A convenient procedure for bismuth-mediated Barbier-type allylation of aldehydes in water containing fluoride ions

Article abstract of DOI:10.1039/b400179f

A new and convenient procedure for synthesis of homoallylic alcohols in generally good to excellent yields has been developed. The bismuth-mediated Barbier-type allylation of aldehydes (aromatic, aliphatic, alicyclic and heterocyclic) with allyl bromide h

Full text of DOI:10.1039/b400179f

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A convenient procedure for bismuth-mediated Barbier-type
allylation of aldehydes in water containing fluoride ions
Keith Smith,*a Sandra Lock,a Gamal A. El-Hiti,†a Makoto Wadab and Norikazu Miyoshib
a Centre for Clean Chemistry, Department of Chemistry, University of Wales Swansea,
Singleton Park, Swansea, UK SA2 8PP
b Department of Chemistry, Faculty of Integrated Arts and Sciences, University of Tokushima,
Minami-Josanjima, Tokushima, Japan 770
Received 8th January 2004, Accepted 11th February 2004
First published as an Advance Article on the web 25th February 2004
A new and convenient procedure for synthesis of homoallylic alcohols in generally good to excellent yields has
been developed. The bismuth-mediated Barbier-type allylation of aldehydes (aromatic, aliphatic, alicyclic and
heterocyclic) with allyl bromide has been carried out smoothly in water in the presence of fluoride ions.
conversions of benzaldehyde and salicylaldehyde, the metal
Introduction
may otherwise have limited general capability when no solvent
is present.20 Very recently, the bismuth-mediated Barbier-type
allylation of carbonyl compounds in the absence of solvent,
affording homoallyl alcohols in good yield, was reported.21
However, the method involves the use of a ball milling
technique and a large excess of bismuth (aldehyde : Bi ratio is
1 : 8). Moreover, the reaction has been applied only on a very
small scale (0.25 mmol of aldehyde).
As part of our continuing interest in the development of
clean chemical processes,22,23 we became interested in aqueous
bismuth-mediated reactions as a possible method for the
synthesis of homoallylic alcohols. We therefore wish to disclose
the results of our own bismuth-mediated allylations performed
in entirely aqueous solutions.
Traditionally performed in organic solvents with the strict
exclusion of air and moisture, the coupling of an organic halide
and a carbonyl compound in the presence of a metal (the
Barbier reaction) is a fundamental procedure for making new
carbon–carbon bonds.1 Interest in the reaction surged in the
early 1980’s with the discovery that allylic halides in particular
reacted with aldehydes in the presence of a range of metals in
aqueous media, sometimes with the assistance of dissolved
salts, organic co-solvents or sonication to boost reactivity.2
Attendant benefits included the ability to dispense with time-
consuming drying regimes and protection–deprotection steps
when dealing with vulnerable substrates, but recently, with the
current emphasis on developing cleaner, safer, more atom-
efficient chemical processes that depend less on organic
solvents,3 aqueous Barbier-type procedures have acquired a
new relevance.
Results and discussion
Bismuth is recognised alongside tin, zinc and indium metals
as an established and successful mediator of aqueous Barbier-
type reactions,4,5 though it is usually prepared in situ from
a bismuth salt and a reducing metal in water/THF solvent
mixtures.6 The toxicity of bismuth is considered to be low;7,8
indeed, bismuth salts have, for a long time, been used in
cosmetics and anti-viral creams and are important components
of orally administered gastrointestinal treatments currently
prescribed on a worldwide basis.8 Accordingly, the metal does
not seem to have the degree of toxicity that makes the use of tin
and its compounds, for instance, much less favourable in
organic synthesis.5 Zinc is commonly accepted to be non-toxic
and is usually activated in aqueous Barbier-type allylations by
the addition of ammonium chloride. However, with some
notable exceptions,9–12 it generally requires the presence of
an organic cosolvent to achieve high product yields.13–17 In
contrast, indium is distinguished by its versatility and ability to
mediate reactions quickly and smoothly in water alone2
without the need for an additional means of activation. On a
mole for mole basis, however, it is by far the most expensive of
the four metals.
As a test case, the allylation reaction of benzaldehyde (1a) with
allyl bromide (2) in the presence of bismuth powder in water
(eqn. (1)) was investigated.
