Allylation of carbonyl compounds by allylic acetates using a cobalt halide as catalyst

Article abstract of DOI:10.1055/s-2003-40999

In acetonitrile as solvent and in the presence of a simple cobalt halide as catalyst, the reduction by zinc dust of a mixture of aldehydes or ketones and allylic acetates affords the corresponding homoallylic alcohols in good yields.

Full text of DOI:10.1055/s-2003-40999

FEATURE ARTICLE
1909
Allylation of Carbonyl Compounds by Allylic Acetates Using a Cobalt Halide
as Catalyst
Allylation of
C
a
a
rbonyl Co
u
mpounds by
l
A
llyli
o
A
cetate
s
Gomes, Corinne Gosmini,* Jacques Périchon
Laboratoire d’Electrochimie, Catalyse et Synthèse Organique, UMR 7582, Université Paris 12 – C.N.R.S 2, Rue Henri Dunant,
94320 THIAIS
E-mail: gosmini@glvt-cnrs.fr
Received 4 March 2003
CoBr2 cat., Zn
OH
R1
R2
R1 R2
O
Abstract: In acetonitrile as solvent and in the presence of a simple
cobalt halide as catalyst, the reduction by zinc dust of a mixture of
aldehydes or ketones and allylic acetates affords the corresponding
homoallylic alcohols in good yields.
OAc
+
MeCN
Scheme 1
Key words: allylation, homo-allylic alcohols, carbonyl cop-
mounds, cobalt halide, catalyst
Allylic alcohols were formed from the ketone (Scheme 1,
Table 1) by reaction of cobalt bromide and zinc dust. This
is a mild reaction that is carried out at room temperature
and the pure allylic alcohol is isolated by column chroma-
tography.
Allylation of carbonyl compounds is one of the most in-
teresting processes for the preparation of homoallylic al-
cohols. Over the past few decades, many reagents have
been developed for such reactions.1 Generally, allylation
of carbonyl compounds from allylic acetates, which are
easily derived from available allylic alcohols, requires ca-
talysis by a palladium complex associated with a reducing
reagent which are metals or salts such as Zn,2 SnCl2,3
SmI2,4 and InI5 in a stoichiometric amount.
The use of DMF and THF as solvent inhibits the reaction
and neither substrate is consumed. Besides acetonitrile,
benzonitrile or adiponitrile can be used but the purifica-
tion of the homoallylic alcohol is therefore difficult. The
use of 2 equivalents of Zn powder and 0.3 equivalents of
catalyst increased the rate of the reaction but smaller
amounts (1 equiv of zinc, 0.2 equiv of CoBr2) also result
in the consumption of all the starting products. With only
0.1 equivalents of cobalt salt, only small amounts of ho-
moallylic alcohol are obtained. The yield is similar even
when the reaction is carried out at 50 °C, but the reaction
time decreases (5 h instead of 7 h). Trifluoroacetic acid is
necessary to activate the zinc dust. Iodine or acetic acid
could also play this part. Undoubtedly, the zinc dust re-
duces CoBr2 to a Co(I) species, which is the reactive spe-
cies towards the allylic acetate. Further mechanistic
studies, including the electrochemical characterisation of
active catalyst species are now in progress. The results of
the allylation of various ketones by allyl acetate are re-
ported in Table 1.
In most cases, only aldehydes are reactive except with
SmI2, which also allows the allylation of ketones. Never-
theless, allylation is restricted since aromatic and , -un-
saturated aldehydes or ketones lead to pinacol formation
with this samarium salt. Another route to allylic anions
from allylic acetate is their electrochemical generation.
Indeed, a Pd(II)–Zn(II) system allows the reaction of al-
lylic acetates with carbonyl compounds via electrochemi-
cal reduction.6 However, this process is carried out in a
divided cell fitted with Pt electrodes and requires a sto-
ichiometric amount of zinc chloride. To our knowledge,
the only catalyst, which can replace palladium, is a ruthe-
nium complex7 in the presence of carbon monoxide to en-
sure the catalytic activity of the ruthenium complex.
Nevertheless, the reaction is limited to aldehydes.
