G. Lemonnier et al. / Tetrahedron 70 (2014) 3123e3133
3131
oil), after flash chromatography (SiO2, cyclohexane/EtOAc, 95:5 to
70:30). Compound 6f anti: Rf¼0.44 cyclohexane/EtOAc 8:2. 1H NMR
pure anti diastereomer (colorless oil) and the mixture of anti/syn
diastereomers (colorless oil), after flash chromatography (SiO2,
cyclohexane/EtOAc, 95:5 to 70:30). Compound 6i anti: Rf¼0.40
(300 MHz, CDCl3)
d
7.28e6.96 (m, 10H), 4.64 (dd, J¼17.7, 3.0 Hz, 1H),
4.45 (dd, J¼50.2, 3.0 Hz, 1H), 4.09e3.94 (m, 1H), 3.35 (dd, J¼25.4,
cyclohexane/EtOAc 8:2. 1H NMR (300 MHz, CDCl3)
d 7.41e6.96 (m,
8.8 Hz, 1H), 2.84e2.69 (m, 1H), 2.60e2.50 (m, 1H), 1.72e1.46 (m,
9H), 4.87 (ddd, J¼17.7, 2.8, 0.7 Hz, 1H), 4.65 (d, J¼8.7 Hz, 1H), 4.47
(dd, J¼50.5, 2.9 Hz, 1H), 2.85e2.65 (m, 1H), 2.60e2.36 (m, 2H),
1.87e1.64 (m, 1H), 1.50e1.32 (m, 1H).∙13C NMR (75 MHz, CDCl3)
2H). 13C NMR (75 MHz, CDCl3)
d
165.3 (d, J¼262 Hz), 141.7, 137.9 (d,
J¼2 Hz), 128.8, 128.5, 128.4, 128.3, 128.3, 127.5, 125.9, 92.9 (d,
J¼20 Hz), 71.1, 56.4 (d, J¼23 Hz), 36.1, 31.8. 19F NMR (282 MHz,
d
164.3 (d, J¼261 Hz), 141.2, 140.1, 133.8, 128.7 (2C), 128.4 (2C), 128.3
CDCl3)
d
ꢀ101.0 (ddd, J¼50, 25, 18 Hz). IR (cmꢀ1): 3413, 3033, 2910,
(2C), 128.2 (2C), 126.0, 94.7 (d, J¼20 Hz), 73.9, 50.6 (d, J¼24 Hz),
1673, 1493, 1451, 1252, 1080. Anal. Calcd for C18H19FO: C, 79.97; H,
33.0, 28.9. 19F NMR (282 MHz, CDCl3)
d
ꢀ107.6 (ddd, J¼50, 28,
7.08. Found: C, 79.91; H, 7.22. Compound 6f syn: Rf¼0.53 cyclo-
18 Hz). IR (cmꢀ1): 3418, 2954, 1670, 1491, 1253, 1087, 1013. Anal.
Calcd for C18H18ClFO: C, 70.93; H, 5.95. Found: C, 71.15; H, 6.17.
Compound 6i syn: Rf¼0.51 cyclohexane/EtOAc 8:2). 1H NMR
hexane/EtOAc 8:2. 1H NMR (300 MHz, CDCl3)
d 7.30e7.08 (m, 10H),
4.57 (dd, J¼18.2, 3.0 Hz, 1H), 4.33 (dd, J¼50.5, 3.0 Hz, 1H), 4.06 (t,
J¼8.3 Hz, 1H), 3.36 (dd, J¼21.8, 7.6 Hz, 1H), 2.89e2.76 (m, 1H),
2.69e2.59 (m, 1H), 2.02e1.87 (m, 1H), 1.77e1.59 (m, 1H). 13C NMR
(300 MHz, CDCl3)
d
7.43e6.97 (m, 9H), 4.79 (d, J¼6.9 Hz, 1H), 4.62
(dd, J¼18.1, 3.0 Hz, 1H), 4.18 (dd, J¼50.9, 3.0 Hz, 1H), 2.86e2.66 (m,
1H), 2.61e2.38 (m, 2H), 2.16e1.99 (m, 1H), 1.97e1.79 (m, 1H).∙13
NMR (75 MHz, CDCl3)
164.8 (d, J¼259 Hz),141.6,140.7,133.4,128.4
(75 MHz, CDCl3)
d
165.6 (d, J¼260 Hz), 141.9, 137.3, 128.9, 128.9,
C
128.5, 128.4, 127.7, 125.9, 92.5 (d, J¼19 Hz), 70.9, 55.8 (d, J¼23 Hz),
d
36.7, 32.1. 19F NMR (282 MHz, CDCl3)
