Wu et al.
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4.52 (d, 1H, J = 11.6 Hz), 4.15 (m, 1H), 3.95 (dt, 1H, J =
3.2, 6.4 Hz), 3.78 (dd, 1H, J = 7.2, 2.0 Hz), 3.65 (dd, 1H,
J = 10.4, 3.2 Hz), 3.56 (dd, 1H, J = 10.8, 6.4 Hz), 2.17 (dd,
1H, J = 13.2, 4.4 Hz), 1.42 (m, 1H), 1.27 (d, 3H, J =
6.0 Hz). 13C NMR (CDCl3) δ: 138.2, 137.8, 128.5, 128.4,
127.9, 127.7, 88.5, 85.9, 83.8, 82.6, 74.7, 73.5, 72.1, 70.2,
41.0, 19.9. ESMS: 355.3 (MH+).
CH2Ph, J = 12.4 Hz), 3.95 (m, 1H, H-2′), 3.77–3.85 (m, 3H,
H-2, H-3, H-5), 3.55–3.67 (m, 3H, H-4, H-6, 6′), 2.25 (m,
1H, H-1′a), 1.62 (m, 1H, H-1′b), 1.34 (d, 3H, H-3′, J =
6.0 Hz). 13C NMR (CDCl3) δ: 138.9, 138.7, 138.4 (Ph),
128.6, 128.4, 127.9, 127.8, 127.6 (Ph), 83.4 (C-3), 83.3 (C-
2), 76.1 (C-1), 75.5 (C-4), 75.2 (C-5), 74.7 (C-2′), 74.6
(CH2Ph), 73.5 (CH2Ph), 73.0 (CH2Ph), 70.1 (C-6), 39.4
(C-1′), 21.6 (C-3′). ESMS: 475.3 (MH+).
1
For 6␣: [α]D –19.5° (c 1.4, CHCl3). H NMR (CDCl3) δ:
7.37–7.22 (m, 15H), 5.58 (m, 1H), 5.10 (m, 2H), 4.50 (m,
6H), 4.21 (m, 1H), 4.07 (m, 1H), 4.06 (dd, 1H, J = 3.2 Hz),
3.87 (dd, 1H, J = 4.4, 2.8 Hz), 3.57 (m, 2H). 13C NMR
(CDCl3) δ: 138.4, 138.0, 134.4, 128.5, 128.4, 128.3, 127.8,
127.7, 87.0, 85.4, 82.0, 81.6, 73.4–71.9, 70.3, 37.7. ESMS:
445.2 (MH+).
1-C-(3′-Iodo-R/S-propan-2′-ol)-3,5-di-O-benzyl-2,2′-
anhydro-␣-D-ribofuranoside (16-trans and 16-cis)
Compounds 16-trans (19%) and 16-cis (39%) obtained
from 2 were separated by chromatography.
1
For 16-trans: oil. [α]D +51.7° (c 0.12, CHCl3). H NMR
(CDCl3) δ: 4.79–4.76 (m, 2H, PhCH2, H-1), 4.66 (dd, J =
4.0, 4.0 Hz, 1H, H-2), 4.57–4.49 (m, 3H, PhCH2), 4.17 (m,
1H, H-2′), 4.02 (m, 1H, H-4), 3.86 (dd, J = 8.0, 4.4 Hz, 1H,
H-3), 3.66 (dd, J = 10.4, 1.6 Hz, 1H, H-5a), 3.46 (dd, J =
10.4, 4.8 Hz, 1H, H-5b), 3.38–3.30 (m, 2H, CH2I), 2.37 (dd,
J = 13.6, 5.2 Hz, 1H, H-1′b), 1.79 (ddd, J = 13.6, 10.0,
5.2 Hz, 1H, H-1′a). 13C NMR (CDCl3) δ: 83.1 (C-2), 81.9
(C-3), 80.7 (C-4), 80.1 (C-1), 79.5 (C-2′), 73.5 (PhCH2), 72.2
(PhCH2), 70.0 (C-5), 41.9 (C-1′), 10.2 (CH2-I). HRFABMS
calcd. for C22H25IO4 m/z: 480.0797 (M+); found: 479.0749.
