8748
J. S. Yadav et al. / Tetrahedron Letters 46 (2005) 8745–8748
Acta 1946, 29, 152; (c) Raunak; Babu, B. R.; Sorensen, M.
3.73 (dd, J = 4.5 Hz, 1H), 3.80–3.98 (m, 3H), 4.09 (dd,
J = 3.0 Hz, 1H), 4.57 (d, J = 3.8 Hz, 1H), 5.86 (d,
J = 3.8 Hz, 1H); LCMS: m/z 257 (M++Na); 2,3-
O-Isopropylidene-1-O-methoxymethyl-a-D-manofuranose
(j): 1H NMR (CDCl3, 200 MHz): d ppm 1.33 (s, 3H), 1.46
(s, 3H), 3.37 (s, 3H), 3.68 (m, 1H), 3.81 (m, 1H), 3.94 (s,
2H), 4.48 (d, J = 6.0 Hz, 1H), 4.59 (d, J = 6.0 Hz, 1H),
4.81 (m, 2H), 5.19 (s, 1H); LCMS: m/z 279 (M++Na); 2,3-
O-Isopropylidene-1-O-propargyl-a-D-manofuranose (k):
1H NMR (CDCl3, 200 MHz): d ppm 1.33 (s, 3H), 1.47
(s, 3H), 2.02 (s, 1H), 3.64–3.95 (m, 4H), 4.15 (m, 2H), 4.57
(d, J = 5.6 Hz, 1H), 4.81 (m, 1H), 5.16 (s, 1H); LCMS:
m/z 281 (M++Na); 1-O-Allyl-2,3-O-isopropylidene-a-D-
manofuranose (l): 1H NMR (CDCl3, 200 MHz): d ppm
1.32 (s, 3H), 1.46 (s, 3H), 3.68–3.80 (m, 2H), 3.93 (m, 3H),
4.09 (m, 1H), 4.58 (d, J = 6.0 Hz, 1H), 4.80 (m, 1H), 5.00
(s, 1H), 5.15–5.27 (m, 2H), 5.83 (m, 1H); LCMS: m/z 283
(M++Na); 2,3-O-Isopropylidene-1-O-p-methoxybenzyl-a-
D-manofuranose (n): 1H NMR (CDCl3, 200 MHz): d ppm
1.36 (s, 3H), 1.53 (s, 3H), 3.64–3.88 (m, 6H), 4.05 (m, 1H),
4.50–4.62 (m, 2H), 4.72–4.83 (m, 3H), 6.84 (d, J = 8.1 Hz,
2H), 7.26 (d, J = 8.9 Hz, 2H); LCMS: m/z 363 (M++Na);
Compound (o): [a]D À16.2 (c 0.4, CHCl3). 1H NMR
(200 MHz, CDCl3): d 1.28 (t, J = 7.4 Hz, 3H), 1.43–1.58
(m, 2H), 2.52 (t, J = 6.7 Hz, 2H), 3.35 (dd, J1,2 = 11.1 Hz,
J2,3 = 5.9 Hz, 1H), 3.5 (dd, J1,2 = 11.1 Hz, J2,3 = 5.9 Hz,
1H), 3.78–3.86 (m, 2H), 4.18 (q, J = 7.4 Hz, 2H), 4.46 (d,
J = 11.1 Hz, 1H), 4.69 (d, J = 11.1 Hz, 1H), 5.85 (d,
J = 15.6 Hz, 1H), 6.98–6.82 (m, 1H), 7.35–7.24 (m, 5H);
MS FAB: m/z 331 (M++Na), 309 (M++1); Compound
(q): [a]D +101.6 (c 1, CHCl3); 1.34 (s, 3H), 1.45 (s, 3H),
3.66 (m, 3H), 4.66 (br s, 1H), 4.82 (d, J = 4.4 Hz, 1H), 5.41
(s, 2H), 5.75 (d, J = 3.7 Hz, 1H); LCMS: m/z 239
(M++Na); Compound (r): [a]D +21.42 (c 1, CHCl3);
0.86 (d, J = 6.8 Hz, 3H), 1.02 (s, 3H), 1.21 (s, 3H), 1.75 (m,
1H), 3.32–3.50 (m, 4H), 4.22 (t, J = 4.5 Hz, 1H), 5.4 (d,
J = 3.77 Hz, 1H); LCMS: m/z 241 (M++Na); Compound
(t): [a]D À0.26 (c 1, CHCl3); 0.73 (d, J = 7.1 Hz, 3H), 0.95
(d, J = 7.1 Hz, 3H), 1.12 (d, J = 7.4 Hz, 3H), 1.82 (m, 2H),
2.02 (m, 1H), 3.50–3.85 (m, 6H), 4.65 (m, 2H), 7.30 (m,
5H); FABMS: m/z 297 (M++1).