(1)
Keeping similar mole ratios of reactants as were previously
used with DMF18 but changing the solvent to distilled water, we
began by stirring benzaldehyde (1a) (1 mmol) and allyl bromide
(2) (1.16 mmol) with bismuth powder (1.2 mmol) in distilled
water (5 ml) for 24 h at room temperature under a static argon
atmosphere. This resulted in a yield of 1-phenylbut-3-en-1-ol
(3a) of only 31% (by GC). The performance of zinc in aqueous
Barbier-type reactions is enhanced by dissolved ammonium
chloride and recent reports indicate that fluoride salts success-
fully activate carbon–carbon bond-forming reactions mediated
by antimony and aluminium in aqueous solution.24,25 Therefore,
we investigated the effect of a variety of additives and mole
ratios of reactants, this time beginning with a similar mole ratio
to that adopted by Li et al.24 in Sb-mediated allylation
reactions. The results are summarized in Table 1.
Bismuth powder is readily available and easy to use and allyl-
ations of a range of aldehydes in DMF and acetonitrile have
been published.6,18,19 However, in a recent paper that compared
the merits of bismuth, indium, copper and zinc powders in
temperature-controlled solvent-free allylations, the reported
results indicated that while bismuth provided worthwhile
Compared to our first experiment in water, the yield of
homoallylic alcohol did not improve, and was, in fact, some-
what depressed in the presence of the larger excesses of bismuth
powder and allyl bromide (Entry 1, Table 1). Various salts
were found to improve the yield, and amongst the fluoride and
† Permanent address: Department of Chemistry, Faculty of Science,
Tanta University, Tanta 31527, Egypt.
T h i s j o u r n a l i s © T h e R o y a l S o c i e t y o f C h e m i s t r y 2 0 0 4
O r g . B i o m o l . C h e m . , 2 0 0 4 , 2, 9 3 5 – 9 3 8
935

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Table 1 Synthesis of 1-phenylbut-3-en-1-ol (3a), according to equation (1),a in the presence of various salts
Entry
Bi (mmol)
Allyl bromide (mmol)
Salt (mmol)
Yield (%)b
1
2
3
4
5
6
7
8
9
10
11
12
13
14
5
5
5
5
5
2
2
2
2
2
1.1
1.1
1.1
1.1
2.3
2.3
2.3
2.3
2.3
2.3
2.3
2.3
2.3
2.3
2.3
1.16
1.16
1.16
—
20c
52c
18c
54
83
82
40
90
59
58
(sonication 3 h)d
NH4Cl (10)
NaCl (10)
KF (10)
KF (10)
NaF (10)
KF (5)
NaF (5)
LiF (5)
KF (5)
KF (5)
KF (1.1)
KF (0.5)
89
> 99e
> 99
83
a A mixture of benzaldehyde (106.2 mg, 1 mmol), allyl bromide, Bi powder and KF in water (5 ml) was stirred for 12 h at room temperature.
b Determined by quantitative GC analysis. c Reaction time 24 h. d Using a Decon® FS100B 47 KHz ultrasonic cleaning bath. e Reaction complete in
3 h.
Table 2 Synthesis of 3 according to equation (2)a
chloride salts tested, potassium fluoride proved to be the most
effective. As the excesses of Bi and/or the allyl bromide were
Entry
Product
R
Yield (%)b
reduced, the yield of the desired product increased. When Bi
and the allyl bromide were each in only slight excess over 1 mole
per mole of benzaldehyde, the yield was almost quantitative
even after 3 hours (Entry 12).
1
2
3
4
5
6
7
8
9
3a
3b
3c
3d
3e
3f
3g
3h
3i
C6H5
99
4-MeC6H4
3-BrC6H4
4-O2NC6H4
2-HOC6H4
2-naphthyl
2-furyl
99 (47)c
90 (28)c
62 (84)d (86)e
Furthermore, the amount of KF could be reduced to 1.1
mmol and still enabled a quantitative yield within 12 hours
(Entry 13). Even with only 0.5 mole equivalents of KF, 83% of
the desired alcohol was achieved in 12 hours (Entry 14). This
suggests that the relationship between the potassium fluoride
and bismuth is not a stoichiometric one. However, reactions
involving different amounts of bismuth but constant amounts
of benzaldehyde (1.0 mmol), allyl bromide (1.16 mmol), and
potassium fluoride (5 mmol) suggest a 1 : 1 metal : allyl depend-
ence (Fig. 1).
