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H. Yu, H. E. Ensley / Tetrahedron Letters 44 (2003) 9363–9366
10. Bock, K.; Fernandez-Bolanos Guzman, J.; Refn, S. Carbo-
hydr. Res. 1992, 232, 353–357.
11. Schmidt, R. R. Angew. Chem., Int. Ed. Engl. 1986, 25,
212–235.
12. A typical experimental procedure, as applied to ethyl
4,6-O-benzylidene-2-O-benzoyl-3-O-t-butyldimethylsilyl-
(m, 4H, H-3%, H-4, H-4%, H-2); 12a 4.99 (t, J=10.0 Hz, 1H,
H-2), 4.25 (d, J=10.0 Hz, 1H, H-1); 12b 5.40 (d, J=3.2
Hz, 1H, H-1), 4.69–4.62 (m, 2H, H-6a, H-2); 12c 6.07 (d,
J=3.6 Hz, 1H, H-1), 3.77 (dd, J=9.6 Hz and 4.0 Hz, 1H,
H-2); 13a 5.33 (dd, J=9.2 Hz and 8.0 Hz, 1H, H-2), 4.84
(d, J=8.0 Hz, 1H, H-1); 13b 5.41 (d, J=3.6 Hz, 1H, H-1);
4.79 (dd, J=10.0 Hz and 3.6 Hz, 1H, H-2).
1-thio-b-D-glucopyranoside 1a, is as follows: Compound 1a
14. Complete spectral data for selected compounds: 6a 1H
NMR l 8.01–7.40 (m, 15H), 5.76 (d, J=5.6 Hz, 1H, H-1),
5.69 (s, 1H), 5.34 (s, 1H), 5.33 (t, J=7.2 Hz, 1H, H-2%), 5.16
(d, J=7.2 Hz, 1H, H-1%), 5.03 (dd, J=9.6 Hz and 6.0 Hz,
1H, H-2), 4.46–4.36 (m, 4H), 4.25–4.20 (m, 2H), 4.03 (dd,
J=8.3 Hz and 7.4 Hz, 1H, H-3%), 3.93 (t, J=9.6 Hz, 1H),
3.87–3.81 (m, 3H), 3.56 (m, 1H), 2.63 (m, 2H, CH2), 2.16
(s, 3H), 2.02–1.98 (m, 2H), 1.34 (t, J=7.6 Hz, 3H), 1.30
(s, 3H), 1.29 (s, 3H), 0.85 (s, 9H), 0.06 (s, 3H), 0.00 (s, 3H);
13C NMR l 176.3, 171.2, 165.2, 137.4, 137.4, 133.3, 130.1,
130.0, 129.5, 129.1, 128.6, 128.5, 128.3, 126.5, 126.4, 102.0,
101.6, 99.5, 82.3, 81.3, 79.8, 75.7, 74.1, 73.8, 73.3, 68.9, 66.3,
62.9, 61.6, 40.9, 38.1, 25.8, 25.2, 25.2, 24.4, 21.3, 18.1, 15.0,
(500 mg, 0.94 mmol) was dissolved in 5 mL of CH2Cl2–H2O
(100:1) and cooled to 0°C. The solution was treated with
1.0 equiv. of N-bromosuccinimide (167 mg, 0.94 mmol) and
0.1 equiv. of TMSOTf. The resulting mixture was stirred
at 0°C, and the reaction was monitored by TLC. After the
reaction was complete, aqueous NaHCO3 was added, and
the reaction mixture was extracted with CH2Cl2 three times.
The combined organic phase was washed with brine, dried
over anhydrous Na2SO4, and concentrated by rotary
evaporation. The resulting oil was purified by flash column
chromatography (hexane/EtOAc 8:1) to yield of 1b (412 mg,
90%) as a white amorphous solid. Compound 1b (400 mg,
0.82 mmol) was dissolved in a mixture of CH2Cl2–Et3N (4:1,
v/v, 5 mL). The solution was stirred at room temperature
for 24 h. After the reaction was complete, the solution was
concentrated and purified by flash column chromatography
to give 1c (380 mg, 95%). To a solution of compound 1c
(350 mg, 0.72 mmol) in anhydrous CH2Cl2 (8 mL) was
added trichloroacetonitrile (Cl3CCN, 0.43 mL, 6.0 equiv.)
and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU, 50 mL) at
0°C. After stirring the resulting mixture for 4 h, the solvent
was evaporated under reduced pressure and the resulting
oil was purified by flash column chromatography to give
pure 1d (431 mg, 95%) as a white amorphous solid.