Good yields are obtained with several aliphatic, aromatic,
and even heteroaromatic ketones. Reaction times range
from 5 to 7 hours. In the case of benzophenone (Table 1,
entry 5), the ketone is not totally consumed, resulting in a
moderate yield, this could result from steric hindrance due
to the phenyl groups. In this case, an excess of allylic ac-
etate is necessary (with 2 equiv of allylic acetate) to in-
crease the the yield to 75%. With a more reactive ketone
such as ethyl pyruvate, no traces of coupling with allyl ac-
etate are detected, only the resulting pinacol is formed.
Recently, we have discovered that cobalt halides are effi-
cient catalysts for some reactions usually catalysed by pal-
ladium complexes.8 This cobalt catalyst associated with
pyridine has also been used for the electroreductive allyl-
ation of aromatic halides by allylic acetates.9
In this paper, we report our investigations of the cobalt-
catalysed coupling reaction of allyl acetates with carbonyl
compounds using zinc dust as a reducing agent, leading to
homoallylic alcohols (Scheme 1).
In order to study the regiochemistry of this carbonyl allyl-
ation, the reaction with cyclohexanone was extended to
various allylic substrates (Table 2).
Synthesis 2003, No. 12, Print: 02 09 2003. Web: 25 08 2003.
Art Id.1437-210X,E;2003,0,12,1909,1915,ftx,en;Z03803SS.pdf.
DOI: 10.1055/s-2003-40999
Substituted acetates are convenient as reagents for the car-
bonyl allylation catalysed by the Co–Zn system. These al-
© Georg Thieme Verlag Stuttgart · New York

1910
P. Gomes et al.
FEATURE ARTICLE
lylic derivatives react more slowly with cyclohexanone tive ketone first undergoes a reduction reaction of the
than simple allyl acetate (Table 2, entries 1–4). The ke- carbon–chlorine bond affording the corresponding ho-
tone regioselectively attacks the more substituted allylic moallylic alcohol 10 in 72% yield.
position to give a single regioisomer. This process exhib-
The reaction of allyl acetate catalysed by Co–Zn system
its the reverse regioselectivity in comparison with the
has also been extended to aldehydes, which are reactive in
Pd(0)–SmI2 system.
most allylation processes. The results are reported in
Allylic alcohol can also be used, avoiding the preparation Table 3.
of the corresponding allylic acetate (Table 2, entry 4).
Several aldehydes such as aromatic (Table 3, entries 1–3),
This last reaction has been poorly developed except for
aliphatic (Table 3, entries 4–6) and heteroaromatic
3
Pd(0)–SnCl2 and Pd(0)–InI5 systems. In our case, the
(Table 3, entries 8,9) reacted with allyl acetate. With an
coupling reaction takes place for the cinnamyl alcohol but
, -unsaturated aldehyde (Table 3, entry 7), the 1,2-addi-
the starting products are consumed more slowly (4 days)
tion product is selectively obtained.
than the corresponding acetate (Table 2, entry 4).
Our mechanistic interpretation is based on the mechanism
As shown in Scheme 2, the allylation of an -chloroke-
described recently concerning the activation of allylic ac-
tone by cinnamyl acetate was also performed but the reac-
Biographical Sketches
Paulo Gomes was born in under the supervision of of Prof. Olivia Reinaud at
France in 1975. He received Prof. Jacques Périchon and the University René Des-
his PhD degree from the Corinne Gosmini. His thesis cartes, France, where he is
University of Paris XII-val work concerned the synthe- currently engaged in post-
de Marne, France, at the sis and electrosynthesis of doctoral research, studying
Laboratoire d’Electrochim- C–C bonds catalyzed by co- the synthesis of water solu-
ie, Catalyse et Synthèse Or- balt complexes. In October ble calix[6]arenes.
ganique in Thiais in 2002 2002, he moved to the group
Corinne Gosmini was born Catalyse et Synthèse Orga- oped new electrochemical
in France and received her nique in Thiais. She com- reactions catalyzed by sim-
PhD degree from the Uni- pleted her habilitation at the ple cobalt complexes. Re-
versity Pierre et Marie Cu- University of Paris XII-Val cently, she has pioneered
rie, Paris, in 1992 under the de Marne in 2001. She was laboratory research devoted
supervision of Prof. Jean F. primarily interested in the to the conversion of electro-
Normant and Raymond electrosynthesis of arylzinc chemical synthetic process-
Sauvêtre. She obtained a re- compounds and in the de- es to industry-adaptable
search position at the CNRS velopment of new electro- pure chemical processes,
in 1993 in the group of Prof. chemical methods devoted notably in the preparation of
Jacques Périchon at the Lab- to C–C bond formation. arylzinc compounds.
