3336
B. Yang et al. / Tetrahedron 69 (2013) 3331e3337
CDCl3)
d
ꢂ125.99 to ꢂ125.80 (2F, m), ꢂ124.45 to ꢂ124.25 (2F, m),
(0.97 g, 3.00 mmol) in DMF (20 mL) was added AIBN (0.66 g,
4.00 mmol). The mixture was stirred under microwave irradiation
(210 W, 2.5 h), and then the solvent was evaporated under reduced
pressure. The resulting residue was purified by silica-gel chroma-
tography (EtOAc/petroleum ether¼1:5), providing 1ac (0.57 g), as
a white solid.
ꢂ112.62 to ꢂ112.50 (2F, m), ꢂ81.94 (3F, t, J¼9.21 Hz). 13C NMR
(107 MHz, CDCl3)
d 39.35 (m), 50.66, 66.39, 119.49, 121.43, 129.21,
136.28, 153.52. IR (KBr) 3444, 3149, 2999, 2939, 2240, 1757, 1506,
1398, 1231, 1185, 1135, 1065, 836, 749, 686, 507 cmꢂ1. HRMS (EI):
C14H9ClF9NO2 calcd: 429.0178, found: 429.0160.
4.5.9. 5-(3-Chloro-2,2,3,3-tetrafluoropropyl)-3-phenethyloxazo-li-
din-2-one (1ea). Yield: 61.1%. White solid. Mp 54.5e56.7 ꢀC. 1H NMR
4.6.1. 5-(2,2-Difluoro-2-(5-phenyl-1,2,4-oxadiazol-3-yl)ethyl)-3-
phenyloxazolidin-2-one (1ac). Yield: 72.3%. White solid. Mp
(400 MHz, CDCl3)
d
2.17e2.35 (1H, m), 2.50e2.67 (1H, m), 2.84e3.02
116.2e117.5 ꢀC. 1H NMR (400 MHz, CDCl3)
d 2.83e3.00 (1H, m),
(2H, m), 3.11 (1H, dd, J1¼8.80 Hz, J2¼6.80 Hz), 3.46e3.64 (3H, m),
3.08e3.24 (1H, m), 3.92 (1H, dd, J1¼9.20 Hz, J2¼7.20 Hz), 4.28 (1H, t,
J¼8.80 Hz), 5.05e5.16 (1H, m), 7.16 (1H, t, J¼8.00 Hz), 7.39 (2H, t,
J¼8.00 Hz) 7.48e7.60 (5H, m), 8.10 (2H, d, J¼6.80 Hz). 19F NMR
4.70e4.84 (1H, m) 7.20e7.26 (3H, m), 7.28e7.37 (2H, m). 19F NMR
(376 MHz, CDCl3)
(107 MHz, CDCl3)
126.86, 128.68, 128.76, 138.00, 156.76. IR (KBr) 3476, 3113, 2956, 1747,
1450, 1405, 1259, 1151, 1089, 945, 908, 883, 801, 754, 699, 684,
494cmꢂ1. HRMS(EI):C14H14ClF4NO2 calcd: 339.0649, found: 339.0647.
d
ꢂ112.50 to ꢂ112.44 (2F, m), ꢂ71.80 (2F, s). 13C NMR
d
33.86, 35.70 (t, J¼22.58 Hz), 45.26, 50.64, 66.93,
(376 MHz, CDCl3)
d
ꢂ95.08 (1F, d, J¼284.25 Hz), 98.62 (1F, d,
J¼283.50 Hz). 13C NMR (107 MHz, CDCl3)
d
40.97 (t, J¼24.08 Hz),
50.68, 66.95 (t, J¼8.24 Hz), 114.17 (t, J¼260.92 Hz) 118.33, 124.48,
125.29, 127.65, 129.09, 129.18, 132.05, 137.72, 153.74, 168.83 170.54
(J¼35.95 Hz). IR (KBr) 3108, 2967, 1739, 1515, 1447, 1421, 1228, 1199,
1112, 1095, 902, 869, 747, 701 cmꢂ1. HRMS (EI): C19H15F2N3O3 calcd:
371.1081, found: 371.1080.