d
ꢀ100.1 (ddd, J¼50, 22,
(4C), 128.3 (2C), 127.6 (2C), 125.9, 93.5 (d, J¼20 Hz), 74.4, 50.5 (d,
18 Hz). IR (cmꢀ1): 3027, 2926, 1667, 1495, 1453, 1244, 1072. Anal.
Calcd for C18H19FO: C, 79.97; H, 7.08. Found: C, 79.73; H, 7.38.
J¼23 Hz), 33.3, 28.3. 19F NMR (282 MHz, CDCl3)
ꢀ103.5 (ddd, J¼51,
d
26, 18 Hz). IR (cmꢀ1): 3420, 2920, 1671, 1452, 1244, 1125. Anal. Calcd
for C18H18ClFO: C, 70.93; H, 5.95. Found: C, 71.12; H, 6.20.
4.3.31. 2-Fluoro-3-Phenyloct-1-en-4-ol 6g (Table 5,entry 7). Following
procedure D, 6g was obtained as the mixture anti/syn diastereomers
(yellow oil), after flash chromatography (SiO2, cyclohexane/EtOAc,
95:5 to 70:30). Compound 6g anti: Rf¼0.55 cyclohexane/EtOAc 8:2. 1H
4.3.34. (E)-2-Fluoro-3-phenethylhepta-1,5-dien-4-ol 6j (Table 5,en-
try 10). Following procedure D, 6j was obtained as the mixture of
anti/syn diastereomer (colorless oil), after flash chromatography
(SiO2, cyclohexane/EtOAc, 95:5 to 70:30, Rf¼0.43 and 0.47 cyclo-
NMR (300 MHz, CDCl3)
d
7.34e7.13 (m, 5H), 4.64 (dd, J¼17.9, 3.0 Hz,
1H), 4.46 (dd, J¼50.3, 3.0 Hz, 1H), 4.12e3.91 (m, 1H), 3.32 (dd, J¼25.5,
hexane/EtOAc 8:2). 1H NMR (300 MHz, CDCl3)
d 7.27e7.05 (m, 10H),
8.5 Hz, 1H), 1.47e1.06 (m, 6H), 0.75 (t, J¼7.2 Hz, 3H). 13C NMR
5.73e5.54 (m, 2H), 5.49e5.25 (m, 2H), 4.71 (dd, J¼20.8, 2.8 Hz, 1H),
4.65 (dd, J¼21.1, 2.8 Hz, 1H), 4.34 (dd, J¼50.6, 2.8 Hz, 1H), 4.28 (dd,
J¼50.7, 2.8 Hz, 1H), 4.08e3.93 (m, 2H), 2.79e2.59 (m, 2H),
2.58e2.37 (m, 2H), 2.36e2.02 (m, 2H), 1.89e1.60 (m, 10H). 13C NMR
(75 MHz, CDCl3)
d
165.4 (d, J¼262 Hz), 138.2 (d, J¼2 Hz), 129.0, 128.7
(2C), 128.3, 127.4, 92.7 (d, J¼20 Hz), 71.8, 56.3 (d, J¼23 Hz), 34.1, 27.7,
22.5, 14.0. 19F NMR (282 MHz, CDCl3)
d
ꢀ100.7 (ddd, J¼50, 25, 18 Hz).
