referenced to the central peak of the deuteriated chloroform
triplet (13C spectra). J Values are given in Hz. The IR spectra
were recorded on a Perkin Elmer FTIR 1600 and the data
obtained from thin films. Microanalyses were carried out on a
Carlo-Erba 1106 apparatus. The chromatographic separations
were carried out on Acros Silica gel (0.200–0.500 mm). Solvents
were purified prior to use and light petroleum refers to the frac-
tion with bp 40–60 ЊC. All the allylic chlorides are commercial
compounds.
distinguished following purification by silica gel chroma-
tography [light petroleum–CH2Cl2 (80:20) as eluent]; δH (200
MHz; CDCl3) 0.91 (3H, t, J 6.5, 9-H), 1.15–1.60 (8H, m, 5-H, 6-
H, 7-H, 8-H), 2.08 (1H, m, OH), 3.29 (1H, dd, J 7.5, 8.5, 3-H),
3.70–3.90 (1H, m, 4-H), 5.10–5.30 (2H, m, 1-H), 6.00–6.30 (1H,
m, 2-H), 7.15–7.45 (5H, m, Ph); δC(200 MHz; CDCl3) 13.8,
22.3, 25.1, 31.5, 34.2, 57.0, 73.7, 117.3, 126.3, 127.3, 128.3,
138.1, 141.5; νmax/cmϪ1 3431 (OH), 3027 (CH arom.), 2954 (CH
aliph.), 1640 (CH᎐CH ) (Found: C, 82.36; H, 10.28. Calc. for
᎐
2
C15H22O: C, 82.52; H, 10.16%).
Preparation of methyl 4-bromobut-2-enoate 10f 15
Methyl 3-hydroxy-2-vinyloctanoate 12f. Compound 12f was
obtained in 45% yield as a mixture of diastereoisomers which
could not be distinguished following Kugelrohr distillation.
δH (200 MHz; CDCl3) 0.84 (3H, t, J 6.4, 8-H), 1.15–1.50 (8H, m,
4-H, 5-H, 6-H, 7-H), 2.61 (1H, m, OH), 3.00–3.10 (1H, m, 2-H),
3.68 (3H, s, CH3), 3.80–3.95 (1H, m, 3-H), 5.15–5.29 (2H, m,
A solution of methyl crotonate (1.0 g, 10 mmol) and N-
bromosuccinimide (1.78 g, 10 mmol) in CCl4 (14 ml), contain-
ing some crystals of benzoyl peroxide, was heated at reflux for
5 h. After cooling, the reaction mixture was filtered. The filtrate
was dried, evaporated and the oily residue was distilled under
reduced pressure to give the title compound (80%), bp 80 ЊC/20
mmHg.
CH ᎐CH), 5.65–6.0 (1H, m, CH ᎐CH); δ (200 MHz; CDCl )
᎐
᎐
2
2
C
3
13.9, 22.4, 25.1, 31.6, 33.9, 51.9, 55.6, 71.3, 120.2, 131.6, 173.7;
νmax/cmϪ1 3469 (OH), 3062 (CH alkene), 2960 (CH aliph.), 1734
(CO) (Found: C, 65.81; H, 9.92. Calc. for C11H20O3: C, 65.97;
H, 10.07%).
Preparation of 6-oxoheptanal 816
According to the literature method,16 1-methylcyclohexene
(1.92 g, 20 mmol) dissolved in CH2Cl2 (75 ml) was treated with
ozone at Ϫ78 ЊC with stirring in the presence of sodium hydro-
gen carbonate (2 g). After the appearance of a blue colour, a
stream of nitrogen was introduced during 10 min and dimethyl
sulfide (15 ml) was added at Ϫ78 ЊC. The stirring was continued
for 3 h at room temperature and the organic solution was
washed with water (4 × 100 ml), dried and evaporated. The
aldehyde 8 was purified by distillation, bp 42 ЊC/0.01 mmHg,
42% yield; δH (200 MHz; CDCl3) 1.40–1.65 (4H, m, 3-H, 4-H),
2.09 (3H, s, 7-H), 2.30–2.50 (4H, m, 2-H, 5-H), 9.71 (1H, t, J
1.7, 1-H).