4.5.10. 5-(2,2,3,3,4,4,5,5,5-Nonafluoropentyl)-3-phenethyloxazolidin-
2-one (1eb). Yield: 67.7%. White solid. Mp 52.7e53.9 ꢀC. 1H NMR
(400 MHz, CDCl3) d 2.16e2.34 (1H, m), 2.46e2.66 (1H, m), 2.84e2.97
(2H, m), 3.10 (1H, dd, J1¼8.80 Hz, J2¼6.80 Hz), 3.46e3.62 (3H, m),
4.6.2. 5-(2,2-Difluoro-2-(5-phenyl-1,2,4-oxadiazol-3-yl)ethyl)-3-p-
tolyloxazolidin-2-one (1bc). Yield: 71.6%. White solid. Mp
4.70e4.84 (1H, m) 7.20e7.26 (3H, m), 7.29e7.36 (2H, m). 19F NMR
(376 MHz, CDCl3)
d
ꢂ126.05 to ꢂ125.90 (2F, m), ꢂ124.64 to ꢂ124.40
103.8e105.6 ꢀC. 1H NMR (400 MHz, CDCl3)
d 2.33 (3H, s), 2.82e3.00
(2F, m), ꢂ112.95 to ꢂ112.85 (2F, m), ꢂ81.01 (3F, t, J¼9.59). 13C NMR
(1H, m), 3.08e3.24 (1H, m), 3.90 (1H, dd, J1¼8.80 Hz, J2¼7.20 Hz), 4.26
(1H, t, J¼8.80 Hz), 5.05e5.15 (1H, m), 7.19 (2H, d, J¼8.40 Hz), 7.40 (2H,
d, J¼8.40 Hz), 7.48e7.60 (3H, m), 8.08e8.14 (2H, m). 19F NMR
(106.6 MHz, CDCl3) d 33.84, 35.93, 45.24, 50.65, 66.58,126.85,128.68,
128.76, 138.00, 156.70. IR (KBr) 3029, 2938, 1732, 1494, 1454, 1221,
1175, 1133, 889, 745, 699, 610, 490 cmꢂ1. HRMS (EI): C16H14 F9NO2
calcd: 423.0881, found: 423.0882.
(376 MHz, CDCl3)
d
ꢂ98.95 (1F, d, J¼278.99 Hz), ꢂ94.57 (1F, d,
J¼278.99 Hz) (2F, m). 13C NMR (107 MHz, CDCl3)
d 20.79, 41.07 (t,
J¼24.02 Hz), 50.93, 66.93, 118.49, 125.33, 127.69, 129.01, 129.71,
132.06, 132.06, 134.27, 135.23, 168.86, 170.89 (t, J¼36.93 Hz). IR (KBr)
3448, 2999, 2233, 1756, 1594, 1295, 1473, 1185, 1148, 968, 764, 7, 703,
692 cmꢂ1. HRMS (EI): C20H17F2N3O3 calcd: 385.1238, found: 385.1236.
4.5.11. 5-(3-Chloro-2,2,3,3-tetrafluoropropyl)-3-(3-fluoro-4-
morpholinophenyl)oxazolidin-2-one (1fa). Yield: 73.6%. White solid.
Mp 98.7e99.9 ꢀC. 1H NMR (400 MHz, CDCl3)
d 2.48e2.66 (1H, m),
2.72e2.90 (1H, m), 3.05 (4H, t, J¼4.60 Hz), 3.75e3.82 (1H, dd,
J1¼9.20 Hz, J2¼7.60 Hz), 3.87 (4H, t, J¼4.60 Hz), 4.19 (1H, t, J¼8.80 Hz),
4.97e5.07 (1H, m), 6.93 (1H, t, J¼9.20 Hz), 7.09 (1H, dd, J1¼8.80 Hz,
J2¼1.60 Hz), 7.41 (1H, dd, J1¼14.40 Hz, J2¼2.80 Hz). 19F NMR (376 MHz,
4.6.3. 5-(2,2-Difluoro-2-(5-phenyl-1,2,4-oxadiazol-3-yl)ethyl)-3-(4-
methoxyphenyl)oxazolidin-2-one (1cc). Yield: 82.4%. White solid.
Mp 64.4e66.5 ꢀC. 1H NMR (400 MHz, CDCl3)
d 2.84e3.00 (1H, m),
CDCl3)
d
ꢂ120.04 (1F, s), ꢂ112.34 to ꢂ112.24 (2F, m), ꢂ71.79 (2F, s). 13
C
3.08e3.24 (1H, m), 3.80 (3H, s), 3.89 (1H, dd, J1¼8.80 Hz,
J2¼7.60 Hz), 4.24 (1H, t, J¼8.60 Hz), 5.05e5.15 (1H, m), 6.92 (2H, d,
J¼8.80 Hz), 7.41 (2H, d, J¼9.20 Hz), 7.48e7.60 (3H, m), 8.08e8.14
NMR (107 MHz, CDCl3)
d
35.79 (t, J¼22.63 Hz), 50.74, 50.96 (d,
J¼3.21 Hz), 66.70, 66.92, 107.56 (d, J¼28.03 Hz), 113.99 (d, J¼3.42 Hz),
118.85 (d, J¼9.52 Hz), 132.70 (d, J¼11.13 Hz), 136.67 (d, J¼9.52 Hz),
153.62,155.96 (d, J¼155.15 Hz). IR (KBr) 3446, 3199, 2955, 2923, 2855,
2357, 1747, 1636, 1531, 1401, 1231, 1153, 1116, 952, 897, 798, 749, 665,
563 cmꢂ1. HRMS(EI):C16H16ClF5NO3 calcd:414.0770, found:414.0760.