oratoire d’Electrochimie, Since 1998, she has devel-
Jacques Périchon is Pro- ganic electrosynthesis (in years, his research has fo-
fessor at the Université Paris particular nickel catalysts) cused on the development of
Val de Marne, France. In in the mid 1980’s. Since electrosynthetic reactions
1985, he created the Labora- 1983, he applied the sacrifi- catalysed by cobalt or iron
toire d’Electrochimie, Ca- cial anode process to the de- halides and on their transpo-
talyse et Synthèse Organ- velopment of a variety of sition to ‘all chemical’ pro-
ique at the CNRS of Thiais, reactions (preparation of cesses, to make organic
which he directed for 12 aryl carboxylates, cross- chemists more familiar with
years. In 1994, he received coupling of aromatic ha- electrosynthesis and easier
an award from the French lides, synthesis of arylzinc to scale up in industry. He is
Academy of Sciences. His compounds, etc…), some of still working on these topics
research interests, originally these electrochemical pro- with his group.
devoted to analytical elec- cesses having no chemical
trochemistry, moved to or- analogues. For the last 5
Synthesis 2003, No. 12, 1909–1915 © Thieme Stuttgart · New York

FEATURE ARTICLE
Allylation of Carbonyl Compounds by Allylic Acetates
1911
Table 1 Ketones Allylation by Allyl Acetate with Co–Zn
En-try
1
Ketone
Product
OH
Yield (%)a
84
Time (h)
7
O
O
1
2
70
5
OH
2
3
4
65
84
5
7
HO
O
3
4
OH
O
5
6
40
55
5
3
HO
O
5
HO
S
O
S
6
a Yields of isolated pure products.
Table 2 Cyclohexanone Allylation by Allylic Substrates with Co–Zn
Entry
1
Allylic Substrate
Product
OH
Yield (%)a
94
Time
24 h
OAc
7
2
69
16 h
Ph
OAc
OH
8
Ph
3
4
24
41
7 d
4 d
OH
OAc
9
8
Ph
OH
OH
Ph
a Yields of isolated pure products.
Synthesis 2003, No. 12, 1909–1915 © Thieme Stuttgart · New York

1912
P. Gomes et al.
FEATURE ARTICLE
Scheme 2
Table 3 Allylation of Aldehydes by Allyl Acetate with Co–Zn
Entry
1
Aldehyde
Product
Yield (%)a
83
Time (h)
5
MeO
MeO
CHO
11
OH
2
3
96
63
6
OMe
CHO
OMe
12
OH
96
13
CHO
HO
4
5
92
73
4
6
CHO
14
OH
CHO
15
HO
6
7
8
94
57
75
4
72
20
CHO
16
HO
CHO
17
OH
O
O
OHC
18
OH
OH
9
89
24
CHO
S
S
19
a Yields of isolated pure products.
etate by CoBr2.10 In a preliminary step, cobalt(II) bromide This reaction using the new system Co–Zn provides a
is reduced to Co(I) by zinc dust previously activated by novel method for forming C–C bonds by coupling carbo-
acid (trace amounts). That latter Co(I) complex undergoes nyl compounds and allylic acetates or alcohols. This pro-
oxidative addition with the allylic acetate which results in cess is interesting since the starting allylating reagents,
a
3-allyl Co(III) species, which is readily reduced by zinc acetates, and alcohols, are easily prepared and relatively
dust into 3-allyl Co(II) species. That latter 3-allyl Co(II) stable. The advantage of this method is its applicability to
complex is most likely the active species toward the car- both ketones and aldehydes. Further studies are in
bonyl compound, as suggested in Scheme 3.
progress to extend that reaction to other electrophilic re-
agents.
Synthesis 2003, No. 12, 1909–1915 © Thieme Stuttgart · New York

FEATURE ARTICLE
Allylation of Carbonyl Compounds by Allylic Acetates
1913
CoIBr
+
1/2 ZnBr2
1/2 Zn
CoIIBr2
CoIBr
+
1/2 Zn
OAc
+
+
1/2 ZnBr
CoIII
OAc
CoIIOAc
Br
OH
R1
R2
R1 R2
O
+
CoIIOAc
Scheme 3
All reactions were conducted under an atmosphere of argon. Reac-
tions were monitored by GC analyses on a Varian 3300 by using a
column CPSiL5CB (l = 25 m) coupled with a Chromjet Spectra-
Physics. NMR spectra were obtained in CDCl3 at r.t. on a Brucker
AC-200 instrument [1H NMR (200MHz), 13C NMR (50MHz)].
