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A. Bouziane et al. / Tetrahedron 64 (2008) 11745–11750
(THF) was distilled from deep blue solutions of sodium/benzo-
phenone ketyl prior to use. Unless otherwise stated, all reagents
were used as received. Most of reactions were monitored by TLC
on pre-coated silica plates (Merck 60 F254 0.25 mm). Silica gel 60
F254 was used for column flash chromatography. Melting points
are uncorrected. NMR spectra were recorded in CDCl3 on a 300 or
200 MHz spectrometer operating in the Fourier transform mode.
1H NMR data are presented as follows: chemical shift, multiplicity,
coupling constant, integration. The following abbreviation are
used in reporting data: s, singlet; br s, broad singlet; d, doublet; t,
triplet; q, quartet; dt, doublet of triplets; dq, doublet of quartets;
dd, doublet of doublets; ddd, doublet of doublets of doublets; m,
multiplet. 13C NMR spectra were obtained with broadband proton
decoupling. Chemical shifts were recorded relative to the internal
tetramethylsilane (TMS) reference signal. Coupling constants (J)
are given in hertz. High resolution mass spectrum (HRMS) were
6.04 (ddd, 1H, J¼5.9, 10.3, 17.2 Hz), 6.87 (dd, 2H, J¼1.8, 8.7 Hz), 7.30
(dd, 2H, J¼2.1, 8.7 Hz). 13C NMR (CDCl3, 75 MHz)
d 55.3, 74.8, 113.9,
114.7, 127.7, 134.9, 140.5, 159.1.
4.2.6. 1-(4-Fluorophenyl)prop-2-en-1-ol (2f)18
Colorless oil (94%). 1H NMR (CDCl3, 300 MHz)
d 2.22 (br s,
1H), 5.18–5.24 (m, 2H), 5.34 (ddd, 1H, J¼1.2, 1.2, 17.1 Hz), 6.01
(ddd, 1H, J¼6.0, 10.3, 17.1 Hz), 7.02–7.08 (m, 2H), 7.31–7.37 (m,
2H). 13C NMR (CDCl3, 75 MHz)
d
74.6, 115.2, 115.3 (d, J¼21.7 Hz),
128.1 (d, J¼7.5 Hz), 138.2 (d, J¼3.1 Hz), 140.1, 162.2 (d,
J¼244.3 Hz, C–F).
4.2.7. 1-(2,4,6-Trimethylphenyl)prop-2-en-1-ol (2g)
White solid (95%), mp 52–54 ꢀC. 1H NMR (CDCl3, 300 MHz)
d
2.30 (s, 3H), 2.39 (s, 6H), 3.05 (br s, 1H), 5.18 (ddd, 1H, J¼1.8, 1.8,
10.5 Hz), 5.22 (ddd, 1H, J¼1.7, 1.7, 17.3 Hz), 5.72 (m, 1H), 6.15 (ddd,
performed by Centre Regional de Mesures Physiques de l’Ouest.
1H, J¼4.5, 10.5, 17.3 Hz), 6.90 (s, 2H). 13C NMR (CDCl3, 75 MHz)
´
1-Phenylpropan-1-one 3a, 1-(4-fluorophenyl)propan-1-one 3f, 4-
phenylbutan-2-one 3n, cyclohexanone 3o are also commercially
available, and these compounds obtained by using our procedure
were confirmed to be identical with those authentic samples.
d 20.5, 20.7, 71.5, 114.3, 130.0, 134.9, 136.5, 137.1, 138.6. HRMS (EI):
m/z calcd for C12H16O: 176.1201; found: 176.1204.
4.2.8. 1-(2,4,6-Trimethoxyphenyl)prop-2-en-1-ol (2h)
Colorless oil (98%). 1H NMR (CDCl3, 300 MHz)
d 2.34 (br s, 1H),
4.2. General procedure for the preparation of allylic alcohols
3.80 (s, 3H), 3.83 (s, 6H), 5.02 (ddd,1H, J¼1.6,1.6,10.2 Hz), 5.12 (ddd,
1H, J¼1.6, 1.6, 17.1 Hz), 5.19 (m, 1H), 5.59 (ddd, 1H, J¼5.5, 10.2,
In an oven-dried Schlenk flask, a solution of aldehyde (1.3 mmol,
1 equiv) in THF (1.8 mL) was prepared under an inert atmosphere at
0 ꢀC. To the solution, the Grignard reagent (1.4 mmol, 1.1 equiv) was
added and the reaction was stirred for 2 h. The reaction was
allowed to warm up to room temperature, quenched with a satu-
rated aqueous NH4Cl solution, and extracted with diethyl ether. The
combined organic layers were washed with brine, dried over
MgSO4, filtered, and evaporated to give the crude allylic alcohol
that was purified by flash chromatography on silica gel (cyclohex-
ane/AcOEt, 8:2 v/v).
