A. Saito et al. / Journal of Fluorine Chemistry 126 (2005) 1166–1173
1171
CDCl3) d; À7.5 (Z–1F, d, J = 13.4 Hz), À12.0 (E–1F, d,
J = 31.3 Hz). EI–MS m/z: 349 (M+–C4H9). HRMS calcd for
C16H15BrFOSi: 349.0060 (M+–C4H9). Found: 349.0054.
(E)- and (Z)-3-bromo-3-fluoro-2-propenyl (1,1-dimethy-
lethyl)(diphenyl)silyl ether (8d): Colorless oil. IR (neat)
n cmÀ1; 3071, 2958, 2857, 1472, 1428, 1113, 1070, 822,
740, 702. 1H NMR (400 MHz, CDCl3) d; 1.09 (9H, s), 4.24
(Z–2H, dd, J = 6.8, 2.2 Hz), 4.28 (E–2H, dd, J = 6.9,
2.7 Hz), 5.30 (E–1H, dd, J = 30.6, 6.9 Hz), 5.74 (Z–1H,
dd, J = 12.3, 6.8 Hz), 7.35–7.53 (6H, m), 7.62–7.78 (4H, m).
13C NMR (100.6 MHz, CDCl3) d; 19.1, 26.8, 57.9 (E, d,
J = 3.3 Hz), 61.0 (Z, d, J = 7.3 Hz), 109.8 (Z, d,
J = 14.7 Hz), 112.4 (E, d, J = 10.7 Hz), 127.8, 129.8,
133.2 (E), 133.2 (Z), 133.4 (E, d, J = 322.5 Hz), 135.5
(E), 135.6 (Z), 136.2 (Z, d, J = 318.6 Hz). 19F NMR
(376.5 MHz, CDCl3) d; À6.6 (Z–1F, dd, J = 12.3, 2.2 Hz),
À8.8 (E–1F, dd, J = 30.6, 2.7 Hz). EI–MS m/z: 335 (M+–
C4H9). HRMS calcd for C15H13BrFOSi: 334.9903 (M+–
C4H9). Found: 334.9908. Anal. Calcd for C19H22BrFOSi: C,
58.01; H, 5.64. Found: C, 58.18; H, 5.73.
J = 4.3 Hz), 31.4, 35.3, 35.4, 70.1 (d, J = 30.3 Hz), 105.9 (d,
J = 13.9 Hz), 126.0, 126.0, 128.3, 128.4, 141.3, 159.5 (d,
J = 257.4 Hz). 19F NMR (376.5 MHz, CDCl3) d; À61.5 (1F,
dd, J = 37.5, 16.6 Hz). EI–MS m/z: 284 (M+). HRMS calcd
for C19H21FO: 284.1576 (M+). Found: 284.1565. Anal.
Calcd for C19H21FO: C, 80.25; H, 7.44. Found: C, 79.98; H,
7.49.
(Z)-2-Fluoro-1,5-diphenyl-2-penten-1-ol (7bb): Color-
less oil. IR (neat) n cmÀ1; 3389, 3028, 2926, 2859, 1496,
1453, 1024, 748, 700. 1H NMR (400 MHz, CDCl3) d; 2.26
(1H, br. s), 2.48 (2H, dt, J = 7.5, 7.5 Hz), 2.73 (2H, t,
J = 7.5 Hz), 4.95 (1H, dt, J = 36.9, 7.5 Hz), 5.17 (1H, d,
J = 12.7 Hz), 7.19–7.25 (3H, m), 7.28–7.39 (7H, m). 13C
NMR (100.6 MHz, CDCl3) d; 25.1 (d, J = 4.0 Hz), 35.3,
72.7 (d, J = 32.0 Hz), 106.7 (d, J = 13.3 Hz), 126.0, 126.6,
128.2, 128.3, 128.4, 128.5, 139.5, 141.3, 158.8 (d,
J = 256.5 Hz). 19F NMR (376.5 MHz, CDCl3) d; À59.4
(1F, dd, J = 36.9, 12.7 Hz). EI–MS m/z: 256 (M+). HRMS
calcd for C17H17FO: 256.1263 (M+). Found: 256.1256.
(Z)-7-{[( 1,1-Dimethylethyl)(diphenyl)silyl]oxy}-4-fluoro
-1-phenyl-4-hepten-3-ol (7ca): Colorless oil. IR (neat)
n cmÀ1; 3388, 3070, 2930, 2858, 1472, 1428, 1111, 740,
701. 1H NMR (400 MHz, CDCl3) d; 1.09 (9H, s), 1.91–2.09
(2H, m), 2.40 (2H, dt, J = 7.4, 6.4 Hz), 2.66–2.85 (2H, m),
3.73 (2H, t, J = 6.4 Hz), 4.07 (1H, ddd, J = 15.8, 9.4,
6.2 Hz), 4.92 (1H, dt, J = 37.8, 7.4 Hz), 7.18–7.26 (3H, m),
7.28–7.33 (2H, m), 7.37–7.47 (6H, m), 7.69–7.71 (4H, m).
13C NMR (100.6 MHz, CDCl3) d; 19.6, 27.3, 27.4 (d,
J = 3.9 Hz), 32.0, 35.8, 63.5, 70.5 (d, J = 30.2 Hz), 103.8 (d,
J = 13.7 Hz), 126.4, 128.1, 128.9, 128.9, 130.0, 134.3,
136.0, 141.8, 160.6 (d, J = 257.5 Hz). 19F NMR
(376.5 MHz, CDCl3) d; À61.9 (1F, dd, J = 37.8, 15.8 Hz).
