D. Zhang, C. Yuan / Tetrahedron 64 (2008) 2480e2488
2487
HPLC analysis: DAICEL Chiralpak AD-H, hexane/2-propanol
90:10, l¼214 nm, flow rate¼0.7 mL minꢁ1, retention time¼
11.1 min (minor) and 13.5 min (major).
DAICEL Chiralpak AD-H, hexane/2-propanol 80:20,
l¼214 nm, flow rate¼0.8 mL minꢁ1, retention time¼9.13 min
(minor) and 10.6 min (major).
4.3.5. (S)-4-Trifluoromethyl-4-hydroxyl-6-(p-fluorophenyl)-
hex-5-ene-2-one (2e)
4.3.8. (S)-4-Trifluoromethyl-4-hydroxyl-6-(p-nitrophenyl)-
hex-5-ene-2-one (2h)
Light yellow liquid 78 mg, yield: 94%, ee%¼87%, [a]D22
Brown solid 84 mg, yield: 92%. Mp: 101e102 ꢀC,
1
1
ꢁ43.1 (c 1.00, CHCl3). H NMR (300 MHz, CDCl3, 25 ꢀC):
ee%¼79%, [a]2D5 ꢁ55.3 (c 1.0, CHCl3). H NMR (300 MHz,
d 7.38 (d, 2H, 3JH, H1 8.7 Hz, J2¼5.4 Hz), 7.02 (t, 2H, 3JH, H2
¼
¼
CDCl3, 25 ꢀC): d 8.19 (d, 2H, JH, H¼8.1 Hz), 7.54 (d, 2H,
3
3
3
3
8.7 Hz), 6.91 (d, 1H, JH, H¼16.2 Hz), 6.05 (d, 1H, JH, H
3JH, H¼8.1 Hz), 7.05 (d, 1H, JH, H¼15.6 Hz), 6.31 (d, 1H,
3
3
16.2 Hz), 5.35 (s, 1H, OH), 3.04 (d, 1H, JH, ¼17.4 Hz,
3JH, ¼15.6 Hz), 5.49 (s, 1H, OH), 3.11 (d, 1H, JH,
19
¼
H
H
H
3
3
CH2CO), 2.87 (d, 1H, JH, H¼17.4 Hz, CH2CO), 2.26 (s, 3H,
13
17.1 Hz, CH2CO), 2.90 (d, 1H, JH, ¼17.1 Hz, CH2CO),
H
CH3CO). 19F NMR (282 MHz, CDCl3, 25 ꢀC): d ꢁ81.0 (s, 3F,
2.29 (s, 3H, CH3CO). F NMR (282 MHz, CDCl3, 25 ꢀC):
13
CF3), ꢁ113.0 (m, 1F). C NMR (50 MHz, CDCl3, 25 ꢀC):
d ꢁ80.6 (s, 3F, CF3). C NMR (50 MHz, CDCl3, 25 ꢀC):
d 208.8, 164.0, 161.6, 132.7, 131.7 (d, 1C, JCeF¼10.5 Hz),
128.5 (d, 2C, JCeF¼23.7 Hz), 126.0 (C*), 124.0, 123.1 (C*),
115.6 (d, 2C, JCeF¼64.8 Hz), 75.1 (q), 44.6, 32.0. IR
(film, cmꢁ1): 3416, 1708, 1604, 1512, 1416, 1365, 1232,
1171, 1097, 976. EIMS (m/z, %): 276 (Mþ, 6), 43 (100). Anal.
Calcd for C13H12O2F4: C, 56.53; H, 4.38. Found: C, 56.41; H,
4.36. HPLC analysis: DAICEL Chiralpak AD-H, hexane/
2-propanol 90:10, l¼214 nm, flow rate¼0.7 mL minꢁ1, reten-
tion time¼9.75 min (minor) and 11.6 min (major).
d 208.7, 147.5, 141.8, 131.9, 129.0, 127.6, 125.8 (C*), 124.0,
122.9 (C*), 75.3 (q), 44.3, 31.9. IR (film, cmꢁ1): 3418, 2851,
1706, 1597, 1517, 1346, 1252, 1192, 1110, 981. EIMS (m/z,
%): 303 (Mþ, 1), 43 (100). Anal. Calcd for C13H12NO4F3: C,
51.49; H, 3.99; N, 4.62. Found: C, 51.53; H, 4.09; N, 4.56.
