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HETEROCYCLES, Vol. 64, 2004
q, J = 8.7 Hz), - 2.38 (3F, q, J = 8.7 Hz). IR (KBr): ν = 3320, 1840, 1750 cm-1. MS (EI, 70 eV): m/z =
584 [M+H]+, 583 [M]+, 540 [M – CH3CO]+, 332 [M – C6H3NO3F6]+, 331 [M – C6H4NO3F6]+, 271, 169,
109, 81. Anal. Calcd for C20H23NO12F6: C, 41.18; H, 3.97; N, 2.40. Found: C, 41.24; H, 3.84; N, 2.35.
(4S)-4-[(1R)-1-(2,3,4,6-Tetra-O-acetyl-β-D-glucopyranosyloxy)ethyl]-2,2-bis(trifluoromethyl)-1,3-
oxazolidin-5-one (3b). 2,3,4,6-Tetra-O-acetyl-β-D-glucopyranosyl trichloroacetimidate (2.46 g, 5.0
.
mmol), 2b (1.34 g, 5.0 mmol) and BF3 Et2O (127 µL, 1.0 mmol) were reacted due to protocol 3.
Purification by flash chromatography (toluene / ethyl acetate, 5:1). Yield: 82% (2.44 g) 3b, mp 112 –
1
113 °C. H NMR (CDCl3, 300 MHz): δ = 1.38 (3H, d, J = 6.5 Hz), 2.01 (3H, s), 2.02 (3H, s), 2.06 (3H,
s), 2.07 (3H, s), 3.66 – 3.76 (3H, m), 4.06 – 4.13 (2H, m), 4.22 (1H, dd, J = 12.5 Hz, J = 4.2 Hz), 4.57
(1H, d, J = 8.0 Hz), 4.95 (1H, dd, J = 9.6 Hz, J = 8.0 Hz), 5.09 (1H, dd, J = 9.7 Hz, J = 9.7 Hz), 5.20
13
(1H, dd, J = 9.7 Hz, J = 9.6 Hz). C NMR (CDCl3): δ = 18.1, 20.4, 20.5, 20.8, 59.9, 61.3, 68.0, 71.2,
72.2, 72.6, 75.7, 89.3 (sept, J = 34 Hz), 100.2, 120.2 (q, J = 286 Hz), 121.1 (q, J = 287 Hz), 169.2,
19
169.3, 169.4, 170.2, 170.7. F NMR (CDCl3, 282 MHz): δ = -0.94 (3F, q, J = 8.6 Hz, CF3), -2.89 (3F,
q, J = 8.6 Hz, CF3). IR (KBr): ν = 3000 – 2940, 1830, 1750 cm-1. MS (EI, 70 eV): m/z = 597 [M]+, 554
[M-CH3CO]+, 331 [M-C7H6NO3F6]+, 271, 169, 109. Anal. Calcd for C21H25NO12F6: C, 42.22; H, 4.22;
N, 2.34. Found: C, 42.22; H, 4.08; N, 2.36.
(5S,7R)-7-[2,3,4,6-Tetra-O-acetyl-β-D-glucopyranosyloxy]-2,2-bis(trifluoromethyl)-1-aza-3-oxabi-
cyclo[3.3.0]octan-4-one (3c). 2,3,4,6-Tetra-O-acetyl-α-D-glucopyranosyl bromide (1.03 g, 2.5 mmol),
2c (0.70 g, 2.5 mmol) and Hg(CN)2 (0.63 g, 2.5 mmol) were reacted due to protocol 1. Purification by
o
flash chromatography (petroleum ether / ethyl acetate, 2:1). Yield: 21% (0.32 g) 3c, mp 106 – 107 C.
1H NMR (CD3CN, 400 MHz): δ = 1.92 (3H, s), 1.96 (3H, s), 1.98 (3H, s), 1.99 (3H, s), 2.11 (1H, ddd, J
= 13.8 Hz, J = 9.1 Hz, J = 4.8 Hz), 2.31 (1H, ddd, J = 13.8 Hz, J = 7.9 Hz, J = 1.6 Hz), 3.31 (1H, dm, J
= 11.1 Hz), 3.51 (1H, ddq, J = 11.1 Hz, J = 4.2 Hz, J = 2.1 Hz), 3.81 (1H, ddd, J = 10.0 Hz, J = 5.3 Hz,
J = 2.5 Hz), 4.06 (1H, dd, J = 12.3 Hz, J = 2.5 Hz), 4.19 (1H, dd, J = 12.3 Hz, J = 5.3 Hz), 4.29 (1H,
dd, J = 9.1 Hz, J = 7.9 Hz), 4.58 (1H, m), 4.72 (1H, d, J = 8.1 Hz), 4.86 (1H, dd, J = 9.7 Hz, J = 8.1
13
Hz), 5.00 (1H, dd, J = 10.0 Hz, J = 9.8 Hz), 5.21 (1H, dd, J = 9.8 Hz, J = 9.7 Hz). C NMR (CD3CN,
100 MHz): δ = 20.8, 20.9, 34.8, 55.7, 61.2, 62.7, 69.3, 71.8, 72.7, 73.3, 81.4, 92.3 (m), 100.6, 121.0 (q,
19
J = 289 Hz), 122.2 (q, J = 287 Hz), 170.3, 170.5, 170.9, 171.3, 172.1. F NMR (CD3CN, 282 MHz): δ
= -3.09 (3F, q, J = 9.6 Hz, CF3), 5.48 (3F, q, J = 9.6 Hz, CF3). IR (KBr): ν = 3454, 1833, 1756 cm-1.
Anal. Calcd for C22H25NO12F6: C, 42.11; H, 4.02; N, 2.23. Found: C, 41.91; H, 3.90; N, 2.26.