EI–MS m/z: 230 (M+–C16H21F). HRMS calcd for
C13H14O2Si: 230.0763 (M+–C16H21F). Found: 230.0780.
Anal. Calcd for C29H35FO2Si: C, 75.28; H, 7.62. Found: C,
75.38; H, 7.66.
3.4. General procedure for CrCl2/NiCl2-mediated
reaction of 1-bromo-1-fluoroalkene
with aldehyde
Under an argon atmosphere, to a mixture of CrCl2
(185 mg, 1.5 mmol) and NiCl2 (2.0 mg, 15 mmol) in DMF
(4 mL) sonicated for 10 min, was added a solution of 8a
(120 mg, 0.25 mmol) and 3-phenylpropanal (50 mL,
0.49 mmol) in DMF (2 mL). After being stirred at room
temperature for 4 h, addition of H2O followed by extractive
work-up and purification by column chromatography
(hexane/AcOEt = 5:1) gave the product 7aa (35.4 mg,
0.14 mmol, 74% yield).
(Z)-2-Fluoro-1,5-diphenyl-1-penten-3-ol (7aa): Color-
less oil. IR (neat) n cmÀ1; 3365, 3027, 2926, 1495, 1451,
1
1032, 752, 695. H NMR (400 MHz, CDCl3) d; 2.02–2.18
(Z)-5-{ [(1,1-Dimethylethyl)(diphenyl)silyl]oxy}-2-fluoro
-1-phenyl-2-penten-1-ol (7cb): Colorless oil. IR (neat)
n cmÀ1; 3397, 3070, 2930, 2858, 1472, 1428, 1111, 739,
702. 1H NMR (400 MHz, CDCl3) d; 1.06 (9H, s), 2.20 (1H,
br. s), 2.40 (2H, dt, J = 7.4, 6.4 Hz), 3.71 (2H, t, J = 6.4 Hz),
5.00 (1H, dt, J = 37.3, 7.4 Hz), 5.21 (1H, dd, J = 12.3,
3.5 Hz), 7.33–7.47 (11H, m), 7.66–7.71 (4H, m). 13C NMR
(100.6 MHz, CDCl3) d; 19.2, 26.8, 27.0 (d, J = 3.7 Hz), 63.0,
72.8 (d, J = 31.7 Hz), 104.5 (d, J = 13.3 Hz), 126.7, 127.6,
128.3, 128.5, 129.6, 133.8, 135.6, 139.5, 159.5 (d,
J = 257.0 Hz). 19F NMR (376.5 MHz, CDCl3) d; À58.7
(1F, dd, J = 37.3, 12.3 Hz). EI–MS m/z: 299 (M+–C10H15).
HRMS calcd for C17H18FO2Si: 299.0904 (M+–C10H15).
Found: 299.0893. Anal. Calcd for C27H31FO2Si: C, 74.61;
H, 7.19. Found: C, 74.37; H, 7.33.
(2H, m), 2.72–2.86 (2H, m), 4.24 (1H, ddd, J = 15.2, 7.2,
6.2 Hz), 5.78 (1H, d, J = 39.6 Hz), 7.20–7.37 (8H, m), 7.49–
7.53 (2H, m). 13C NMR (100.6 MHz, CDCl3) d; 31.5, 35.5,
70.6 (d, J = 30.1 Hz), 106.5 (d, J = 6.7 Hz), 126.0, 127.4,
128.5, 128.7, 128.7, 132.7, 141.2, 160.1 (d, J = 269.7 Hz).
19F NMR (376.5 MHz, CDCl3) d; À55.2 (1F, dd, J = 39.6,
15.2 Hz). EI–MS m/z: 256 (M+). HRMS calcd for
C17H17FO: 256.1263 (M+). Found: 256.1252. Anal. Calcd
for C17H17FO: C, 79.66; H, 6.69. Found: C, 79.27; H, 6.94.
1
(Z)-2-Fluoro-1,3-diphenyl-2-propen-1-ol (7ab): H and
19F NMR spectra of this compound was identical with those
reported by Hiyama et al [24].
(Z)-4-Fluoro-1,7-diphenyl-4-hepten-3-ol (7ba): Color-
less oil. IR (neat) n cmÀ1; 3377, 3027, 2925, 2858, 1496,
1
1454, 1030, 748, 699. H NMR (400 MHz, CDCl3) d; 1.86
(Z)-6-{ [(1,1-Dimethylethyl)(diphenyl)silyl]oxy}-4-fluoro
-1-phenyl-4-hexen-3-ol (7da): Colorless oil. IR (neat)
n cmÀ1; 3388, 3070, 2931, 2858, 1471, 1428, 1111, 1065,
740, 701. 1H NMR (400 MHz, CDCl3) d; 1.08 (9H, s), 1.72
(1H, br. s), 1.87–2.01 (2H, m), 2.64–2.81 (2H, m), 4.04 (1H,
(1H, br. s), 1.91–2.05 (2H, m), 2.47 (2H, dt, J = 7.5, 7.5 Hz),
2.59–2.78 (4H, m), 4.06 (1H, ddd, J = 16.6, 7.3, 6.5 Hz),
4.85 (1H, dt, J = 37.5, 7.5 Hz), 7.15–7.26 (6H, m), 7.29–
7.33 (4H, m). 13C NMR (100.6 MHz, CDCl3) d; 24.9 (d,