86
94f
91
94
80
93
91
99
C6H5CH᎐CH
᎐
C6H5CH2CH2
C6H5CH(CH3)
nC7H15
10
11
12
3j
3k
3l
cyclohexyl
a A mixture of aldehyde (1.0 mmol), allyl bromide (1.16 mmol), Bi (1.1
mmol) and KF (5 mmol) in water (5 ml) was stirred at room temper-
ature for 12 h. b Determined by quantitative GC analysis. c Using KF
(1.1 mmol). d Using KF (7.5 mmol). e Using KF (10.0 mmol). f Isolated
yield.
Benzaldehyde (Entry 1, Table 2) was transformed into an
essentially quantitative yield of 3a, with just small traces of
benzyl alcohol and benzoic acid as by-products. Hydrobenzoin,
the pinacol coupling product, was not detected. Allylations of
the majority of other aromatic aldehydes examined also
proceeded smoothly in water containing 5 mmol of potassium
fluoride within the 12 h period to afford good to excellent yields
of the corresponding homoallylic alcohols. However, although
4-tolualdehyde and 3-bromobenzaldehyde gave excellent yields
(99 and 90% of 3b and 3c, respectively) under these standard
conditions, they reacted more sluggishly and gave poorer yields
(47 and 28%, respectively) when the amount of KF was reduced
to 1.1 mmol (Entries 2 and 3, Table 2). 4-Nitrobenzaldehyde
gave only a modest yield (62%) under the standard conditions,
but responded satisfactorily, giving a yield of 86%, when the
amount of fluoride salt was increased to 10 mmol (Entry 4,
Table 2). Thus, the reaction is quite general for a range of
substituted aromatic aldehydes.
In order to assess the usefulness of the reaction with
other types of aldehydes, reactions were conducted with a
heterocyclic aldehyde, 2-furaldehyde (Entry 7, Table 2), an
αβ-unsaturated aldehyde, cinnamaldehyde (Entry 8, Table 2),
various aliphatic aldehydes (3-phenylpropanal; 2-phenyl-
propanal; octanal; Entries 9–11, Table 2) and an alicyclic
aldehyde, cyclohexanecarboxaldehyde (Entry 12, Table 2). In all
cases a high yield of the corresponding homoallylic alcohol was
obtained (Table 2). The new method therefore appears to be
quite general.
Fig. 1 Effect of amount of Bi upon the GC yield of 3a in the reaction
of 1a (1 mmol) and 2 (1.16 mmol) in aq. KF (1 M, 5 ml) for 12 h at
room temperature.
The generality of the method was investigated with a range
of aldehydes 1 (4-tolualdehyde, 3-bromobenzaldehyde, 4-nitro-
benzaldehyde, 2-hydroxybenzaldehyde, 2-naphthaldehyde, 2-
furaldehyde, cinnamaldehyde, 3-phenylpropanal, 2-phenyl-
propanal, octanal, cyclohexanecarboxaldehyde), using allyl
bromide (1.16 mmol), Bi (1.1 mmol) and potassium fluoride (5
mmol, unless otherwise stated), according to eqn. (2), to afford
allylic alcohols 3 in excellent yields (Table 2).
(2)
O r g . B i o m o l . C h e m . , 2 0 0 4 , 2, 9 3 5 – 9 3 8
936

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CH᎐CH ), 5.13–5.06 (m, 2 H, CH᎐CH ), 4.62 (t, J = 7 Hz, 1 H,
Conclusion
᎐
᎐
2
2
CHOH), 2.48–2.32 (m, 2 H, CH2), 2.24 (br s, exch., 1 H, OH);
δ (CDCl ) 146.6 (s), 134.3 (d, CH᎐CH ), 131.0 (d), 130.4 (d),
A new method for allylation of aldehydes, involving use of
bismuth metal and allyl bromide in water containing KF, has
been developed. The method affords excellent yields of
homoallylic alcohols. Unfortunately, from a green chemistry
viewpoint a reaction using potassium fluoride is not ideal.