17.1 Hz), 6.16 (s, 2H). 13C NMR (CDCl3, 75 MHz)
d 55.3, 55.7, 68.1,
91.1, 111.1, 112.9, 140.5, 158.3, 160.6. HRMS (EI): m/z calcd for
C12H16O4: 224.1048; found: 224.1051.
4.2.9. 1-(Naphthalen-2-yl)prop-2-en-1-ol (2i)21
Colorless oil (90%). 1H NMR (CDCl3, 200 MHz)
d
2.20 (br s, 1H),
5.20 (m, 1H), 5.35–5.45 (m, 2H), 6.25 (m, 1H), 7.40–7.50 (m, 3H),
7.80–8.10 (m, 4H). 13C NMR (CDCl3, 50 MHz)
75.5, 115.4, 124.4,
d
124.8, 125.8, 126.0, 127.5, 127.9, 128.1, 132.8, 133.1, 139.6, 140.0.
4.2.10. 1-(Naphthalen-1-yl)prop-2-en-1-ol (2j)19
4.2.1. 1-Phenylprop-2-en-1-ol (2a)18
Colorless oil (95%). 1H NMR (CDCl3, 300 MHz)
d 2.18 (br s, 1H),
Colorless oil (95%). 1H NMR (CDCl3, 200 MHz)
d
3.10 (br s, 1H),
5.30 (ddd, 1H, J¼1.2, 1.2, 10.3 Hz), 5.48 (ddd, 1H, J¼1.3, 1.3, 17.3 Hz),
5.97 (d, 1H, J¼5.3 Hz), 6.27 (ddd, 1H, J¼5.3, 10.3, 17.3 Hz), 7.50–7.66
(m, 4H), 7.80–7.90 (m, 2H), 8.23 (d, 1H, J¼9.1 Hz). 13C NMR (CDCl3,
5.10–5.20 (m, 2H), 5.40 (m, 1H), 6.10 (ddd, 1H, J¼6.0, 10.2, 16.4 Hz),
7.25–7.50 (m, 5H). 13C NMR (CDCl3, 50 MHz)
127.4, 128.3, 138.5, 141.4.
d 76.8, 116.2, 126.2,
75 MHz)
d 72.3, 115.6, 123.7, 123.9, 125.4, 125.6, 126.0, 128.5, 128.8,
130.6, 133.9, 138.0, 139.6.
4.2.2. 1-(2-Nitrophenyl)prop-2-en-1-ol (2b)18
Colorless oil (70%). 1H NMR (CDCl3, 300 MHz)
d
3.20 (br s, 1H),
4.2.11. 5-Phenylpent-1-en-3-ol (2k)22
5.22 (ddd, 1H, J¼1.1, 1.1, 10.4 Hz), 5.35 (ddd, 1H, J¼1.1, 1.1, 17.1 Hz),
5.71 (d, 1H, J¼5.3 Hz), 6.05 (ddd, 1H, J¼5.3, 10.4, 17.1 Hz), 7.40 (m,
1H), 7.63 (m, 1H), 7.77 (m, 1H), 7.95 (dd, 1H, J¼0.9, 8.1 Hz). 13C NMR
Colorless oil (59%). 1H NMR (CDCl3, 300 MHz)
d 1.85–1.91 (m,
3H), 2.67–2.81 (m, 2H), 4.14 (m, 1H), 5.15 (ddd, 1H, J¼1.3, 1.3,
10.4 Hz), 5.26 (ddd, 1H, J¼1.3, 1.3, 17.2 Hz), 5.95 (ddd, 1H, J¼6.1, 10.4,
(CDCl3, 75 MHz)
148.2.