HPLC analysis: DAICEL Chiralpak AD-H, hexane/2-propanol
80:20, l¼214 nm, flow rate¼0.8 mL minꢁ1, retention time¼
9.93 min (minor) and 12.8 min (major).
4.3.9. (S)-4-Trifluoromethyl-4-hydroxyl-6-(m-nitrophenyl)-
hex-5-ene-2-one (2i)
4.3.6. (S)-4-Trifluoromethyl-4-hydroxyl-6-(p-chlorophenyl)-
hex-5-ene-2-one (2f)
Brownish yellow solid 81 mg, yield: 89%. Mp: 83e84 ꢀC,
1
White solid 84 mg, yield: 96%. Mp: 69e71 ꢀC, ee%¼80%,
ee%¼82%, [a]2D4 ꢁ54.5 (c 1.0, CHCl3). H NMR (300 MHz,
[a]2D2 ꢁ48.8 (c 1.0, CHCl3). 1H NMR (300 MHz, CDCl3,
CDCl3, 25 ꢀC): d 8.26 (s, 1H), 8.12 (dt, 1H, JH, H1¼8.1 Hz,
3
3
3
25 ꢀC): d 7.23 (s, 4H), 6.82 (d, 1H, JH, H¼16.2 Hz), 6.03 (d,
3JH,
¼0.9 Hz), 7.70 (d, 1H, JH, ¼7.8 Hz), 7.52 (d,
H2
H
3
3
3
3
1H, JH, H¼16.2 Hz), 5.30 (s, 1H, OH), 2.96 (d, 1H, JH, H
19
¼
1H, JH, H¼8.7 Hz), 7.04 (d, 1H, JH, H¼15.9 Hz), 6.30 (d,
3
3
3
16.5 Hz, CH2CO), 2.79 (d, 1H, JH, ¼16.5 Hz, CH2CO),
1H, JH, H¼15.9 Hz), 5.48 (s, 1H, OH), 3.11 (d, 1H, JH, H
19
¼
H
3
2.17 (s, 3H, CH3CO). F NMR (282 MHz, CDCl3, 25 ꢀC):
17.1 Hz, CH2CO), 2.93 (d, 1H, JH, ¼17.1 Hz, CH2CO),
H
13
d ꢁ80.9 (s, 3F, CF3). C NMR (50 MHz, CDCl3, 25 ꢀC):
2.30 (s, 3H, CH3CO). F NMR (282 MHz, CDCl3, 25 ꢀC):
13
d 208.7, 134.2, 134.0, 132.7, 128.9, 128.1, 125.9 (C*),
124.8, 123.1 (C*), 75.2 (q), 44.5, 32.0. IR (film, cmꢁ1):
3454, 2919, 1716, 1492, 1335, 1246, 1192, 1089, 1012, 995.
EIMS (m/z, %): 292 (Mþ, 6), 43 (100). Anal. Calcd for
C13H12O2F3Cl: C, 53.35; H, 4.13. Found: C, 53.41; H, 4.13.
HPLC analysis: Nucleocel Delta S (OD), hexane/2-propanol
95:5, l¼214 nm, flow rate¼0.5 mL minꢁ1, retention time¼
16.9 min (minor) and 19.2 min (major).
d ꢁ80.8 (s, 3F, CF3). C NMR (50 MHz, CDCl3, 25 ꢀC):
d 208.8, 148.6, 137.2, 133.0, 131.8, 129.7, 128.6 (C*),
127.6, 125.8 (C*), 122.9, 121.2, 75.3 (q), 44.3, 31.9. IR
(film, cmꢁ1): 3441, 3072, 1714, 1527, 1413, 1355, 1282,
1164, 1099, 973. EIMS (m/z, %): 303 (Mþ, 1), 43 (100).