Nevertheless the reaction has demonstrated that there are cir-
cumstances in which it is possible to dispense completely with
the usual organic solvent (THF) yet still retain useful product
yields. Therefore, there is still room for considerable improve-
ment in the clean synthesis of allylic alcohols. We continue to
investigate other synthetic capabilities of bismuth in water.
᎐
C
3
2
129.3 (d), 124.9 (d), 123.0 (s), 119.4 (t, CH᎐CH ), 72.9 (d,
᎐
2
CHOH), 44.2 (t, CH2).
1-(4-Nitrophenyl)but-3-en-1-ol (3d)21,27,29
Oil, δH(CDCl3) 8.12 (d, J = 8.7 Hz, 2 H, ArH), 7.46 (d,
J = 8.7 Hz, 2 H, ArH), 5.76–5.66 (m, 1 H, CH᎐CH ), 5.14–5.07
᎐
2
(m, 2 H, CH᎐CH ), 4.79 (dd, J = 8.9, 4.7 Hz, 1 H, CHOH),
᎐
2
2.52–2.34 (m, 2 H, CH2), 1.52 (br s, exch., 1 H, OH); δC(CDCl3)
151.6 (s), 147.6 (s), 133.6 (d, CH᎐CH ), 127.0 (d), 124.0 (d),
᎐
2
120.0 (t, CH᎐CH ), 72.6 (d, CHOH), 44.3 (t, CH ).
᎐
2
2
Experimental
1-(2-Hydroxyphenyl)but-3-en-1-ol (3e)31
Commercially available starting materials (Aldrich) were used
as supplied. GC was carried out using a PU 4400 Gas Chro-
matograph (Philips) fitted with a carbowax capillary column
(15 m × 0.32 mm id). Hexadecane was added as an internal
standard to allow quantification. Infrared spectra were
Oil, δH(CDCl3) 7.99 (s, exch., 1 H, OH), 7.15–6.74 (m, 4 H,
ArH), 5.84–5.73 (m, 1 H, CH᎐CH ), 5.19–5.12 (m, 2 H,
᎐
2
CH᎐CH ), 4.80 (t, J = 6.6 Hz, 1 H, CHOH), 2.67 (br s, exch.,
᎐
2
1 H, OH), 2.60–2.48 (m, 2 H, CH2); δC(CDCl3) 155.9 (s), 134.3
(d, CH᎐CH ), 129.4 (d), 127.5 (d), 126.5 (s), 120.2 (d), 119.9
1
᎐
2
recorded on a Horiba FT-IR 210 spectrophotometer. H and
(t, CH᎐CH ), 117.7 (d), 75.1 (d, CHOH), 42.6 (t, CH ).
13C NMR spectra were recorded on a Bruker AC-400 Fourier
Transform spectrometer operating at 400 MHz for 1H and 100
MHz for 13C measurement. Chemical shifts are reported
relative to tetramethylsilane. Assignments of signals are based
on coupling patterns and expected chemical shift values and
have not been rigorously confirmed. Signals with similar
characteristics might be interchanged. Flash column chromato-
graphy was performed using Merck Matrix Silica 60 (35–70
micron) silica gel.
᎐
2
2
1-(2-Naphthyl)but-3-en-1-ol (3f)32
Oil, δH(CDCl3) 7.77–7.71 (m, 4 H, ArH), 7.42–7.36 (m, 3 H,
ArH), 5.81–5.69 (m, 1 H, CH᎐CH ), 5.14–5.05 (m, 2 H,
᎐
2
CH᎐CH ), 4.82 (dd, J = 7.4, 5.4 Hz, 1 H, CHOH), 2.57–2.45
᎐
2
(m, 2 H, CH2), 2.12 (br s, exch., 1 H, OH); δC(CDCl3) 141.7 (s),
134.9 (d, CH᎐CH ), 133.7 (s), 133.4 (s), 128.7 (d), 128.5 (d),
᎐
2
128.4 (d), 126.6 (d), 126.3 (d), 125.0 (d), 124.5 (d), 118.9 (t,
CH᎐CH ), 73.9 (d, CHOH), 44.1 (t, CH ).