Mass spectra (MS) were determined on a Thermofinnigan GCQ re-
corded with a spectrometer coupled with a gas chromatograph
(25m). All reagents and solvents were obtained from commercial
suppliers and were used without further purification. All reactions
involved the use of anhydrous CoBr2 (Acros). Chromatography was
carried out using Merck 60 230–400 mesh silica gel. The starting
substituted allylic acetates were prepared from the commercially
available corresponding alcohols as described in the literature.11
umn chromatography on silica gel with pentane–Et2O (95:5) as elu-
ent to give 3 in 65% (1.02 g) yield.
IR(film): 3420, 2940 cm–1.
1H NMR: = 5.97–5.76 (m, 1 H), 5.16–5.05 (m, 2 H), 2.22 (d, 2 H,
J = 7.4 Hz), 1.68 (s, 1 H), 1.50–1.21 (m, 8 H), 1.16 (s, 3 H), 0.89 (t,
3 H, J = 6.6 Hz).
13C NMR: = 134.1, 118.4, 72.1, 46.2, 41.7, 32.3, 26.6, 23.4, 22.5,
13.9.
MS: m/z (%) = 139 (M – OH, 12), 115 (53), 97 (43), 69 (26), 55
(100).
2-Phenylpent-4-en-2-ol (4)
By a similar procedure to that described for the synthesis of 1, stir-
ring acetophenone (1.2 g, 10 mmol) with allylic acetate (1.1 mL, 10
mmol) for 7 h afforded 4. The residue was purified by column chro-
matography on silica gel with pentane–Et2O (95:5) as eluent to give
4 in 84% (1.36 g) yield.
IR(film): 3440, 2980, 2940, 1640, 1600 cm–1.
1H NMR: = 7.36–7.08 (m, 5 H), 5.62–5.41 (m, 1 H), 5.06–4.97
(m, 2 H), 2.42 (d, 2 H, J = 8.0 Hz), 2.17 (s, 1 H),1.43 (s, 3 H).
13C NMR: = 147.4, 133.5, 127.9, 126.4, 124.6, 119.1, 73.4, 48.2,
29.6.
1-(Prop-2-enyl)cyclohexan-1-ol (1); Typical Procedure
In a solution of MeCN (20 mL) containing zinc dust (1.3 g, 20
mmol) and CoBr2 (0.66 g, 3 mmol), allylic acetate (1.1 mL,10
mmol) and a stoichiometric amount of cyclohexanone (0.98 g,10
mmol) were added. The reaction medium is then activated by add-
ing trifluoroacetic acid (0.05 mL) at r.t. The mixture was stirred at
r.t. for 7 h, one of the two starting compounds was consumed. The
mixture was quenched with HCl (2 N) and extracted with Et2O
(2 × 25 mL). The combined organic layers were washed with brine,
dried (MgSO4), and the solvent evaporated under vacuum to afford
1. The residue was purified by column chromatography on silica gel
with pentane–Et2O (90:10) as eluent to give 1 in 84% (1.18 g) yield.
MS: m/z(%) = 145 (M – OH, 57), 129 (10), 122 (11), 121 (100), 105
IR(film): 3440, 2940, 1720 cm–1.
(26), 77 (32), 51 (20).
1H NMR: = 5.69–5.48 (m, 1 H), 4.82–4.73 (m, 2 H), 1.91 (d, 2 H,
J = 7.3 Hz), 1.72 (s, 1 H), 1.42–1.15 (m, 10 H).
13C NMR: = 133.8, 117.9, 71.3, 46.6, 37.0, 25.6, 22.0.
1,1-Diphenylbut-3-en-1-ol (5)
By a similar procedure to that described for the synthesis of 1, stir-
ring benzophenone (1.82 g, 10 mmol) with allylic acetate (1.1 mL,
10 mmol) for 5 h afforded 5. The residue was purified by column
chromatography on silica gel with pentane–Et2O (95:5) as eluent to
give 5 in 40% (0.9 g) yield.