(2H, m). 19F NMR (376 MHz, CDCl3)
d
ꢂ95.11 (1F, d, J¼284.26 Hz),
ꢂ98.03 (1F, d, J¼283.50 Hz). 13C NMR (107 MHz, CDCl3)
d 40.01 (t,
J¼12.09 Hz), 51.23, 55.521, 66.94 (t, J¼4.17 Hz), 114.38, 120.47,
125.34, 127.67, 129.10, 130.87, 132.05, 154.09, 156.66, 168.85, 170.61
(t, J¼35.90 Hz). IR (KBr) 3460, 3178, 2950, 2838, 2232, 1753, 1736,
1668, 1515, 1403, 1250, 1129, 972, 831, 752, 690, 520 cmꢂ1. HRMS
(EI): C20H17F2N3O4 calcd: 401.1187, found: 401.1182.
4.5.12. 3-(3-Fluoro-4-morpholinophenyl)-5-(2,2,3,3,4,4,5,5,5-
nonafluoropentyl)oxazolidin-2-one (1fb). Yield: 78.9%. White solid.
Mp 90.6e91.8 ꢀC. 1H NMR (400 MHz, CDCl3)
d 2.49e2.66 (1H, m),
2.72e2.90 (1H, m), 3.09 (4H, t, J¼4.60 Hz), 3.77e3.84 (1H, dd,
J1¼8.80 Hz, J2¼7.60 Hz), 3.89 (4H, t, J¼4.40 Hz), 4.22 (1H, t,
J¼8.80 Hz), 5.00e5.10 (1H, m), 6.95e6.70 (1H, t, J¼8.80 Hz), 7.10 (1H,
dd, J1¼8.80 Hz, J2¼2.00 Hz), 7.44 (1H, dd, J1¼14.00 Hz, J2¼2.00 Hz).
4.6.4. 3-(4-Chlorophenyl)-5-(2,2-difluoro-2-(5-phenyl-1,2,4-
oxadiazol-3-yl)ethyl)oxazolidin-2-one (1dc). Yield: 84.3%. White
solid. Mp 53.1e57.4 ꢀC. 1H NMR (400 MHz, CDCl3)
d 2.84e3.00 (1H,
m), 3.10e3.24 (1H, m), 3.91 (1H, dd, J1¼8.80 Hz, J2¼7.60 Hz), 4.27
(1H, t, J¼8.60 Hz), 5.06e5.18 (1H, m), 7.35 (2H, d, J¼9.20 Hz),
7.46e7.60 (5H, m), 8.08e8.13 (2H, m). 19F NMR (376 MHz, CDCl3)
19F NMR (376 MHz, CDCl3)
d
ꢂ125.97 to ꢂ125.80(2F, m), ꢂ124.42 to
ꢂ124.26(2F, m), ꢂ119.97 (1F, s), ꢂ112.64 to ꢂ112.50 (2F, m), ꢂ81.92
(3F, t, J¼9.40 Hz). 13C NMR (107 MHz, CDCl3)
d
35.79 (t, J¼22.63 Hz),
d
ꢂ95.06 (1F, d, J¼284.26 Hz), ꢂ98.59 (1F, d, J¼284.63 Hz). 13C NMR
50.74, 50.90, (d, J¼3.21 Hz), 66.69, 66.90, 107.54 (d, J¼28.03 Hz),
113.89 (d, J¼3.42 Hz), 118.85 (d, J¼9.52 Hz), 132.66 (d, J¼11.13 Hz),
136.68 (d, J¼9.52 Hz), 153.63, 154.46 (d, J¼262.15 Hz). IR (KBr) 3125,
(107 MHz, CDCl3)
d
40.98 (t, J¼12.09 Hz), 50.63, 67.02, 119.46,
125.27, 127.66, 129.11, 129.21, 129.75, 132.09, 136.34, 153.54, 168.86,
170.48 (t, J¼35.85 Hz). IR (KBr) 3502, 3104, 2955, 1769, 1594, 1499,
1405, 1296, 1227, 1128, 1094, 956, 826, 751, 700, 516 cmꢂ1. HRMS
(EI): C19H14F2N3O3 calcd: 405.0692, found: 405.0670.
2951, 2859, 1746, 1515, 1400, 1225, 1138, 935, 885, 744, 665 cmꢂ1
.
HRMS (EI): C18H16F10N2O3 calcd: 498.1001, found: 498.0995.
4.6. Typical procedure for synthesis of 5-(fluoroalkyl)-3-aryl/
alkyl oxazolidin-2-one (1ace1fc)
4.6.5. 5-(2,2-Difluoro-2-(5-phenyl-1,2,4-oxadiazol-3-yl)ethyl)-3-
phenethyloxazolidin-2-one (1ec). Yield: 74.3%. White solid. Mp
65.4e69.3 ꢀC. 1H NMR (400 MHz, CDCl3)
d 2.52e2.70 (1H, m),
To a stirred solution of benzyl allyl phenylcarbamates 4a (0.54 g,
mmol) and 5-(difluoroiodomethyl)-3-phenyl-1,2,4-oxadiazole
2.84e3.02 (3H, m), 3.14e3.21 (1H, m), 3.47e3.56 (2H, t, J¼7.40 Hz),
2
3.60 (1H, t, J¼8.80 Hz), 4.79e4.88 (1H, m), 7.20e7.25 (3H, m), 7.31