Compound 6g syn: Rf¼0.60 cyclohexane/EtOAc 8:2. 1H NMR
(75 MHz, CDCl3)
d
165.2 (d, J¼261 Hz), 164.9 (d, J¼261 Hz), 141.8,
(300 MHz, CDCl3)
d
7.34e7.13 (m, 5H), 4.58 (dd, J¼17.9, 2.4 Hz, 1H),
141.7, 131.3, 131.2, 129.8, 128.5 (2C), 128.4 (2C), 128.4 (5C), 126.0,
125.9, 93.8 (d, J¼21 Hz), 93.3 (d, J¼20 Hz), 73.8, 73.3, 49.2 (d,
J¼24 Hz), 48.8 (d, J¼23 Hz), 33.3, 33.3, 29.4, 29.0, 17.8 (2C). 19F NMR
4.38 (dd, J¼50.6, 3.0 Hz, 1H), 4.12e3.91 (m, 1H), 3.34 (dd, J¼21.3,
7.1 Hz, 1H), 1.47e1.06 (m, 6H), 0.81 (t, 7.1 Hz, 3H). 13C NMR (75 MHz,
CDCl3)
d
165.9 (d, J¼260 Hz), 137.5, 129.0, 128.8 (2C), 128.3, 127.6, 92.3
(282 MHz, CDCl3)
d
ꢀ102.2 (ddd, J¼51, 27, 18 Hz), ꢀ105.9 (ddd, J¼51,
(d, J¼20 Hz), 71.5, 55.7 (d, J¼24 Hz), 34.6, 27.9, 22.6, 14.1. 19F NMR
28,18 Hz). IR (cmꢀ1): 3420, 3021, 2932,1668,1452,1250,1001. Anal.
Calcd for C15H19FO: C, 76.89; H, 8.17. Found: C, 76.66; H, 8.13.
(282 MHz, CDCl3)
1494, 1454, 1254. Anal. Calcd for C14H19FO: C, 75.64; H, 8.61. Found: C,
75.42; H, 8.48.
d
ꢀ99.7, ꢀ100.1 (m). IR (cmꢀ1): 2956, 2936, 1668,
4.3.35. 2-Fluoro-3-phenethyloct-1-en-4-ol
6k
(Table
5,entry
11). Following procedure D, 6k was obtained as the mixture of anti/
syn diastereomers (colorless oil), after flash chromatography (SiO2,
cyclohexane/EtOAc, 95:5 to 70:30, Rf¼0.55 cyclohexane/EtOAc 8:2).
4.3.32. 2-Fluoro-3-phenyldodec-1-en-4-ol
6h
(Table
5,entry
8). Following procedure D, 6h was obtained as the pure anti di-
astereomer (colorless oil) and the pure syn diastereomer (colorless
oil), after flash chromatography (SiO2, cyclohexane/EtOAc, 95:5 to
70:30). Compound 6h anti: Rf¼0.58 cyclohexane/EtOAc 8:2. 1H
1H NMR (300 MHz, CDCl3)
d
7.40e7.13 (m, 10H), 4.81 (dd, J¼17.9,
2.4 Hz,1H), 4.76 (dd, J¼18.3, 2.5 Hz,1H), 4.41 (dd, J¼51.1, 2.8 Hz,1H),
4.39 (dd, J¼50.9, 2.8 Hz, 1H), 3.65 (br s, 2H), 2.90e2.72 (m, 2H),
2.70e2.50 (m, 2H), 2.39e2.17 (m, 2H), 2.02e1.76 (m, 4H), 1.72e1.25
NMR (300 MHz, CDCl3)
d
7.37e7.08 (m, 5H), 4.65 (d, J¼17.8 Hz, 1H),
4.47 (d, J¼50.3 Hz, 1H), 4.09e3.90 (m, 1H), 3.32 (dd, J¼25.3, 8.7 Hz,
(m, 12H), 0.93 (t, J¼6.8 Hz, 6H). 13C NMR (75 MHz, CDCl3)
d 165.9 (d,
1H), 1.42e1.06 (m, 14H), 0.79 (t, J¼6.5 Hz, 3H). 13C NMR (75 MHz,
J¼261 Hz), 165.5 (d, J¼261 Hz), 141.9, 141.7, 128.5 (2C), 128.4 (2C),
128.4 (2C), 128.4 (2C), 126.0, 125.9, 93.6 (d, J¼20 Hz), 92.9 (d,
J¼20 Hz), 72.6, 72.0, 48.9 (d, J¼23 Hz), 48.6 (d, J¼23 Hz), 34.4, 34.2,
33.4 (2C), 29.8, 28.7, 28.1, 27.8, 22.7, 22.6, 14.1 (2C). 19F NMR
CDCl3)
d
165.4 (d, J¼261 Hz),138.2,128.7 (2C),128.3 (2C),127.4, 92.7
(d, J¼20 Hz), 71.7, 56.3 (d, J¼23 Hz), 34.4, 31.8, 29.5, 29.4, 29.2, 25.5,
22.6, 14.1. 19F NMR (282 MHz, CDCl3)