MS: m/z (%) = 123 (M – OH, 11), 99 (39), 81(100), 79 (72), 77 (15),
55 (15).
IR(film): 3500, 3060, 3040, 1640, 1600 cm–1.
1-(Prop-2-enyl)cyclohex-2-en-1-ol (2)
By a similar procedure to that described for the synthesis of 1, stir-
ring cyclohexenone (0.96 g, 10 mmol) with allylic acetate (1.1 mL,
10 mmol) for 5 h afforded 2. The residue was purified by column
chromatography on silica gel with pentane–Et2O (95:5) as eluent to
give 2 in 70% (0.98 g) yield.
1H NMR: = 7.75–7.02 (m, 10 H), 5.72–5.51 (m, 1 H), 5.08–5.02
(m, 2 H), 3.00 (d, 2 H, J = 7.1 Hz), 2.70 (s, 1 H).
13C NMR: = 146.9, 137.7, 135.1, 130.2, 128.3, 127.0, 126.2,
118.8, 78.1, 46.9.
IR(film): 3440, 3060, 2980, 2940, 1640, 1600 cm–1.
MS: m/z (%) = 206 (10), 184 (160), 183 (100), 105 (93), 77 (27).
1H NMR: = 5.98–5.77 (m, 2 H), 5.64–5.59 (m, 1 H), 5.15–5.00
(m, 2 H), 2.29 (d, 2 H, J = 7.2 Hz), 2.02 (s, 1 H), 2.16–1.59 (m, 6 H).
13C NMR: = 133.5, 132.0, 129.7, 118.1, 68.9, 46.5, 35.2, 24.9,
18.7.
2-(2-Thienyl)pent-4-en-2-ol (6)12
By a similar procedure to that described for the synthesis of 1, stir-
ring 2-acetylthiophene (0.94 g, 10 mmol) with allylic acetate (1.1
mL, 10 mmol) for 3 h afforded 6. The residue was purified by col-
umn chromatography on silica gel with pentane–Et2O (90:10) as
eluent to give 6 in 55% (0.75 g) yield.
MS: m/z (%) = 121 (M – OH, 25), 97 (100), 79(44), 77 (30), 67 (14),
55 (20).
IR(film): 3450, 3060 cm–1.
4-Methylnon-1-en-4-ol (3)
1H NMR: = 7.02 (dd, 1 H, J = 1.5, 4.7 Hz), 6.81–6.75 (m, 2 H),
5.72–5.51 (m, 1 H), 5.02–4.93 (m, 2 H), 2.92 (s, 1 H), 2.59–2.40 (m,
2 H), 1.47 (s, 3 H).
By a similar procedure to that described for the synthesis of 1, the
stirring of heptan-2-one (1.14 g,10 mmol) with allylic acetate (1.1
ml, 10 mmol) for 5 h afforded 3. The residue was purified by col-
Synthesis 2003, No. 12, 1909–1915 © Thieme Stuttgart · New York

1914
P. Gomes et al.
FEATURE ARTICLE
1-(4-Methoxyphenyl)but-3-en-1-ol (11)
By a similar procedure to that described for the synthesis of 1, stir-
ring 4-methoxybenzaldehyde (1.36 g, 10 mmol) with allylic acetate
(1.1 mL, 10 mmol) for 5 h afforded 11. The residue was purified by
column chromatography on silica gel with pentane–Et2O (95:5) as
eluent to give 11 in 83% (1.48 g).
13C NMR: = 153.2, 133.6, 126.7, 123.9, 122.4, 119.2, 73.0, 46.3,
30.1.
MS: m/z (%) = 151 (M – OH, 10), 127 (160), 111 (13).
1-(1-Methylprop-2-en-1-yl)cyclohexan-1-ol (7)
By a similar procedure to that described for the synthesis of 1, stir-
ring cyclohexanone (0.98 g, 10 mmol) with crotyl acetate (1.14 g,
10 mmol) for 24 h afforded 7. The residue was purified by column
chromatography on silica gel with pentane–Et2O (90:10) as eluent
to give 7 in 94% (1.45 g) yield.
IR(film): 3420, 3000, 2920, 2840, 1620 cm–1.
1H NMR: = 7.41 (d, 2 H, J = 8.7 Hz), 7.02 (d, 2 H, J = 8.7 Hz),
6.00–5.83 (m, 1 H), 5.32–5.23 (m, 2 H), 4.80 (t, 1 H, J = 6.6 Hz),
3.94 (s, 3 H), 2.68–2.61 (m, 2 H), 2.19 (s, 1 H).