13. All compounds gave satisfactory 1H, COSY and 13C NMR
1
−4.05, −4.76; 6b H NMR l 8.21–7.41 (m, 15H), 6.25 (d,
J=4.0 Hz, 1H, H-1), 5.72 (s, 1H), 5.67 (s, 1H), 5.43 (dd,
J=8.8 Hz and 8.0 Hz, 1H, H-2%), 5.12 (d, J=8.0 Hz, 1H,
H-1%), 4.44–4.36 (m, 2H), 4.24–4.01 (m, 4H), 3.96–3.89 (m,
3H, H-2, H-5, H-6b), 3.88–3.77 (m, 3H), 3.58 (m, 1H), 2.12
(s, 3H), 1.98–1.84 (m, 2H), 1.18 (s, 3H), 1.13 (s, 3H), 0.81
(s, 9H), 0.09 (s, 3H), 0.00 (s, 3H); 13C NMR l 180.3, 176.1,
171.2, 142.0, 138.3, 134.8, 134.7, 134.2, 134.1, 133.5, 133.3,
133.2, 131.3, 130.8, 107.5, 106.8, 106.2, 96.3, 86.2, 85.4, 84.9,
81.2, 77.8, 75.5, 73.7, 73.6, 71.5, 69.9, 66.1, 45.9, 43.1, 30.5,
30.3, 29.7, 25.9, 22.9, 0.82, 0.00; 13a 1H NMR l 7.96–7.15
(m, 25H), 5.58 (t, J=9.2 Hz, 1H, H-3%), 5.53 (t, J=9.2 Hz,
1H, H-4%), 5.33 (dd, J=9.2 Hz and 8.0 Hz, 1H, H-2%), 5.12
(t, J=9.6 Hz, 2H, H-2, H-3¦), 5.00 (t, J=9.6 Hz, 1H, H-4¦),
4.92 (dd, J=9.2 Hz and 8.0 Hz, 1H, H-2¦), 4.84 (d, J=8.0
Hz, 1H, H-1%), 4.83(t, J=9.6Hz, 1H, H-4), 4.56(dd, J=12.4
Hz and 3.2 Hz, 1H), 4.59 (d, J=8.0 Hz, 1H, H-1¦), 4.43
(dd, J=12.4 Hz and 5.2 Hz, 1H), 4.33 (d, J=10.0 Hz, 1H,
H-1), 4.21 (dd, J=12.4 Hz and 4.4 Hz, 1H), 4.13–3.99 (m,
3H), 3.83–3.47 (m, 3H), 2.58–2.46 (m, 2H), 2.00 (s, 3H),
1.98 (s, 3H), 1.95 (s, 3H), 1.93 (s, 3H), 1.92 (s, 3H), 1.06
(t, J=7.6 Hz, 3H); 13C NMR l 170.9, 170.4, 169.9, 169.7,
169.7, 166.3, 165.9, 165.3, 165.2, 164.6, 133.7, 133.5, 133.1,
130.0, 129.9, 129.8, 129.6, 129.4, 129.3, 128.8, 128.7, 128.6,
128.5, 128.3, 101.3, 101.0, 83.5, 80.0, 77.9, 73.1, 73.0, 72.1,
72.0, 72.0, 71.9, 71.3, 69.8, 69.2, 69.0, 68.5, 63.3, 62.0, 24.0,
1
spectra. The H NMR signals (400 MHz, CDCl3) for H-1
and H-2 of the corresponding thioglycosides and products
are given: 1a 5.42 (dd, J=10.0 Hz and 8.4 Hz, 1H, H-2),
4.76 (d, J=10.0 Hz, 1H, H-1); 1b 6.41 (d, J=4.0 Hz, 1H,
H-1), 3.80 (dd, J=9.2 Hz and 4.0 Hz, 1H, H-2); 2a 5.52
(t, J=9.2 Hz, 1H, H-2), 4.82 (d, J=10.0 Hz, 1H, H-1); 2b
6.52 (d, J=4.0 Hz, 1H, H-1), 4.16–4.10 (m, 2H, H-2, H-5);
3a 5.03 (dd, J=10.0 Hz and 9.2 Hz, 1H, H-2), 4.57 (d,