d
ꢀ100.8 (ddd, J¼50, 25,
17 Hz). IR (cmꢀ1): 3435, 2917, 2851, 1669, 1466, 1454, 1250, 1081.
Anal. Calcd for C18H27FO: C, 77.65; H, 9.78. Found: C, 77.96; H, 9.88.
Compound 6h syn: Rf¼0.69 cyclohexane/EtOAc 8:2. 1H NMR
(282 MHz, CDCl3)
d
ꢀ101.9 (ddd, J¼51, 28, 18 Hz), ꢀ102.7 (ddd, J¼51,
27, 18 Hz). IR (cmꢀ1): 3450, 2955, 2931, 1667, 1454, 1251, 1001. Anal.
Calcd for C16H23FO: C, 76.76; H, 9.26. Found: C, 76.33; H, 9.19.
(300 MHz, CDCl3)
d
7.37e7.11 (m, 5H), 4.59 (d, J¼18.2 Hz, 1H), 4.39
(d, J¼50.6 Hz, 1H), 4.15e3.93 (m, 1H), 3.34 (dd, J¼21.4, 7.4 Hz, 1H),
4.3.36. 2-(4-Bromophenyl)-1-(4-chlorophenyl)-3-fluorobut-3-en-1-
ol 6l (Table 5, entry 12). Following procedure D, 6l was obtained as
the pure anti diastereomer (colorless oil) and the pure syn di-
astereomer (colorless oil), after flash chromatography (SiO2, cy-
clohexane/EtOAc, 95:5 to 70:30). Compound 6l anti: Rf¼0.43
1.62e1.08 (m, 14H), 0.81 (t, J¼6.0 Hz, 3H). 13C NMR (75 MHz, CDCl3)
d
165.8 (d, J¼260 Hz), 137.4, 129.0 (2C), 128.8 (2C), 127.6, 92.32 (d,
J¼20 Hz), 71.5, 55.7 (d, J¼23 Hz), 34.9, 31.9, 29.6 (2C), 29.3, 25.7,
22.7, 14.1. 19F NMR (282 MHz, CDCl3)
ꢀ100.0 (ddd, J¼50, 21, 18 Hz).
IR (cmꢀ1): 3430, 2923, 2853, 1667, 1463, 1189. Anal. Calcd for
18H27FO: C, 77.65; H, 9.78. Found: C, 77.99; H, 9.66.
d
cyclohexane/EtOAc 8:2. 1H NMR (300 MHz, CDCl3)
d 7.29e7.19 (m,
C
2H), 7.14e7.03 (m, 2H), 7.02e6.90 (m, 2H), 6.90e6.79 (m, 2H), 4.92
(d, J¼9.4 Hz, 1H), 4.73 (dd, J¼17.7, 3.2 Hz, 1H), 4.54 (dd, J¼50.0,
3.2 Hz, 1H), 3.53 (dd, J¼24.7, 9.4 Hz, 1H).∙13C NMR (75 MHz, CDCl3)
4.3.33. 1-(4-Chlorophenyl)-3-fluoro-2-phenethylbut-3-en-1-ol
(Table 5, entry 9). Following procedure D, 6i was obtained as the
6i
d
164.1 (d, J¼262 Hz), 139.4, 136.0 (d, J¼2 Hz), 133.7, 131.6 (2C),