D.; Parmar, V. S.; Harrit, N. H.; Wengel, J. Org. Biomol.
Chem. 2004, 2, 80–89; (d) Shing, T. K. M.; Leung, G. Y.
C. Tetrahedron 2002, 58, 7545–7552; (e) Ates, A.; Gautier,
A.; Leroy, B.; Plancher, J.-M.; Yannick, Q.; Vanherck,
J.-C.; Marko, I. E. Tetrahedron 2003, 59, 8989–8999.
13. (a) Azhayeu, A. V. Tetrahedron 1999, 55, 787–800; (b)
Czemecki, S.; Georgoulis, C.; Stevens, C. L.; Vijay-
kumaran, R. Tetrahedron Lett. 1985, 26, 1699.
14. Experimental procedure: Iodine (30 mol %) was added to
a solution of glucose diacetonide (0.384 mmol) in aceto-
nitrile (2 mL) and after adding water (40 lL) the reaction
was stirred at room temperature for 2–3 h. After complete
conversion, as indicated by TLC, the reaction mixture was
diluted with aqueous Na2S2O3 (10 mL) and extracted with
ethyl acetate (2 · 20 mL). The organic layers were dried
over anhydrous Na2SO4 and filtered through silica gel
(Merck, 100–200 mesh) using hexane–ethyl acetate (7:3) to
afford the pure diol. Spectral data: 1,2-O-Isopropylidene-
3-O-p-methoxybenzyl-a-D-glucofuranose (c): 1H NMR
(CDCl3, 200 MHz), d ppm 1.30 (s, 3H), 1.46 (s, 3H),
3.63–3.75 (m, 2H), 3.80 (s, 3H), 3.91 (m, 1H), 4.0–4.08 (m,
2H), 4.46 (d, J = 11.1 Hz, 1H), 4.53 (d, J = 3.7 Hz, 1H),
4.65 (d, J = 11.9 Hz, 1H), 5.87 (d, J = 3.7 Hz, 1H), 6.86
(d, J = 8.9 Hz, 2H), 7.25 (d, J = 8.2 Hz, 2H); 1,2-O-
Isopropylidene-3-O-propargyl-a-D-glucofuranose (e): [a]D
1
À37.7 (c 1, CHCl3); H NMR (CDCl3, 200 MHz): d ppm
1.00 (s, 3H), 1.18 (s, 3H), 2.24 (t, J = 2.3 Hz, 1H), 3.28 (br
s, 1H), 3.35 (dd, J = 5.3 Hz, 1H), 3.47–3.62 (m, 2H), 3.75
(dd, J = 3.0 Hz, 1H), 3.85 (d, J = 3.0 Hz, 1H), 4.00 (t,
J = 3.7 Hz, 2H), 4.27 (d, J = 3.7 Hz, 1H), 5.55 (d,
J = 3.7 Hz, 1H). LCMS: m/z 281 (M++Na); 1,2-O-
Isopropylidene-3-O-methoxymethyl-a-D-glucofuranose (f):
[a]D +79.6 (c 1, CHCl3); 1H NMR (CDCl3, 200 MHz):
d ppm 1.31 (s, 3H), 1.48 (s, 3H), 3.43 (s, 3H), 3.69 (dd,
J = 4.5 Hz, 1H), 3.79–3.89 (m, 2H), 4.06 (dd, J = 3.0 Hz,
1H), 4.20 (d, J = 3.0 Hz, 1H), 4.52 (d, J = 3.8 Hz, 1H),
4.72 (m, 2H), 5.84 (d, J = 3.0 Hz, 1H). LCMS: m/z 279
(M++Na); 1,2-O-Isopropylidene-3-O-methyl-a-D-gluco-
furanose (g): [a]D À38.75 (c 1, CHCl3); 1H NMR (CDCl3,
200 MHz): d ppm 1.34 (s, 3H), 1.51 (s, 3H), 3.50 (s, 3H),