For 16-cis: oil. [α]D +79.5° (c 0.2, CHCl3). 1H NMR
(CDCl3) δ: 4.79–4.73 (m, 2H, PhCH2, H-1), 4.57–4.49 (m,
3H, PhCH2), 4.45 (dd, J = 4.4, 4.4 Hz, 1H, H-2), 4.20–4.15
(m, 2H, H-2 H-4), 3.89 (dd, J = 8.4, 4.4 Hz, 1H, H-3), 3.67
(dd, J = 10.8, 1.6 Hz, 1H, H-5a), 3.50 (dd, J = 10.8, 4.8 Hz,
1H, H-5b), 3.41 (dd, J = 10.0, 5.2 Hz, 1H, CH2I), 3.32 (dd,
J = 9.2, 8.4 Hz, 1H, CH2I), 2.42 (dt, J = 14.0, 6.8 Hz, 1H,
H-1), 1.99 (ddd, J = 14.0, 6.8, 2.4 Hz, 1H, H-1). 13C NMR
1-C-(R-Propan-2′-ol)-3,5-di-O-benzyl-2,2′-anhydro-␣-D-
xylofuranoside (9-trans)
Under the same conditions, 9-trans (35%) and 8 (42%)
were obtained from 8 (α:β, 1:1).
For 9-trans: [α]D –44.0° (c 1.12, CHCl3). 1H NMR
(CDCl3) δ: 7.37–7.24 (m, 10H), 4.87 (dd, 1H, J = 4.4 Hz),
4.67 (d, 1H, J = 12.0 Hz), 4.63 (d, 1H, J = 11.6 Hz), 4.59
(m, 1H), 4.52 (d, 1H, J = 6.4 Hz), 4.49 (d, 1H, J = 6.4 Hz),
4.18 (m, 1H), 4.12 (m,1H), 3.97 (d, 1H, J = 4.0 Hz), 3.68 (d,
2H, J = 5.6 Hz), 2.25 (dd, 1H, J = 13.6 Hz, 5.2 Hz), 1.50
(m, 1H), 1.24 (d, 3H, J = 6.4 Hz). 13C NMR (CDCl3) δ:
128.5, 128.4, 127.9, 127.7, 85.9, 83.8, 83.5, 81.3, 75.9, 73.6,
72.2, 68.9, 42.5, 20.6. ESIMS: 355.3 (MH+).
1
For 8: [α]D –19.5° (c 1.4, CHCl3). H NMR (CDCl3) δ:
7.37–7.22 (m, 15H), 5.80 (m, 1H), 5.08 (m, 2H), 4.63–4.44
(m, 6H), 4.20 (dt, 1H, J = 1.6, 4.4 Hz), 3.96 (d, 1H, J =
3.6 Hz), 3.90 (dt, 1H, J = 3.6, 6.8 Hz), 3.79 (dd, 1H, J = 9.6,
5.6 Hz), 3.76 (m, 1H), 3.73 (dd, 1H, J = 9.6, 6.0 Hz), 2.49–
2.32 (m, 2H). 13C NMR (CDCl3) δ: 138.4, 138.0, 134.4,
128.5, 128.4, 127.9, 127.8, 127.7, 87.0, 85.4, 82.0, 81.6,
73.4–71.9, 70.3, 37.7. ESMS: 455.3 (MH+).
(CDCl ) : 82.9 (C-1), 82.2 (C-2), 80.8 (C-2 ), 79.2 (C-3),
δ
′
3
79.0 (C-4), 73.4 (PhCH2), 72.1 (PhCH2), 69.6 (C-5), 40.2
(C-1 ), 8.5 (CH I). HRFABMS calcd. for C H IO m/z:
′
2
22 25
4
480.0797 (M+); found: 479.0711.
1-C-(S-Propan-2′-ol)-3-O-benzyl-4,6-O-benzylidene-2,2′-
anhydro-␣-D-galactopyranoside (11-cis)
1-C-(3′-Iodo-R/S-propan-2′-ol)-3-O-benzyl-4,6-O-
benzylidene-2,2′-anhydro-␣-D-galactopyranoside (17-
This compound was obtained from 10 as an oil in 56%
trans and 17-cis)
Compounds 17-trans (20%) and 17-cis (60%) obtained
from 10 were separated by chromatography.