J=10.0 Hz, 1H, H-1); 3b 6.19 (d, J=4.0 Hz, 1H, H-1), 3.84
(dd, J=10.0 Hz and 4.0 Hz, 1H, H-2); 4a 5.28 (dd, J=10.0
Hz and 8.8 Hz, 1H, H-2), 4.83 (d, J=10.0 Hz, 1H, H-1);
4b 6.48 (d, J=3.6 Hz, 1H, H-1), 3.97 (dd, J=9.2 Hz and
3.6 Hz, 1H, H-2); 5a 5.82 (dd, J=10.0 Hz and 8.8 Hz, 1H,
H-2), 4.69 (d, J=10.0 Hz, 1H, H-1); 5b 6.21 (d, J=3.2 Hz,
1H, H-1), 3.94–3.84 (m, 3H, H-2, H-3, H-5); 6a 5.76 (d,
J=5.6 Hz, 1H, H-1), 5.03 (dd, J=9.6 Hz and 6.0 Hz, 1H,
H-2); 6b 6.25 (d, J=4.0 Hz, 1H, H-1), 3.96–3.89 (m, 3H,
H-2, H-5, H-6b); 7a 5.34 (t, J=10.0 Hz, 1H, H-2), 4.55 (d,
J=10.4 Hz, 1H, H-1); 7b 6.36 (d, J=4.0 Hz, 1H, H-1),
4.00–3.91 (m, 3H, H-2, H-5, H-5%); 8a 5.07 (t, J=9.6 Hz,
1H, H-2), 4.40 (d, J=9.6 Hz, 1H, H-1); 8b 6.11 (d, J=4.0
Hz, 1H, H-1), 3.82–3.68 (m, 3H, H-2, H-4, H-6b); 9a 5.58
(dd, J=10.0 Hz and 8.0 Hz, 1H, H-2), 4.86 (d, J=10.0 Hz,
1H, H-1); 9b 6.46 (d, J=3.6 Hz, 1H, H-1), 4.02 (dd, J=9.2
Hz and 4.0 Hz, 1H, H-2); 10a 4.99 (t, J=10.0 Hz, 1H, H-2),
4.48 (d, J=10.0 Hz, 1H, H-1); 10b 5.40 (d, J=3.2 Hz, 1H,
H-1), 4.84 (dd, J=10.0 Hz and 3.2 Hz, 1H, H-2); 10c 6.21
(d, J=4.0 Hz, 1H, H-1), 3.87 (dd, J=10.0 Hz and 4.0 Hz,
1H, H-2); 11a 5.39 (t, J=9.6 Hz, 1H, H-2), 4.68 (d, J=10.0
Hz, 1H, H-1); 11b 5.65 (d, J=3.6 Hz, 1H, H-1), 5.24–5.15
1
21.0, 20.9, 20.9, 20.8, 15.0; 13b H NMR l 7.99–6.94 (m,
25H), 5.70 (t, J=9.6 Hz, 1H, H-3%), 5.61 (t, J=9.6 Hz, 1H,
H-4%), 5.49–5.38 (m, 2H, H-1, H-2%), 5.14 (t, J=9.6 Hz, 1H,
H-3¦), 5.05 (d, J=8.0 Hz, 1H, H-1%), 5.01 (t, J=9.6 Hz,
1H, H-4¦), 4.91–4.78 (m, 3H, H-2¦, H-4, H-2), 4.59 (dd,
J=12.0 Hz and 2.8 Hz, 1H), 4.48 (d, J=8.0 Hz, 1H, H-1¦),
4.45–4.38 (m, 2H), 4.18–4.03 (m, 4H), 3.81–3.78 (m, 1H),
3.64–3.60 (m, 1H), 3.51–3.47 (m, 1H), 2.00 (s, 3H), 1.98 (s,
3H), 1.95 (s, 3H), 1.93 (s, 3H), 1.90 (s, 3H); 13C NMR l
171.1, 170.5, 170.3, 170.0, 169.7, 166.4, 165.9, 165.3, 165.3,
165.1, 133.8, 133.7, 133.6, 133.4, 133.0, 130.0, 130.0, 129.9,
129.8, 129.6, 129.5, 129.3, 128.9, 128.8, 128.7, 128.6, 128.5,
128.3, 101.8, 101.5, 89.9, 76.3, 74.2, 73.2, 72.7, 72.2, 72.1,
71.9, 71.5, 69.7, 69.7, 68.8, 68.6, 68.3, 63.3, 61.8, 29.8, 21.0,
20.9, 20.9, 20.8.