334
D. Watanabe et al. / Journal of Fluorine Chemistry 132 (2011) 327–338
reduced pressure to leave a residue, which was purified by silica
gel column chromatography (hexane/EtOAc = 40: 1) and then by
MPLC (hexane/EtOAc = 20:1) to give (Z)-syn-12b (183 mg,
0.40 mmol, 79% yield) and (E)-syn-12b (18 mg, 0.04 mmol, 8%
yield) in the order of elution.
4.4.3. (2S,3R,Z)-1-{[tert-Butyl(diphenyl)silyl]oxy}-4-fluoro-2,7-
dimethyloct-4-en-3-ol (Z)-syn-12d and (2S,3R,E)-1-{[tert-
butyl(diphenyl)silyl]oxy}-4-fluoro-2,7-dimethyloct-4-en-3-ol (E)-
syn-12d
By the similar procedure for the preparation of syn-12b,
reaction of syn-11a (99% ee, 202 mg, 0.50 mmol), i-PrMgBr (1.0 M
solution in THF, 1.3 ml, 1.3 mmol) and CuI (19 mg, 0.10 mmol)
provided (Z)-syn-12c (195 mg, 0.44 mmol, 88% yield) and (E)-syn-
12c (11 mg, 0.025 mmol, 5% yield), respectively after the
chromatographic purification by silica gel column (hexane/
EtOAc = 40:1) followed by MPLC (hexane/EtOAc = 20:1).
(Z)-syn-12b. Colorless oil; [
3476, 3070, 823 cmꢁ1 1H NMR (400 MHz, CDCl3)
d 0.98 (3H, d,
a]
25 +4.5 (c = 1.0, CHCl3); IR (neat)
D
n
;
J = 7.1 Hz), 1.11 (9H, s), 2.12–2.22 (1H, m), 3.27 (1H, brs), 3.45–3.60
(2H, m), 3.80 (2H, d, J = 5.4 Hz), 4.49 (1H, d, J = 10.0 Hz), 5.18 (1H,
dt, J = 37.0, 10.0 Hz), 7.24–7.27 (3H, m), 7.29–7.33 (2H, m), 7.42–
7.49 (6H, m), 7.70–7.72 (4H, m); 13C NMR (100 MHz, CDCl3)
d 10.8,
19.1, 26.8, 29.5 (d, J = 5.7 Hz), 37.5, 67.8, 72.7 (d, J = 32.9 Hz), 105.2
(d, J = 12.5 Hz), 126.0, 127.8, 128.3, 128.4, 129.9, 132.9 (d,
J = 14.2 Hz), 135.6 (d, J = 9.7 Hz), 140.3, 158.8 (d, J = 256.2 Hz);
(Z)-syn-12d. Colorless oil; [
3467, 3072, 823 cmꢁ1 1H NMR (400 MHz, CDCl3)
d 0.95 (6H, d
a]
25 +1.3 (c = 1.0, CHCl3); IR (neat)
D
n
;
J = 6.7 Hz), 0.98 (3H, d, J = 7.1 Hz), 1.12 (9H, s), 1.60–1.75 (1H, m),
2.02–2.10 (2H, m), 2.12–2.17 (1H, m), 3.28 (1H, brs), 3.79 (2H, d,
J = 5.3 Hz), 4.44 (1H, dd, J = 11.0, 3.2 Hz), 4.95 (1H, dt, J = 38.5,
7.7 Hz), 7.41–7.50 (6H, m), 7.71–7.74 (4H, m); 13C NMR (100 MHz,
19F NMR (376 MHz, CDCl3)
d
ꢁ59.6 (1F, dd, J = 37.0, 10.0 Hz); MS
(ESI-TOF) m/z 463 [M+H]+; HRMS calcd for C29H36FO2Si [M+H]+:
463.2482, found: 463.2469.
(E)-syn-12b. Colorless oil; IR (neat)
822 cmꢁ1 1H NMR (400 MHz, CDCl3)
n
3465, 3070, 2931,
CDCl3) d 10.9, 19.1, 22.2 (d, J = 3.6 Hz), 26.8, 28.4, 32.2 (d,
J = 4.0 Hz), 37.6, 67.7, 72.8 (d, J = 33.4 Hz), 104.9 (d, J = 12.9 Hz),
;
d
0.96 (3H, d, J = 6.9 Hz),
1.07 (9H, s), 2.15–2.21 (1H, m), 3.34 (1H, dd, J = 15.9, 7.5 Hz), 3.45
(1H, dd, J = 15.9, 8.7 Hz), 3.66 (1H, dd, J = 10.2, 4.6 Hz), 3.77 (1H, dd,
J = 10.0, 7.8 Hz), 4.75 (1H, dd, J = 25.0, 4.8 Hz), 5.41 (1H, m), 7.18–
7.21 (3H, m), 7.26–7.29 (2H, m), 7.38–7.45 (6H, m), 7.66–7.70 (4H,
127.8, 127.8, 129.8, 132.8, 133.0, 135.5, 135.6, 158.7 (d,
J = 254.2 Hz); 19F NMR (376 MHz, CDCl3)
d
ꢁ59.8 (1F, dd,
J = 38.5, 11.0 Hz); MS (ESI-TOF) m/z 429 [M+H]+; HRMS calcd for
26H38FO2Si [M+H]+: 429.2597, found: 429.2625.