13C NMR: = 159.0, 136.1, 134.7, 127.2, 118.0, 113.8, 73.1, 55.2,
43.6.
IR(film): 3460, 2940, 1640, cm–1.
1H NMR: = 5.92–5.74 (m, 1 H), 5.09–5.00 (m, 2 H), 2.24–2.09
(m, 1 H), 1.61 (s, 1 H), 1.56–1.08 (m, 10 H), 1.02 (d, 3 H, J = 6.9
Hz).
MS: m/z (%) = 161 (M – OH, 19), 160 (100), 159 (86), 145 (27),
144 (27), 129 (41), 128 (22), 115 (36), 151 (M – OH,10), 127 (160),
111 (13).
13C NMR: = 140.4, 115.6, 72.3, 48.3, 34.8, 34.3, 25.8, 21.7, 14.0.
MS: m/z (%) = 137 (M – OH, 5), 99 (47), 81(100), 81 (100), 79 (71),
77 (15).
1-(2-Methoxyphenyl)but-3-en-1-ol (12)
By a similar procedure to that described for the synthesis of 1, stir-
ring 2-methoxybenzaldehyde (1.36 g, 10 mmol) with allylic acetate
(1.1 mL, 10 mmol) for 6 h afforded 12. The residue was purified by
column chromatography on silica gel with pentane/e–Et2Other
(95:5) as eluent to give 12 in 96% (1.71 g) yield.
1-(1-Phenylpropen-2-yl)cyclohexan-1-ol (8)
By a similar procedure to that described for the synthesis of 1, stir-
ring cyclohexanone (0.98 g, 10 mmol) with cinnamyl acetate (1.76
g, 10 mmol) for 16 h afforded 8. The residue was purified by col-
umn chromatography on silica gel with pentane–Et2O (90:10) as
eluent to give 8 in 69% (1.49 g) yield.
IR(film): 3450, 3030, 2920, 2860, 1640, 1600 cm–1.
1H NMR: = 7.26–7.08 (m, 5 H), 6.34–6.15 (m, 1 H), 5.11–4.98
(m, 2 H), 3.16 (d, 1 H, J = 9.8Hz), 1.62–1.05 (m, 11 H).
13C NMR: = 140.9, 137.7, 129.2, 128.1, 126.4, 117.1, 72.5, 61.0,
35.7, 35.4, 25.6, 21.8.
IR (film): 3440, 2940, 1740, 1600 cm–1.
1H NMR: = 7.26–7.10 (m, 2 H,), 6.90–6.71 (m, 2 H,), 5.81–5.64
(m, 1 H,), 5.08–4.80 (m, 3 H,), 3.72 (s, 3 H,), 2.50–2.37 (m, 2 H,),
1.98 (s, 1 H,).
13C NMR: = 156.2, 135.1, 131.5, 128.2, 126.7, 120.5, 117.3,
110.3, 69.5, 55.1, 41.7.
MS: m/z (%) = 161 (M – OH, 5), 138 (11), 137 (100), 107 (61), 77
(11).
MS: m/z(%) = 199 (M-OH, 5), 118 (89), 117(100), 115 (33), 99
(17), 81 (52), 79 (37).
1-Naphthylbut-3-en-1-ol (13)
By a similar procedure to that described for the synthesis of 1, stir-
ring 1-naphtaldehyde (1.59 g, 10 mmol) with allylic acetate (1.1
mL, 10 mmol) for 96 h afforded 13. The residue was purified by col-
umn chromatography on silica gel with pentane–Et2O (95:5) as elu-
ent to give 13 in 63% (1.25 g) yield.
1-(1,1-Dimethylprop-2-en-1-yl)cyclohexan-1-ol (9)
By a similar procedure to that described for the synthesis of 1, the
stirring of cyclohexanone (0.98 g, 10 mmol) with 1,1-dimethyl
prop-2-enyl acetate 21 (1.28 g, 10 mmol) for 7 d afforded 9. The res-
idue was purified by column chromatography on silica gel with pen-
tane–Et2O (90:10) as eluent to give 9 in 24% (0.4 g) yield.
IR (film): 3400, 3060, 2940, 1680 cm–1.
IR(film): 3450 cm–1.