᎐
2
2
Typical reaction procedure
1-(2-Furyl)but-3-en-1-ol (3g)26
Bismuth powder (231.8 mg, 1.1 mmol) was weighed into a 50 ml
two-necked flask equipped with a magnetic stirrer bar and
capped with a septum. The vessel was flushed with argon for 5
min and aq. KF solution (1 M, 5 ml) was added. The argon flow
was stopped and allyl bromide (0.10 ml, 1.16 mmol) and alde-
hyde (1.0 mmol) were added in quick succession. The mixture
was stirred for 12 h at room temperature and the organic
materials were then extracted with diethyl ether (3 × 20 ml). The
combined extract was washed with aq. NaCl solution (2 × 15
ml) and dried over anhydrous MgSO4. The organic phase was
filtered and evaporated to leave oily residue, which was purified
by flash column chromatography on silica gel using hexane–
EtOAc (4 : 1) as the solvent to give pure 3, which was analysed
by GC. Confirmation of the product was achieved by use of
NMR and by comparison with literature values.21,26–32
Oil, δH(CDCl3) 7.31 (dd, J = 1.8, 0.8 Hz, 1 H, furyl), 6.26 (dd,
J = 3.2, 1.8 Hz, 1 H, furyl), 6.18 (dd, J = 3.2, 0.8 Hz, 1 H, furyl),
5.79–5.68 (m, 1 H, CH᎐CH ), 5.15–5.06 (m, 2 H, CH᎐CH ),
᎐
᎐
2
2
4.68 (t, J = 6.5 Hz, 1 H, CHOH), 2.63–2.49 (m, 2 H, CH2), 2.05
(br s, exch., 1 H, OH); δC(CDCl3) 156.4 (s), 142.4 (d), 134.1
(d, CH᎐CH ), 119.0 (t, CH᎐CH ), 110.6 (d), 106.5 (d), 67.3
᎐
᎐
2
2
(d, CHOH), 40.5 (t, CH2).
1-Phenylhexa-1,5-dien-3-ol (3h)27,29,31
Oil, δH(CDCl3) 7.31 (d, J = 7.2 Hz, 2 H, ArH), 7.24 (t,
J = 7.2 Hz, 2 H, ArH), 7.17 (m, 1 H, ArH), 6.53 (d, J = 15.9 Hz,
1 H, CH), 6.17 (dd, J = 15.9, 6.4 Hz, 1 H, CH), 5.83–5.73
(m, 1 H, CH᎐CH ), 5.15–5.08 (m, 2 H, CH᎐CH ), 4.29 (t,
᎐
᎐
2
2
J = 6.4 Hz, 1 H, CHOH), 2.41–2.27 (m, 2 H, CH2), 1.82 (br s,
exch., 1 H, OH); δ (CDCl ) 137.0 (s), 134.4 (d, CH᎐CH ), 131.9
᎐
C
3
2
1-Phenylbut-3-en-1-ol (3a)26–29
(d), 130.2 (d), 129.0 (d), 128.1 (d), 126.9 (d), 119.0 (t, CH᎐CH ),
᎐
2
72.1 (d, CHOH), 42.4 (t, CH2).
Oil, δH(CDCl3) 7.36–7.25 (m, 5 H, ArH), 5.74–5.33 (m, 1 H,
CH᎐CH ), 5.09–5.00 (m, 2 H, CH᎐CH ), 4.61 (t, J = 6 Hz, 1 H,
᎐
᎐
2
2
6-Phenylhex-1-en-4-ol (3i)28
CHOH), 2.43–2.38 (m, 2 H, CH2), 2.15 (br s, exch., 1 H, OH);
δ (CDCl ) 144.8 (s), 134.9 (d, CH᎐CH ), 128.8 (d), 128.0 (d),
᎐
C
3
2
Oil, δH(CDCl3) 7.18–7.03 (m, 5 H, ArH), 5.76–5.62 (m, 1 H,
126.3 (d), 118.8 (t, CH᎐CH ), 73.8 (d, CHOH), 44.2 (t, CH ).