(E)-syn-12d. Colorless oil; IR (neat)
3452, 3071, 827 cmꢁ1; 1H
NMR (CDCl3, 400 MHz) 0.89–0.94 (9H, m), 1.08 (9H, s), 1.59–1.64
C
m); 13C NMR (100 MHz, CDCl3)
d
12.0, 19.1, 26.8, 30.8 (d,
n
J = 9.5 Hz), 39.2, 67.2, 69.6 (d, J = 27.3 Hz), 107.4 (d, J = 22.1 Hz),
d
126.3, 127.8, 128.1, 128.5, 129.8, 129.8, 132.9, 133.1, 135.5, 135.7,
(1H, m), 1.86–1.93 (2H, m), 2.13–2.16 (1H, m), 2.96 (1H, brs), 3.61
(1H, dd, J = 10.1, 4.7 Hz), 3.75 (1H, dd, J = 10.1, 8.0 Hz), 4.64 (1H, dd,
J = 25.0, 4.9 Hz), 5.20 (1H, dt, J = 23.2, 8.1 Hz), 7.38–7.46 (6H, m),
7.67–7.71 (4H, m); 13C NMR (CDCl3, 100 MHz)
d 12.1, 19.2, 22.0,
139.8, 159.0 (d, J = 252.6 Hz); 19F NMR (376 MHz, CDCl3)
d
ꢁ54.9
(1F, t, J = 25.0 Hz); MS (ESI-TOF) m/z 463 [M+H]+; HRMS calcd for
29H36FO2Si [M+H]+: 463.2324, found: 463.2469.
C
22.3, 26.8, 28.8, 33.9 (d, J = 8.0 Hz), 39.4, 67.0, 69.0 (d, J = 26.5 Hz),
107.3 (d, J = 19.8 Hz), 127.7, 129.7, 129.8, 133.0, 133.3, 135.5,
4.4.2. (2S,3S,Z)-1-{[tert-Butyl(diphenyl)silyl]oxy}-4-fluoro-2-
methyl-6-phenylhex-4-en-3-ol (Z)-anti-12b and (2S,3S,E)-1-{[tert-
butyl(diphenyl)silyl]oxy}-4-fluoro-2-methyl-6-phenylhex-4-en-3-ol
(E)-anti-12b
135.7, 158.6 (d, J = 251.1 Hz); 19F NMR (CDCl3, 376 MHz)
d
ꢁ56.4
(1F, m); MS (ESI-TOF) m/z 429 [M+H]+; HRMS calcd for C26H38FO2Si
[M+H]+: 429.2640, found: 429.2625. Anal. Calcd for C26H37FO2Si: C,
72.85; H, 8.70. Found: C, 72.67; H, 8.36.
By the similar procedure for the preparation of syn-12b,
reaction of anti-11a (99% ee, 202 mg, 0.50 mmol), PhMgBr (1.0 M
solution in THF, 1.3 ml, 1.3 mmol) and CuI (19 mg, 0.10 mmol)
provided (Z)-anti-12b (179 mg, 0.39 mmol, 77% yield) and (E)-
anti-12b (16 mg, 0.034 mmol, 6.8% yield), respectively after the
chromatographic purification by silica gel column (hexane/
EtOAc = 40:1) followed by MPLC (hexane/EtOAc = 20:1).
4.4.4. (2S,3S,Z)-1-{[tert-Butyl(diphenyl)silyl]oxy}-4-fluoro-2,7-
dimethyloct-4-en-3-ol (Z)-anti-12d and (2S,3S,E)-1-{[tert-
butyl(diphenyl)silyl]oxy}-4-fluoro-2,7-dimethyloct-4-en-3-ol (E)-
anti-12d
By the similar procedure for the preparation of syn-12d,
reaction of anti-11a (99% ee, 202 mg, 0.50 mmol), i-PrMgBr (1.0 M
solution in THF, 1.3 ml, 1.3 mmol) and CuI (19 mg, 0.10 mmol)
provided (Z)-anti-12d (205 mg, 0.46 mmol, 92% yield) and (E)-
anti-12d (15 mg, 0.03 mmol, 6.7% yield), respectively after the
chromatographic purification by silica gel column (hexane/
(Z)-anti-12b. Colorless oil; [
3465, 3070, 822 cmꢁ1 1H NMR (400 MHz, CDCl3)
d 0.18 (3H, d,
a]
25 +5.3 (c = 1.0, CHCl3); IR (neat)
D
n
;
J = 7.0 Hz), 0.93 (9H, s), 1.95–2.02 (1H, m), 3.51 (1H, dd, J = 10.3,
6.7 Hz), 3.68 (1H, dd, J = 10.3, 3.6 Hz), 4.00 (1H, dd, J = 18.0, 7.3 Hz),
5.02 (1H, dt, J = 37.0, 7.6 Hz), 7.05–7.17 (5H, m), 7.24–7.32 (6H, m),
7.53–7.55 (4H, m); 13C NMR (100 MHz, CDCl3)
d
13.7, 19.1, 26.8,
EtOAc = 40: 1) followed by MPLC (hexane/EtOAc = 20:1).
