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HETEROCYCLES, Vol. 65, No. 5, 2005
(Prop-2-ynyloxy) 2,3:5,6-di-O-isopropylidene-α-D-mannofuranoside (14). 69% yield. 1H NMR
(CDCl3): δ 1.33 (s, 3H, -CH3), 1.38 (s, 3H, -CH3), 1.46 (s, 3H, -CH3), 1.48 (s, 3H, -CH3), 2.44 (t, 1H,
HCCCH2, J = 2.4 Hz), 3.96 (dd, 1H, H-4, J = 3.6, 7.8 Hz), 4.06 (dd, 1H, H-6, J = 4.2, 8.7 Hz), 4.11 (dd, 1H,
H-6’, J = 6.2, 8.7 Hz), 4.19 (dd, 2H, -OCH2CCH, J = 2.3, 4.3 Hz), 4.41 (ddd, 1H, H-5, J = 4.3, 6.2, 7.8 Hz),
4.63 (d, 1H, H-2, J = 5.9 Hz), 4.79 (dd, 1H, H-3, J = 3.6, 5.9 Hz), 5.18 (s, 1H, H-1). 13C NMR (CDCl3): δ
25.7, 26.4, 27.1, 28.2, 55.3, 70.0, 74.1, 75.8, 78.8, 80.5, 81.7, 86.1, 105.9, 110.3, 113.7. APCI-MS (m/z)
calcd: 298.33, found: 299.2 (M+H). HRMS (M+Na) calcd: 321.1314, found: 321.1306.
1,2:3,4-Di-O-isopropylidene-6-O-(prop-2-ynyloxy)-D-galactopyranose (15). 67% yield. 1H NMR
(CDCl3): δ 1.33 (s, 3H, -CH3), 1.35 (s, 3H, -CH3), 1.46 (s, 3H, -CH3), 1.55 (s, 3H, -CH3), 2.44 (t, 1H,
HCCCH2, J = 2.4 Hz), 3.67 (dd, 1H, H-6, J = 7.1, 10.1 Hz), 3.78 (dd, 1H, H-6’, J = 5.2, 10.1 Hz), 4.00 (ddd,
1H, H-5, J = 1.9, 5.2, 7.1 Hz), 4.21 (d, 1H, -OCH2CCH, J = 2.4 Hz), 4.24 (d, 1H, -OCH2CCH, J = 2.4 Hz),
4.26 (dd, 1H, H-4, J = 1.8, 7.9 Hz), 4.32 (dd, 1H, H-2, J = 2.4, 5.1 Hz), 4.61 (dd, 1H, H-3, J = 2.4, 7.9 Hz),
5.55 (d, 1H, H-1, J = 5.1 Hz). 13C NMR (CDCl3): δ 25.7, 26.2, 27.2, 27.3, 59.7, 67.9, 69.8, 71.6, 71.8, 72.3,
75.8, 80.7, 97.4, 109.6, 110.3. APCI-MS (m/z) calcd: 298.33, found: 299.0 (M+H). HRMS (M+Na) calcd:
321.1314, found: 321.1290.
1,2-O-Isopropylidene-3,5-di-O-(prop-2-ynyloxy)-D-xylofuranose (16). 73% yield. 1H NMR (CDCl3): δ
1.32 (s, 3H, -CH3), 1.50 (s, 3H, -CH3), 2.47 (t, 1H, -CH2CCH, J = 2.6 Hz), 2.50 (t, 1H, -CH2CCH, J = 2.6
Hz), 3.72 (dd, 1H, H-5, J = 6.6, 10.0 Hz), 3.81 (dd, 1H, H-5’, J = 5.6, 10.0 Hz), 4.11 (d, 1H, H-3, J = 3.1 Hz),
4.19-4.25 (m, 4H, 2 x -OCH2CCH), 4.40 (m, 1H, H-4), 4.62 (d, 1H, H-2, J = 3.8 Hz), 5.92 (d, 1H, H-1, J =
3.8 Hz). 13C NMR (CDCl3): δ 27.6, 28.0, 58.9, 59.8, 68.4, 75.8, 76.2, 80.0, 80.2, 80.6, 82.6, 83.4, 106.1,
112.9. APCI-MS (m/z) calcd: 266.29, found: 267.2 (M+H). HRMS (M+Na) calcd: 289.1052, found:
289.1039.
1,4-Disubstituted triazole (17).
Mannofuranosyl azide (3) (0.25 g, 0.88 mmol), alkyne (13) (0.288 g, 0.96 mmol), (PPh3)3•CuBr (0.268 g,
0.29 mmol) and DBU (0.432 mL) were refluxed in toluene (15 mL) overnight. The reaction was
concentrated and purified by chromatography (2:1 hexane : EtOAc) to give 0.360 g (73%) of 17 as a
colorless solid. mp = 196-198 ˚C, recrystallized from ethanol. 1H NMR (CDCl3): δ 1.29 (s, 3H, -CH3), 1.33,
1.34 (2s, 6H total, 2 x -CH3), 1.39 (s, 6H, 2 x -CH3), 1.46, 1.48, 1.56 (3s, 9H total, 3 x -CH3), 3.76 (dd, 1H,
H-4man, J = 3.7, 8.1 Hz), 4.07 (m, 9H, H-6 and H-6’man, H-3, H-4, H-5, H-6, and H-6’glc, -OCH2CNCH-),
4.50 (ddd, 1H, H-5man, J = 4.0, 5.9, 8.1 Hz), 4.61 (d, 1H, H-2glc, J = 3.7 Hz), 4.87 (dd, 1H, H-2man, J = 3.6,
5.9 Hz), 4.96 (dd, 1H, H-3man, J = 3.7, 5.9 Hz), 5.88 (d, 1H, H-1glc, J = 3.7 Hz), 6.10 (d, 1H, H-1man, J = 3.6
Hz), 7.87 (s, 1H, triazole-H). 13C NMR (CDCl3): δ 25.2, 26.3, 26.7 (double intensity), 27.4, 28.1 (double
intensity), 28.3, 65.1, 68.0, 68.4, 73.7 (double intensity), 80.3, 80.35, 80.7, 82.2, 82.8, 83.6, 89.9, 106.3,
110.0, 100.7, 112.9, 114.8, 124.5, 145.2. APCI-MS (m/z) calcd: 583.27, found 584.3 (M+H). HRMS
(M+Na) calcd: 606.2639, found: 606.2645. [α]D = +55.6˚ (c 5.0, CH2Cl2). Anal. Calcd for C27H41N3O11: C,