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R. Johnsson et al. / Tetrahedron 61 (2005) 11657–11663
3H each). 13C NMR (C6D6): d 169.8, 169.3, 155.3, 137.8,
134.8, 130.7, 130.1, 129.3, 128.7, 128.4, 127.6, 127.4, 127.0,
126.7, 124.9, 119.1, 112.0, 101.8, 99.7, 78.3, 72.8, 72.2, 68.5,
66.6, 20.4, 20.3. HRMS calcd for C27H27O8 (MCH)
479.1706, found 479.1682.
tetra-O-acetyl-b-D-galactopyranosyl)-b-D-glucopyranoside
(31) (188 mg, 0.25 mmol) and In(OTf)3 (69 mg, 0.12 mmol)
were dissolved in MeCN (5 mL). ICl (1 M in CH2Cl2,
0.275 mL, 0.28 mmol) was added dropwise and the mixture
was stirred for 60 min at room temperature. Triethylamine
(1.5 mL) followed by Na2S2O3 (1.5 g) were added and the
mixture was concentrated and chromatographed (SiO2, 2:3
heptane/EtOAc) to give 2-(1-iodonaphthyl) 2,3,6-tri-O-
acetyl-4-O-(2,3,4,6-tetra-O-acetyl-b-D-galactopyranosyl)-
b-D-glucopyranoside (212 mg, 97%). Recrystallization from
ether gave an analytical sample of white crystals; mp 195.0–
196.0 8C; [a]2D1K50.0 (c 1.2, CHCl3). 1H NMR (CDCl3): d
8.15 (d, 1H, JZ8.4 Hz), 7.78 (d, 1H, JZ9.0 Hz), 7.75 (d,
1H, JZ8.2 Hz), 7.56 (dt, 1H, JZ6.9, 1.0 Hz), 7.44 (dt, 1H,
JZ7.9, 0.7 Hz), 7.29 (d, 1H, JZ9.0 Hz), 5.37 (t, 1H, JZ
9.0 Hz), 5.36 (d, 1H, JZ3.5 Hz), 5.31 (t, 1H, JZ8.8 Hz),
5.17 (d, 1H, JZ7.2 Hz), 5.14 (dd, 1H, JZ10.4, 7.9 Hz),
4.98 (dd, 1H, JZ10.4, 3.4 Hz), 4.56 (dd, 1H, JZ11.8,
2.1 Hz), 4.55 (d, 1H, JZ7.9 Hz), 4.18 (t, 1H, JZ5.5 Hz),
4.15–4.08 (m, 2H), 4.01 (t, 1H, JZ8.6 Hz), 3.91 (t, 1H, JZ
6.9 Hz), 3.86–3.83 (m, 1H), 2.16, 2.12, 2.11, 2.08, 2.07,
2.06, 1.97 (s, 3H each). 13C NMR (CDCl3): d 170.5, 170.4,
170.3, 170.2, 169.9, 169.7, 169.2, 154.5, 135.5, 131.9,
131.0, 130.5, 128.5, 128.3, 125.6, 116.6, 101.3, 99.8, 90.0,
76.2, 73.1, 71.4, 71.1, 70.9, 69.2, 66.8, 62.0, 61.0, 21.4,
21.0, 20.9, 20.81, 20.80, 20.78, 20.7. HRMS calcd for
C36H41IO18Na (MCNa) 911.1235, found 911.1212.
6.1.16. 2-(1-Iodonaphthyl) 4,6-O-benzylidene-2,3-di-O-
acetyl-b-D-glucopyranoside (30). 2-Naphthyl 4,6-O-
benzylidene-2,3-di-O-acetyl-b-D-glucopyranoside (29)
(121 mg, 0.25 mmol), In(OTf)3 (70 mg, 0.12 mmol) and
˚
molecular sieves 3 A (1 g) were dissolved in MeCN (5 mL).