1H NMR: = 5.93 (dd, 1 H, J = 11, 17.4 Hz), 5.04–4.91 (m, 2 H),
1.61–1.31 (m, 11 H), 0.93 (s, 6 H).
13C NMR: = 145.5, 113.3, 74.4, 44.2, 31.3, 25.8, 21.9, 21.8, 21.7.
1H NMR: = 8.12–7.47 (m, 7 H), 6.07–5.86 (m, 1 H), 5.57–5.30
(m, 1 H), 5.29–5.19 (m, 2 H), 4.99 (s, 1 H), 2.86–2.59 (m, 2 H).
13C NMR: = 139.3, 134.6, 133.7, 130.2, 128.1, 127.8, 125.9,
125.4, 122.9, 117.9, 70.0, 42.6.
MS: m/z (%) = 199 (M + 1, 23), 158 (12), 157 (100), 129 (64), 128
(25), 127 (11).
MS: m/z (%) = 151 (M – OH, 5), 99 (38), 81 (100), 77 (14), 70 (10),
55 (27).
Dodec-1-en-4-ol (14)
3-Methyl-4-phenylhex-5-en-3-ol (10)13
By a similar procedure to that described for the synthesis of 1, stir-
ring nonyl aldehyde (1.42 g, 10 mmol) with allylic acetate (1.1 mL,
10 mmol) for 4 h afforded 14. The residue was purified by column
chromatography on silica gel with pentane–Et2O (95:5) as eluent to
give 14 in 92% (1.69 g) yield.
By a similar procedure to that described for the synthesis of 1, stir-
ring 3-chloro 2-butanone (1.07 g, 10 mmol) with cinnamyl acetate
(1.76 g, 10 mmol) for 7 h afforded 10. The residue was purified by
column chromatography on silica gel with pentane–Et2O (98:2) as
eluent to give 10 in 72% (1.37 g) yield.
IR (film): 3460, 2920, 1730 cm–1.
IR(film): 3450, 3030, 2920, 1640, 1600 cm–1.
1H NMR: = 5.75–5.54 (m, 1 H), 4.96–4.88 (m, 2 H), 3.51–3.46
(m, 1 H), 2.16–1.91 (m, 2 H), 1.86 (s, 1 H), 1.44–1.10 (m, 14 H),
0.70 (t, 3 H, J = 6.3 Hz).
13C NMR: = 134.6, 117.4, 70.9, 41.5, 36.4, 31.7, 29.4, 29.1, 25.4,
22.4, 20.3, 13.8.
1H NMR: = 7.23–7.05 (m, 5 H,), 6.31–6.09 (m, 1 H), 5.09–4.97
(m, 2 H), 3.20 (2 d, 1 H, J = 4.8 Hz), 1.88 (s, 1 H), 1.37 (2 q, 2 H,
J = 7.4 Hz), 0.99 (2 s, 3 H), 0.81 (2 t, 3 H, J = 7.4 Hz).
13C NMR: = 141.2, 141.0, 137.9, 137.8, 129.1, 128.1, 126.4,
117.2, 117.1, 74.1, 74.0, 59.9, 32.6, 32.4, 24.1, 24.0, 7.9.
MS: m/z (%) = 167 (M – OH, 69), 153 (64), 149 (60), 135 (76), 121
(60), 109 (60), 107 (55), 98 (100), 97 (48), 95 (57), 93 (84), 84 (47),
83 (69), 81 (82), 79 (73), 67 (79), 55 (41).
MS: m/z (%) = 173 (M – OH, 5), 118 (69), 117 (100), 115 (38), 91
(12), 73 (12), 55 (26).
Synthesis 2003, No. 12, 1909–1915 © Thieme Stuttgart · New York

FEATURE ARTICLE
Allylation of Carbonyl Compounds by Allylic Acetates
IR (film): 3400, 3080, 2920, 1740, 1700, 1600 cm–1.
1915
6,10-Dimethylundeca-1,9-dien-4-ol (15)
By a similar procedure to that described for the synthesis of 1, stir-
ring of 3,7-dimethyl-6-octenal (1.54 g, 10 mmol) with allylic ace-
tate (1.1 mL, 10 mmol) for 6 h afforded 15. The residue was purified
by column chromatography on silica gel with pentane–Et2O (95:5)
as eluent to give 15 in 73% (1.43 g) yield.