1
yield. [α]D +44.8° (c 0.67, CHCl3). H NMR (CDCl3) δ:
5.47 (s, 1H, PhCH), 5.07 (m, 1H, H-1), 4.87 (d, J = 12.4 Hz,
1H, CH2Ph), 4.73 (d, J = 12.4 Hz, 1H, CH2Ph), 4.39 (bd, J =
2.4 Hz, 1H, H-4), 4.33 (d, J = 12.4 Hz, 1H, H-6a), 4.08–4.03
(m, 2H, H-6b, H-2), 3.92 (m, 1H, H-2, 3.71 (dd, J = 5.6,
2.0 Hz, 1H, H-3), 3.58 (bs, 1H, H-5), 2.38 (m, 1H, H-1),
1.82 (ddd, J = 13.6, 8.4, 3.2 Hz, 1H, H-1), 1.34 (d, J = 6 Hz,
3H, CH3). 13C NMR (CDCl3) δ: 100.5 (PhCH), 82.8 (C-2),
79.5 (C-3), 78.0 (C-1), 74.2 (C-2′), 73.3 (C-4), 72.6 (C-6),
71.1 (PhCH2), 67.5 (C-5), 40.8 (C-1′), 21.0 (CH3).
HRFABMS calcd. for C23H27O5 m/z: 383.1780 (MH+);
found: 383.2146.
For 17-trans: oil. [α]D –8° (c 5.8, CHCl3). 1H NMR
(CDCl3) δ: 5.48 (s, 1H, PhCH), 5.20 (dd, J = 8.8, 4.4 Hz,
1H, H-1), 4.86 (d, J = 12.4 Hz, 1H, CH2Ph), 4.73 (d, J =
12.8 Hz, 1H, CH2Ph), 4.48 (dd, J = 9.2, 4.4 Hz, 1H, H-2),
4.40 (bs, 1H, H-4), 4.33 (d, J = 12.4 Hz, 1H, H-6a), 4.23 (m,
1H, H-2, 4.05 (d, J = 12.8 Hz, 1H, H-6b), 3.63 (d, J =
5.2 Hz, 1H, H-3), 3.56 (bs, 1H, H-5), 3.34–3.25 (m, 2H,
CH2I), 2.23 (dd, J = 13.6, 5.6 Hz, 1H, H-1), 1.82 (ddd, J =
13.6, 9.2, 5.6 Hz, 1H, H-1). 13C NMR (CDCl3) δ: 100.5
(PhCH), 84.0 (C-2), 79.2 (C-3), 78.1 (C-1), 77.7 (C-2′), 73.5
(C-4), 72.6 (C-6), 70.8 (PhCH2), 67.4 (C-5), 39.8 (C-1′),
10.1 (CH2I). HRFABMS calcd. for C23H25IO5 m/z: 508.0747
(M+); found: 507.0730.
1-C-(S-Propan-2′-ol)-3,4,6-tri-O-benzyl-2,2′-anhydro-␣-
D-glucopyranoside (13-cis)
This compound was obtained from 12 as an oil in 62%
For 17-cis: oil. [α]D +6.8° (c 9.4, CHCl3). 1H NMR
(CDCl3) δ: 5.48 (s, 1H, PhCH), 5.15 (m, 1H, H-1), 4.86 (d,
J = 12.4 Hz, 1H, CH2Ph), 4.73 (d, J = 12.4 Hz, 1H, CH2Ph),
4.39 (bs, 1H, H-4), 4.33 (d, J = 12.4 Hz, 1H, OCH2), 4.25
(dd, J = 9.6, 4.8 Hz, 1H, H-2), 4.23 (m, 1H, H-2′), 4.05 (d,
J = 12.4 Hz, 1H, H-6a), 3.66 (bd, J = 5.2 Hz, 1H, H-3), 3.57
1
yield. [α]D +76° (c 0.1, CHCl3). H NMR (CDCl3) δ: 7.18–
7.40 (m, 15H, 3 × Ph), 4.90 (d, 1H, CH2Ph, J = 11.6 Hz),
4.83 (d, 1H, CH2Ph, J = 11.2 Hz), 4.73 (d, 1H, CH2Ph, J =
11.6 Hz), 4.59 (d, 1H, H-1), 4.53 (d, 1H, CH2Ph, J =
12.4 Hz), 4.46 (d, 1H, CH2Ph, J = 11.2 Hz), 4.43 (d, 1H,
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