᎐
2
2
CH᎐CH ), 5.05–4.98 (m, 2 H, CH᎐CH ), 3.59–3.51 (m, 1 H,
᎐
᎐
2
2
CHOH), 2.74–2.51 (m, 2 H, CH2), 2.23–2.01 (m, 2 H, CH2),
1.81 (br s, exch., 1 H, OH), 1.70–1.62 (m, 2 H, CH2); δC(CDCl3)
142.5 (s), 135.0 (d, CH᎐CH ), 128.8 (d), 128.7 (d), 126.3 (d),
1-(4-Methylphenyl)but-3-en-1-ol (3b)26,27
Oil, δH(CDCl3) 7.18 (d, J = 8 Hz, 2 H, ArH), 7.09 (d, J = 8 Hz,
2 H, ArH), 5.79–5.68 (m, 1 H, CH᎐CH ), 5.12–5.04 (m, 2 H,
᎐
2
118.8 (t, CH᎐CH ), 70.4 (d, CHOH), 42.5 (t, CH ), 38.9 (t,
᎐
2
2
᎐
2
CH2), 32.5 (t, CH2).
CH᎐CH ), 4.63 (t, J = 6 Hz, 1 H, CHOH), 2.45–2.41 (m, 2 H,
᎐
2
CH2), 2.27 (s, 3 H, CH3), 1.94 (br s, exch., 1 H, OH); δC(CDCl3)
5-Phenylhex-1-en-4-ol (3j)
141.3 (s), 137.6 (s), 135.0 (d, CH᎐CH ), 129.5 (d), 126.2 (d),
᎐
2
118.7 (t, CH᎐CH ), 73.6 (d, CHOH), 44.2 (t, CH ), 21.5 (q,
CH3).
᎐
2
2
Oil, mixture of syn and anti diastereoisomers in almost equal
proportions, δH(CDCl3) 7.39–7.22 (m, 5 H, ArH), 5.98–5.78 (m,
1 H, CH᎐CH ), 5.20–5.10 (m, 2 H, CH᎐CH ), 3.81–3.73 (m,
᎐
᎐
1-(3-Bromophenyl)but-3-en-1-ol (3c)30
2
2
1 H, CHOH), 2.88–2.78 (m, 1 H, CHCH3), 2.47–2.02 (m, 2 H,
CH2), 1.78 (br s, exch., 1 H, OH), 1.39, 1.34 (2 dd, J = 7.0,
1.3 Hz, 3 H, CH3); δC(CDCl3) 144.9, 143.8 (2 s, C-1 of Ph),
Oil, δH(CDCl3) 7.45 (d, J = 1.2 Hz, 1 H, ArH), 7.33 (dd, J = 7.2,
1.2 Hz, 1 H, ArH), 7.21–7.11 (m, 2 H, ArH), 5.77–5.65 (m, 1 H,
O r g . B i o m o l . C h e m . , 2 0 0 4 , 2, 9 3 5 – 9 3 8
937

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10 C.-J. Li and T.-H. Chan, Organometallics, 1991, 10, 2548.
135.6, 135.5 (2 d, CH᎐CH ), 128.9, 128.7, 128.2, 127.9 (4 d, C-2
and C-3 of Ph), 127.1, 126.9 (2 d, C-4 of Ph), 118.4, 118.1 (2 t,
᎐
2
11 T.-H. Chan and C.-J. Li, Can. J. Chem., 1992, 70, 2726.
12 M. Lombardo, R. Girotti, S. Morganti and C. Trombini, Chem.
Commun., 2001, 2310.
CH᎐CH ), 75.6, 75.5 (2 d, CHOH), 45.8, 45.7 (2 t, CH ), 39.9,
᎐
2
2
39.4 (2 d, CHCH3), 18.2, 16.9 (2 q, CH3).
13 C. Petrier and J.-L. Luche, J. Org. Chem., 1985, 50, 910.
14 C. Petrier, J. Einhorn and J.-L. Luche, Tetrahedron Lett., 1985, 26,
1445.
15 C. Einhorn and J.-L. Luche, J. Organomet. Chem., 1987, 322, 177.
16 S. R. Wilson and M. E. Guazzaroni, J. Org. Chem., 1989, 54, 3087.
17 R. Sjoholm, R. Rairama and M. Ahonen, J. Chem. Soc.,Chem.
Commun., 1994, 1217.
18 M. Wada and K. Akiba, Tetrahedron Lett., 1985, 26, 4211.
19 N. Miyoshi, M. Nishio, S. Murakami, T. Fukuma and M. Wada,
Bull. Chem. Soc. Jpn., 2000, 73, 689.