ICl (1 M in CH2Cl2, 0.275 mL, 0.28 mmol) was added
dropwise and the mixture was stirred for 60 min at room
temperature. Triethylamine (1.5 mL) followed by Na2S2O3
(1.5 g) were added and the mixture was concentrated and
chromatographed (SiO2, 2:1 heptane/EtOAc) to give 2-(1-
iodonaphthyl) 4,6-O-benzylidene-2,3-di-O-acetyl-b-D-
glucopyranoside (131 mg, 86%). Recrystallization from
EtOAc/heptane gave an analytical sample of white crystals;
mp 223.0–225.0 8C; [a]2D2K100.1 (c 1.0, CHCl3). 1H NMR
(CDCl3): d 8.17 (d, 1H, JZ8.6 Hz), 7.82 (d, 1H, JZ9.0 Hz),
7.77 (d, 1H, JZ8.0 Hz), 7.57 (dt, 1H, JZ8.5, 1.3 Hz), 7.48–
7.43 (m, 3H), 7.39–7.37 (m, 3H), 7.31 (d, 1H, JZ8.9 Hz),
5.57 (s, 1H), 5.50–5.40 (m, 2H), 5.31 (d, 1H, JZ7.4 Hz),
4.45 (dd, 1H, JZ10.5, 5.0 Hz), 3.92 (t, 1H, JZ9.6 Hz), 3.89
(t, 1H, JZ10.4 Hz), 3.74 (dt, 1H, JZ9.7, 4.9 Hz), 2.12, 2.10
(s, 3H each). 13C NMR (CDCl3): d 170.5, 169.8, 154.6,
136.9, 132.0, 131.1, 130.7, 129.5, 128.6, 128.5, 128.4,
126.4, 125.7, 116.5, 101.9, 100.8, 90.0, 78.2, 72.2, 72.1,
68.8, 67.0, 21.5, 21.1. HRMS calcd for C27H25IO8Na (MC
Na) 627.0492, found 627.0530.
Figure 2. General procedure for NMR reactions with
mesitylene. To CD3CN (0.4 mL) were added mesitylene
(17) (0.0025 mL, 0.018 mmol) and Cu(OTf)2 (0.25–
1.0 equiv). The reaction was initiated by the addition of
IBr (0.018 mL, 1.0 M in CH2Cl2). The NMR spectrum of
bromomesitylene was in agreement with published data.
6.1.17. 2-Naphthyl 2,3,6-tri-O-acetyl-4-O-(2,3,4,6-tetra-
O-acetyl-b-D-galactopyranosyl)-b-D-glucopyranoside
(31). Peracetylated lactose (683 mg, 1.00 mmol) and
2-naphthol (231 mg, 1.6 mmol) were dissolved in CH2Cl2
(10 mL, filtered through Al2O3). BF3$OEt2 (0.190 mL,
1.5 mmol) was added and the mixture was stirred for
60 min at room temperature under argon. Triethylamine
(1.5 mL) was added and the mixture was concentrated and
chromatographed (SiO2, 1:2 heptane/EtOAc) to give
2-naphthyl 2,3,6-tri-O-acetyl-4-O-(2,3,4,6-tetra-O-acetyl-
b-D-galactopyranosyl)-b-D-glucopyranoside (609 mg,
79%). Recrystallization from EtOAc/heptane gave an
analytical sample of white crystals; mp 169.5–170.5 8C;
[a]2D1K19.1 (c 0.9, CHCl3). 1H NMR (CDCl3): d 7.80–7.71
(m, 3H), 7.46 (dt, 1H, JZ7.1, 1.0 Hz), 7.39 (dt, 1H, JZ7.0,
1.0 Hz), 7.32 (d, 1H, JZ2.3 Hz), 7.16 (dd, 1H, JZ8.9,
2.4 Hz), 5.37 (d, 1H, JZ3.0 Hz), 5.32 (t, 1H, JZ8.3 Hz),
5.26–5.19 (m, 2H), 5.14 (dd, 1H, JZ10.4, 7.9 Hz), 4.98 (dd,
1H, JZ10.4, 3.4 Hz), 4.55–4.49 (m, 1H), 4.53 (d, 1H, JZ
8.0 Hz), 4.19–4.07 (m, 3H), 3.92 (t, 1H, JZ9.9 Hz), 3.92–
3.88 (m, 2H), 2.16, 2.09 (s, 3H each), 2.07 (s, 12H), 1.97 (s,
3H). 13C NMR (CDCl3): d 170.52, 170.48, 170.3, 170.2,
169.9, 169.8, 169.3, 154.7, 134.2, 130.2, 129.8, 127.9,
127.2, 126.8, 124.8, 118.9, 111.5, 101.3, 98.9, 76.5, 73.00,
72.97, 71.7, 71.1, 70.9, 69.2, 66.8, 62.3, 61.0, 21.0, 20.92,
20.85, 20.8, 20.7. HRMS calcd for C36H42O18Na (MCNa)
785.2269, found 785.2239.
Acknowledgements
This work was supported by the Swedish Research Council
and the Crafoord Foundation.
References and notes
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6.1.18. 2-(1-Iodonaphthyl) 2,3,6-tri-O-acetyl-4-O-(2,3,4,
6-tetra-O-acetyl-b-D-galactopyranosyl)-b-D-glucopyra-
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