3,3-Dimethylnon-1-en-4-ol 12g.25 Oil, 68% yield.
5-Methyloct-1-en-4-ol 13a.26 Oil, 67% yield. 60:40 Mixture of
diastereoisomers which have not been separated.
2-Phenylhex-5-en-3-ol 14a.27 Oil, 78% yield.
Nona-1,5-dien-4-ol 15a.28 Oil. Isolated in 53% yield after
chromatographic separation from its regioisomer 23 on silica gel,
eluting with a mixture of light petroleum–CH2Cl2 (50:50);
δH (200 MHz; CDCl3) 0.86 (3H, t, J 7.3, 9-H), 1.36 (2H, m, J 7.3,
8-H), 1.82 (1H, m, OH), 1.97 (2H, q, J 7.2, 7-H), 2.20–2.30 (2H,
m, 3-H), 4.08 (1H, q, J 6.2, 4-H), 4.95–5.15 (2H, m, 1-H), 5.35–
5.85 (3H m, 2-H, 5-H, 6-H).
Nona-5,8-dien-4-ol 23. Compound 23 was isolated as an
impure oil containing small amounts of alcohol 15a; δH (200
MHz; CDCl3) 0.88 (3H, t, J 7.2, 1-H), 1.20–1.55 (4H, m, 2-H,
3-H), 1.60 (1H, m, OH), 2.75 (2H, dt, J 10, 6.4, 7-H), 4.06 (1H,
m, 4-H), 4.95–5.05 (2H, m, 9-H), 5.40–5.50 (1H, m, 5-H),
5.55–5.65 (1H, m, 6-H), 5.70–5.85 (1H, m, 8-H).
Preparation of 6-oxo-6-phenylhexanal 917
This aldehyde was prepared from 1-phenylcyclohexene accord-
ing to the same procedure, bp 100 ЊC/0.05 mmHg, mp 33 ЊC,
48% yield; δH (200 MHz; CDCl3) 1.60–1.80 (4H, m, 3-H, 4-H),
2.45 (2H, dt, J 1.6, 6.3, 2-H), 2.96 (2H, t, J 6.8, 5-H), 7.35–7.55
(3H, m, Ph), 7.9–8.0 (2H, m, Ph), 9.73 (1H, t, J 1.6, 1-H); δC(200
MHz; CDCl3) 21.4, 23.3, 37.8, 43.4, 127.7, 128.3, 132.7, 136.7,
199.4, 202.0; νmax/cmϪ1 3062 (CH arom.), 2945 (CH aliph.),
1714 and 1678 (CO).
6,10-Dimethylundeca-1,9-dien-4-ol 16a.29 Oil, 40% yield
(Kugelrohr distillation). 50:50 Mixture of diastereoisomers.
7-Hydroxydec-9-en-2-one 17a.30 Oil, 79% yield.
6-Hydroxy-1-phenylnon-8-en-1-one 18a.31 Oil, 71% yield.
1-Phenylbut-3-yn-1-ol 24.32 This oily compound was prepared
in 71% yield using benzaldehyde and prop-2-ynyl chloride
according to the general procedure used for the synthesis of
but-3-enylic alcohols; δH (200 MHz; CDCl3) 2.05 (1H, t, J 2.6, 4-
H), 2.59 (1H, d, J 2.7, OH), 2.63 (2H, dd, J 2.6, 6.3, 2-H), 4.83
(1H, dt, J 2.7, 6.3, 1-H), 7.20–7.45 (5H, m, Ph); δC(200 MHz;
Preparation of homoallylic alcohols (general procedure)
The aldehyde (2 mmol) was added to water (10 ml) containing
potassium iodide (1.0 g, 6 mmol), stannous chloride dihydrate
(0.677 g, 3 mmol) and allyl chloride 10 (3 mmol). The mixture
faded in colour and saturated aqueous ammonium chloride
(5 ml) was added when the allylic chlorides 10b–10g were used.
