
H-5), 5.06 (dd, 3 H, J
13,14 = 10.0
Hz, 3 H-13), 4.91 (dd, 3 H, J
10,11 = 9.9
Hz, 3 H-11), 4.86 (dd, 3 H, J
3,4 = 9.9
Hz, 3 H-4), 4.86 (dd, 3 H, J
6,7 = 9.9
Hz, 3 H-6), 4.29 (dd, 3 H, J
14,15a = 5.0, J
15a,15b = 12.2 Hz, 3
H-15a), 4.11 (dd, 3 H, J
14,15b = 2.2
Hz, 3 H-15b), 3.67 (ddd, 3 H, 3 H-14), 3.46-3.33 (m, 9 H, 3 H-3,
3 H-7, 3 H-10), 2.87-2.76, 2.51-2.40, 1.94-1.85,
1.77-1.68, and 1.52-1.39 (5 m, 24 H), 2.12, 2.08,
2.06, 2.02, 2.01, and 1.98 (6 s, 63 H, 21 Ac).
16
Dondoni A.
Giovannini PP.
Marra A.
J.
Chem. Soc., Perkin Trans. 1
2001,
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17
Mattern DL.
J.
Org. Chem.
1984,
49:
3051
18 A solution of 2 (157
mg, 0.44 mmol) and 16 (58 mg, 0.10 mmol)
in anhydrous DMF (1.6 mL) and Et3N (1.6 mL) was degassed
by bubbling argon at r.t. for 20 min. To the solution was added
commercially available Pd(PPh3)4 (23 mg, 0.02 mmol)
and the suspension was stirred at 60 °C in an argon atmosphere.
After an additional 24 h at 60 °C the red-brown solution
was concentrated, then diluted with CH2Cl2 (50 mL),
washed with 1 M phosphate buffer at pH = 7 (20 mL), dried
(Na2SO4), and concentrated. The residue was
eluted from a column of silica gel with EtOAc-cyclohexane
(from 2:1 to 3:1) to give 17 (94 mg) slightly
contaminated by uncharacterized byproducts. Trituration of this
material with Et2O (ca. 2 mL) afforded pure 17 (74 mg, 49%) as a white solid;
mp 119-120 °C (MeOH); [α]D
20 = -70.0
(c 1.0, CHCl3); 1H
NMR (C6D6): δ 7.30 (s, 2 H, Ar),
5.58-5.51 (m, 4 H, 4 H-4), 5.42-5.31 (m, 8 H,
4 H-5, 4 H-6), 4.31 (d, 4 H, J
3,4 = 9.8
Hz, 4 H-3), 4.30 (dd, 4 H, J
7,8a = 4.5
Hz, J
8a,8b = 12.3 Hz,
4 H-8a), 4.14 (dd, 4 H, J
7,8b = 1.8
Hz, 4 H-8b), 3.35-3.29 (m, 4 H, 4 H-7), 1.84, 1.74, 1.72,
and 1.64 (4 s, 48 H, 16 Ac); MALDI-TOF MS: 1519.3 (M + Na),
1535.8 (M + K).
19 Compound 18:
mp 292-294 °C, dec. (MeOH); [α]D
20 = -4.1 (c 0.3, H2O); 1H
NMR (D2O): δ 7.65 (s, 2 H, Ar), 4.29-4.24 (m,
4 H, 4 H-3), 3.81 (dd, 4 H, J
7,8a = 1.1
Hz, J
8a,8b = 12.5
Hz, 4 H-8a), 3.63 (dd, 4 H, J
7,8b = 5.1
Hz, 4 H-8b), 3.48-3.30 (m, 16 H). Compound 19: [α]D
20 = -39.6
(c 0.6, H2O); 1H
NMR (D2O): δ 6.98 (s, 2 H, Ar), 3.75 (dd, 4
H, J
7,8a = 0.8 Hz,
J
8a,8b = 12.5 Hz,
4 H-8a), 3.54 (dd, 4 H, J
7,8b = 3.8
Hz,
4 H-8b), 3.23-3.12 (m, 12 H), 3.03-2.98
(m, 8 H), 2.71-2.56 (m, 8 H), 1.95-1.83 (m, 4
H), 1.60-1.46 (m, 4 H).