Anal. Calcd for C13H12NO4F3: C, 51.49; H, 3.99; N, 4.62.
Found: C, 51.68; H, 4.03; N, 4.47. HPLC analysis: DAICEL
Chiralpak AD-H, hexane/2-propanol 90:10, l¼254 nm, flow
rate¼0.7 mL minꢁ1, retention time¼48.3 min (minor) and
60.5 min (major).
4.3.7. (S)-4-Trifluoromethyl-4-hydroxyl-6-(p-cyanophenyl)-
hex-5-ene-2-one (2g)
Brown solid 82 mg, yield: 97%. Mp: 86e87 ꢀC, ee%¼80%,
[a]D29 ꢁ55.9 (c 1.0, CHCl3). 1H NMR (300 MHz, CDCl3, 25 ꢀC):
d 7.63 (d, 2H, 3JH, H¼8.1 Hz), 7.49 (d, 2H, 3JH, H¼8.1 Hz), 6.99
(d, 1H, 3JH, H¼15.9 Hz), 6.25 (d, 1H, 3JH, H¼15.9 Hz), 5.46 (s,
3JH, H¼16.8 Hz, CH2CO), 2.28 (s, 3H, CH3CO). 19F NMR
(282 MHz, CDCl3, 25 ꢀC): d ꢁ80.7 (s, 3F, CF3). 13C NMR
(50 MHz, CDCl3, 25 ꢀC): d 208.6, 139.9, 132.5, 132.4, 128.1,
127.4, 125.8 (C*), 122.9 (C*), 118.6, 111.8, 75.2 (q), 44.4,
32.0. IR (film, cmꢁ1): 3375, 2225, 1700, 1606, 1507, 1436,
1340, 1256, 1133, 1097, 985. EIMS (m/z, %): 283 (Mþ, 1), 43
(100). Anal. Calcd for C14H12NO2F3: C, 59.37; H, 4.27; N,
4.94. Found: C, 59.44; H, 4.14; N, 4.78. HPLC analysis:
4.3.10. (S)-4-Trifluoromethyl-4-hydroxyl-6-(p-bromo-
phenyl)-hex-5-ene-2-one (2j)
White solid 84 mg, yield: 90%. Mp: 76e77 ꢀC, ee%¼91%,
[a]2D2 ꢁ63.9 (c 1.0, CHCl3). 1H NMR (300 MHz, CDCl3,
3
3
3
1H, OH), 3.09 (d, 1H, JH, H¼16.8 Hz, CH2CO), 2.88 (d, 1H,
25 ꢀC): d 7.39 (d, 2H, JH, H¼8.4 Hz), 7.19 (d, 2H, JH, H
¼
¼
3
3
8.4 Hz), 6.82 (d, 1H, JH, H¼16.2 Hz), 6.05 (d, 1H, JH, H
3
16.2 Hz), 5.28 (s, 1H, OH), 2.97 (d, 1H, JH, ¼16.8 Hz,
H
3
CH2CO), 2.79 (d, 1H, JH, H¼16.8 Hz, CH2CO), 2.19 (s, 3H,
13
CH3CO). 19F NMR (282 MHz, CDCl3, 25 ꢀC): d ꢁ81.5 (s, 3F,
CF3). C NMR (50 MHz, CDCl3, 25 ꢀC): d 208.7, 134.4,
132.8, 131.8, 128.4, 125.9, 125.0 (C*), 123.0, 122.4 (C*),
75.2 (q), 44.5, 32.0. IR (film, cmꢁ1): 3450, 1716, 1490, 1244,
1195, 1131, 813. EIMS (m/z, %): 337 (Mþ, 2), 43 (100). Anal.