The stirring was continued for 15 h at 35 ЊC. Extraction with
CH2Cl2 (3 × 30 ml) gave an organic phase which was washed
with water, dried and concentrated. The oily residue was chro-
matographed on silica gel. Traces of the aldehydic substrate
were first removed by eluting with light petroleum–CH2Cl2
(95:5) and then pure but-3-enylic alcohol was obtained by elut-
ing with a 60:40 mixture of the same solvents. The following
compounds were prepared by this method.
CDCl3) 29.0, 70.7, 72.1, 125.6, 127.7, 128.2, 129.9, 142.3; νmax
/
cmϪ1 3620 (OH), 3330 (HC᎐), 3080 (CH arom.), 2930 (CH
᎐
᎐
aliph.).
Non-1-yn-4-ol 2633 and nona-1,2-dien-4-ol 27.34 The two alco-
hols 26 and 27 were obtained as a 70:30 mixture (78% yield).
26: δH (200 MHz; CDCl3) 0.83 (3H, t, J 6.5, 9-H), 1.15–1.55
(8H, m, 5-H, 6-H, 7-H, 8-H), 2.00 (1H, t, J 2.6, 1-H), 2.25 (1H,
m, OH), 2.15–2.45 (2H, m, 3-H), 3.60–3.75 (1H, m, 4-H); 27:
δH (200 MHz; CDCl3) 0.83 (3H, t, J 6.5, 9-H), 1.15–1.55 (8H, m,
5-H, 6-H, 7-H, 8-H), 2.25 (1H, m, OH), 4.05–4.15 (1H, m, 4-H),
4.78 (2H, m, 1-H), 5.15 (1H, q, J 6.7, 3-H).
1-Phenylbut-3-en-1-ol 11a.12 Oil, 92% yield.
3-Methyl-1-phenylbut-3-en-1-ol 11b.18 Oil, 74% yield.
3-Chloro-1-phenylbut-3-en-1-ol 11c.19 Oil, 82% yield.
2-Methyl-1-phenylbut-3-en-1-ol 11d and 1-phenylpent-3-en-1-
ol 21.20 Obtained as a mixture (11d:21 = 65:35), 79% yield.
1,2-Diphenylbut-3-en-1-ol 11e.21 Oil, 71% yield (syn:anti =
1:99).
References
1 Y. Yamamoto and N. Asao, Chem. Rev., 1993, 93, 2207.
2 D. Houllemare, F. Outurquin and C. Paulmier, unpublished
results.
3 Reviews for Barbier type allylations in aqueous media: C. J. Li,
Chem. Rev., 1993, 93, 2023; T. H. Chan, C. J. Li, M. C. Lee and
Z. Y. Wei, Can. J. Chem., 1994, 72, 1181; C. J. Li, Tetrahedron, 1996,
52, 5643; P. Cintas, Synlett, 1995, 1087.
2,2-Dimethyl-1-phenylbut-3-en-1-ol 11g.12 Oil, 75% yield.
Non-1-en-4-ol 12a.22 Oil, 90% yield.
2-Methylnon-1-en-4-ol 12b.23 Oil, 71% yield.
2-Chloronon-1-en-4-ol 12c.24 Oil, 74% yield.
3-Phenylnon-1-en-4-ol 12e. Compound 12e was obtained in
57% yield as a mixture of diastereoisomers which could not be
4 C. Petrier, J. Einhorn and J. L. Luche, Tetrahedron Lett., 1985, 26,
1449.
J. Chem. Soc., Perkin Trans. 1, 1997
1631