20 P. C. Andrews, A. C. Peatt and C. L. Raston, Green Chem., 2001, 3,
313.
Undec-1-en-4-ol (3k)29
Oil, δ (CDCl ) 5.82–5.71 (m, 1 H, CH᎐CH ), 5.10–5.04 (m,
᎐
H
3
2
2 H, CH᎐CH ), 3.61–3.53 (m, 1 H, CHOH), 2.28–2.02 (m, 2 H,
᎐
2
CH2), 1.80 (br s, exch., 1 H, OH), 1.43–1.33 (m, 2 H, CH2),
1.28–1.15 (m, 10 H, 5 CH2), 0.81 (t, J = 7 Hz, 3 H, CH3);
δ (CDCl ) 135.3 (d, CH᎐CH ), 118.5 (t, CH᎐CH ), 71.1 (d,
᎐
᎐
C
3
2
2
CHOH), 41.3 (t, CH2), 37.2 (t, CH2), 33.2 (t, CH2), 30.0 (t,
CH2), 29.7 (t, CH2), 26.1 (t, CH2), 23.1 (t, CH2), 14.5 (q, CH3).
21 S. Wada, N. Hayashi and H. Suzuki, Org. Biomol. Chem., 2003, 1,
1-Cyclohexylbut-3-en-1-ol (3l)28
2160.
22 See for example; K. Smith, G. A. El-Hiti, M. A. Abdo and M. F.
Abdel-Megeed, J. Chem. Soc., Perkin Trans. 1, 1995, 1029; K. Smith,
G. A. El-Hiti, M. F. Abdel-Megeed and M. A. Abdo, J. Org. Chem.,
1996, 61, 647–656; K. Smith, G. A. El-Hiti and A. Hamilton,
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G. A. El-Hiti and S. A. Mahgoub, Synthesis, 2003, 2345.
23 See for example; K. Smith, A. Musson and G. A. DeBoos, J. Org.
Chem., 1998, 63, 8448; K. Smith, Z. Zhenhua and P. K. G. Hodgson,
J. Mol. Catal. A, 1998, 134, 121; K. Smith, P. He and A. Taylor,
Green Chem., 1999, 1, 35; K. Smith, M. Butters, W. E. Paget,
D. Goubet, E. Fromentin and B. Nay, Green Chem., 1999, 1, 83;
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A. Jayne and M. Butters, Org. Biomol. Chem., 2003, 1, 1560–2321.
24 L.-H. Li and T. H. Chan, Tetrahedron Lett., 2000, 41, 5009.
25 L.-H. Li and T. H. Chan, Org. Lett., 2000, 2, 1129.
26 Y.-Z. Huang and Y. Liao, J. Org. Chem., 1991, 56, 1381.
27 A. Hosomi, S. Kohra, K. Ogata, T. Yanagi and Y. Tominaga, J. Org.
Chem., 1990, 55, 2415.
Oil, δ (CDCl ) 5.82–5.71 (m, 1 H, CH᎐CH ), 5.11–5.04 (m,
᎐
H
3
2
2 H, CH᎐CH ), 3.35–3.29 (m, 1 H, CHOH), 2.30–2.01 (m, 2 H,
᎐
2
CH2), 1.78 (br s, exch., 1 H, OH), 1.70–1.55 (m, 5 H, cyclo-
hexyl), 1.34–0.90 (m, 6 H, cyclohexyl); δC(CDCl3) 135.9 (d,
CH᎐CH ), 118.4 (t, CH᎐CH ), 75.1 (d, CHOH), 43.5 (t, CH ),
᎐
᎐
2
2
2
39.2 (d, CH), 29.5 (t, CH2), 28.5 (t, CH2), 26.9 (t, CH2), 26.7 (t,
CH2), 26.5 (t, CH2).
Acknowledgements
We thank the EPSRC and the University of Wales Swansea for
financial support. We also thank the EPSRC, the Higher
Education Funding Council for Wales (ELWa-HEFCW) and
the University of Wales Swansea for grants that enabled
the purchase and upgrading of NMR equipment used in the
course of this work. G. A. El-Hiti thanks the Royal Society of
Chemistry for an international author grant.
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