d
69.8, 116.1, 124.5, 128.4, 128.8, 133.6, 137.6, 138.1,
17.2 Hz), 7.17–7.42 (m, 5H). 13C NMR (CDCl3, 75 MHz)
72.4, 114.9, 125.8, 128.4, 128.5, 141.0, 141.9.
d 31.6, 38.5,
4.2.3. 1-(4-Nitrophenyl)prop-2-en-1-ol (2c)18
4.2.12. (4E)-1-Phenylpenta-1,4-dien-3-ol (2l)23
Colorless oil (68%). 1H NMR (CDCl3, 200 MHz)
d
2.20 (br s, 1H),
Colorless oil (96%). 1H NMR (CDCl3, 300 MHz)
d 2.86 (br s,
5.22 (ddd, 1H, J¼1.1, 1.1, 10.4 Hz), 5.30 (d, 1H, J¼6.7 Hz), 5.40 (ddd,
1H), 4.81 (m, 1H), 5.23 (dd, 1H, J¼1.5, 10.4 Hz), 5.35 (ddd, 1H,
J¼1.5, 1.5, 17.2 Hz), 5.98 (ddd, 1H, J¼6.0, 10.4, 17.2 Hz), 6.25 (dd,
1H, J¼6.4, 15.9 Hz), 6.61 (d, 1H, J¼15.9 Hz), 7.28–7.44 (m, 5H). 13C
1H, J¼1.1,1.1,17.4 Hz), 6.00 (ddd,1H, J¼6.5,10.4,17.4 Hz), 7.60 (d, 2H,
J¼8.6 Hz), 8.20 (d, 2H, J¼8.6 Hz). 13C NMR (CDCl3, 50 MHz)
d 74.7,
116.4, 123.7, 127.1, 139.5, 147.3, 149.5.
NMR (CDCl3, 75 MHz)
130.7, 136.7, 139.4.
d 73.7, 115.4, 126.6, 127.8, 128.6, 130.5,
4.2.4. 1-(4-Bromophenyl)prop-2-en-1-ol (2d)19
Colorless oil (96%). 1H NMR (CDCl3, 300 MHz)
d
3.05 (br s, 1H),
4.2.13. (4E)-Deca-1,4-dien-3-ol (2m)
5.08 (d, 1H, J¼6.1 Hz), 5.20 (ddd, 1H, J¼1.3, 1.3, 10.3 Hz), 5.35 (ddd,
Colorless oil (74%). 1H NMR (CDCl3, 300 MHz)
d 2.78 (br s,
1H, J¼1.3,1.3,17.1 Hz), 5.96 (ddd,1H, J¼6.1,10.3,17.1 Hz), 7.25 (d, 2H,
1H), 0.85 (t, 3H, J¼7.5 Hz), 1.09–1.40 (m, 6H), 2.00 (dt, 2H, J¼6.7,
6.7 Hz), 4.52 (dd, 1H, J¼6.0, 6.0 Hz), 5.05 (ddd, 1H, J¼1.4, 1.4,
10.5 Hz), 5.19 (ddd, 1H, J¼1.4, 1.4, 17.3 Hz), 5.44 (dd, 1H, J¼6.7,
16.5 Hz), 5.64 (dt, 1H, J¼7.5, 16.5 Hz), 5.82 (ddd, 1H, J¼6.0, 10.5,
J¼8.4 Hz), 7.50 (d, 2H, J¼8.4 Hz). 13C NMR (CDCl3, 75 MHz)
d 74.6,
115.6, 121.5, 128.6, 131.5, 139.7, 141.5.
4.2.5. 1-(4-Methoxyphenyl)prop-2-en-1-ol (2e)20
17.3 Hz). 13C NMR (CDCl3, 75 MHz)
d 13.9, 22.4, 28.7, 31.1, 32.1,
Colorless oil (98%). 1H NMR (CDCl3, 300 MHz)
d
3.05 (br s, 1H),
73.6, 114.3, 131.0, 132.4, 140.0. HRMS (EI): m/z calcd for C10H18O:
3.80 (s, 3H), 5.09–5.21 (m, 2H), 5.35 (ddd, 1H, J¼1.4, 1.4, 17.2 Hz),
154.1357; found: 154.1361.