25
29.7 (d, J = 5.4 Hz), 37.2, 68.1, 76.0 (d, J = 29.7 Hz), 106.7 (d,
J = 13.1 Hz), 126.1, 127.8, 128.3, 128.5, 129.9, 132.6 (d, J = 3.8 Hz),
135.6 (d, J = 3.7 Hz), 140.1, 159.7 (d, J = 259.3 Hz); 19F NMR
(Z)-anti-12d. Colorless oil; [
a
]
+18.6 (c = 1.0, CHCl3); IR
D
(neat)
n
3475, 3070, 823 cmꢁ1; 1H NMR (400 MHz, CDCl3)
d 0.92–
0.95 (9H, m), 1.09 (9H, s), 1.63–1.70 (1H, m), 2.02–2.13 (3H, m),
3.65 (1H, dd, J = 10.2, 6.7 Hz), 3.90 (1H, dd, J = 10.2, 3.7 Hz), 3.95
(1H, brs), 4.10 (1H, dd, J = 18.0, 6.7 Hz), 4.94 (1H, dt, J = 37.0,
7.7 Hz), 7.40–7.48 (6H, m), 7.70 (4H, m); 13C NMR (100 MHz,
(376 MHz, CDCl3)
d
ꢁ63.1 (1F, dd, J = 37.0, 18.0 Hz); MS (ESI-
TOF) m/z 485 [M+Na]+; HRMS calcd for C29H35FNaO2Si [M+Na]+:
485.2278, found: 485.2288. Anal. Calcd for C29H35FO2Si: C, 75.28;
H, 7.62. Found: C, 75.29; H, 7.59.
CDCl3)
68,1, 76.1 (d, J = 30.6 Hz), 106.6 (d, J = 13.8 Hz), 127.8, 129.8, 132.6,
135.6, 159.0 (d, J = 257.4 Hz); 19F NMR (376 MHz, CDCl3)
d 13.6, 19.1, 22.2, 22.3, 26.8, 28.3, 32.3 (d, J = 3.5 Hz), 37.2,
(E)-anti-12b. Colorless oil; IR (neat)
823; 1H NMR (400 MHz, CDCl3)
0.84 (3H, d, J = 7.0 Hz), 1.07 (9H,
n
cmꢁ1: 3465, 3068, 1704,
d
d
ꢁ63.5
s), 2.13–2.19 (1H, m), 3.38 (1H, dd, J = 15.8, 8.2 Hz), 3.43–3.49 (1H,
m), 3.69 (1H, dd, J = 10.2, 7.4 Hz), 3.72 (1H, brs), 3.88 (1H, dd,
J = 10.2, 3.9 Hz), 4.51–4.60 (1H, m), 5.43 (1H, dt, J = 22.0, 8.2 Hz),
7.19–7.30 (5H, m), 7.39–7.45 (6H, m), 7.68–7.70 (4H, m); 13C NMR
(1F, dt, J = 37.0, 18.0 Hz); MS (ESI-TOF) m/z 429 [M+H]+; HRMS
calcd for C26H38FO2Si [M+H]+: 429.2645, found: 429.2625. Anal.
Calcd for C26H37FO2Si: C, 72.85; H, 8.70. Found: C, 72.47; H, 8.65.
(E)-anti-12d. Colorless oil; IR (neat)
NMR (400 MHz, CDCl3) 0.83 (3H, d, J = 6.9 Hz), 0.91 (3H, d,
n
3466, 3071, 822 cmꢁ1; 1H
(100 MHz, CDCl3)
71.4 (d, J = 27.3 Hz), 108.1 (d, J = 22.1 Hz), 126.1, 127.8, 128.2,
128.6, 129.9, 132.7, 132.8, 135.6, 139.8, 158.8 (d, J = 158.8 Hz); 19
d
13.3, 19.1, 26.8, 31.0 (d, J = 9.3 Hz), 37.7, 68.3,
d
J = 6.0 Hz), 0.93 (3H, d, J = 5.6 Hz), 1.08 (9H, s), 1.60–1.67 (1H, m),
1.91–1.96 (2H, m), 2.08–2.14 (1H, m), 3.69 (1H, dd, J = 10.2, 7.1 Hz),
3.88 (1H, dd, J = 10.2, 3.5 Hz), 4.45 (1H, dd, J = 28.2, 9.0 Hz), 5.24
F
NMR (376 MHz, CDCl3)
d
ꢁ59.6 (1F, dd, J = 28.0, 22.0 Hz); MS (ESI-
TOF) m/z 463 [M+H]+; HRMS calcd for C29H36FO2Si [M+H]+:
(1H, dt, J = 22.5, 8.1 Hz), 7.36–7.48 (6H, m), 7.65–7.70 (4H, m); 13
NMR (100 MHz, CDCl3) d 13.3, 19.1, 22.1, 22.3, 26.8, 28.8, 34.0 (d,
C
463.2438, found: 463.2469.