1H NMR: = 7.26 (dd, 1 H, J = 0.9 Hz, 1.9 Hz), 6.22 (dd, 1 H,
J = 1.9, 3.1 Hz), 6.13 (d, 1 H, J = 3.1 Hz), 5.79–5.59 (m, 1 H), 5.10–
4.98 (m 2 H), 4.61 (t, 1 H, J = 6.6 Hz) 2.68 (s, 1 H) 2.54–2.46 (m, 2
H).
13C NMR: = 156.2, 141.9, 133.9, 118.3, 110.1, 106.1, 67.0, 40.1.
IR (film): 3400, 2920 cm–1.
MS: m/z (%) = 138 (5), 121 (M – OH, 5), 97 (100), 69 (20).
1H NMR: = 5.94–5.73 (m, 1 H), 5.15–5.08 (m, 3 H), 3.80–3.68
(m, 1 H), 2.33–2.01 (m, 3 H), 1.97 (s 1 H), 1.68 (s, 3 H) 1.60 (s, 3
H), 1.55–1.11 (m, 6 H), 0.92 (2 d, 3 H, J = 6.5 Hz).
13C NMR: = 134.8, 130.9, 124.6, 117.8, 68.6, 68.3, 44.2, 42.7,
42.0, 37.8, 36.6, 29.2, 28.8, 20.1, 19.0, 17.5.
1-(3-Thienyl)but-3-en-1-ol (19)
By a similar procedure to that described for the synthesis of 1, stir-
ring 3-thiophenecarboxaldehyde (1.12 g, 10 mmol) with allylic ac-
etate (1.1 mL, 10 mmol) for 20 h afforded 19. The residue was
purified by column chromatography on silica gel with pentane–
Et2O (95:5) as eluent to give 19 in 89% (1.37 g) yield.
MS: m/z (%) = 155 (46), 137 (47), 121 (22), 107 (32), 95 (71), 93
(28), 81 (100), 79 (50), 69 (29), 67 (79).
IR (film): 3400, 3080, 2920, 1640 cm–1.
1-Phenylpent-4-en-2-ol (16)
1H NMR: = 7.11 (dd, 1 H, J = 3.0, 4.9 Hz), 6.99 (dd, 1 H, J = 1.2,
3.0 Hz), 6.91 (dd, 1 H, J = 1.2, 4.9 Hz), 5.74–5.53 (m, 1 H), 5.02–
4.92 (m, 2 H), 4.60 (t, 1 H, J = 7.1 Hz), 4.06 (s, 1 H), 2.40–2.33 (m,
2 H).
By a similar procedure to that described for the synthesis of 1, stir-
ring phenylacetaldehyde (1.2 g, 10 mmol) with allylic acetate (1.1
mL, 10 mmol) for 4 h afforded 16. The residue was purified by col-
umn chromatography on silica gel with pentane–Et2O (95:5) as elu-
ent to give 16 in 94% (1.52 g) yield.
13C NMR: = 145.3, 134.3, 125.7, 120.6, 117.7, 65.6, 42.7.
IR (film): 3420, 2980, 2920, 1620 cm–1.
MS: m/z (%) = 154 (5), 137 (M – OH, 26), 113 (78), 85 (100).
1H NMR: = 7.22–7.04 (m, 5 H), 5.86–5.65 (m, 1 H), 5.06–4.99
(m, 2 H), 3.81–3.68 (m, 1 H), 2.74–2.54 (m, 2 H), 2.24–2.05 (m, 3
H)
13C NMR: = 138.6, 134.1, 129.5, 128.5, 126.4, 117.9, 71.8, 43.3,
41.2.
References
(1) Yamamoto, Y.; Asao, N. Chem. Rev. 1993, 93, 2207.
(2) Masuyama, Y.; Kinugawa, N.; Kurusu, Y. J. Org. Chem.
1987, 52, 3704.
MS: m/z (%) = 145 (M – OH, 19), 144 (16), 121 (37), 103 (33), 92
(70), 91 (100), 79 (16), 77 (13), 65 (13).
(3) (a) Masuyama, Y.; Takahara, J. P.; Kurusu, Y. J. Am. Chem.
Soc. 1988, 110, 4473. (b) Takahara, J. P.; Masuyama, Y.;
Kurusu, Y. J. Am. Chem. Soc. 1992, 114, 2577.
(4) Tabuchi, T.; Inanaga, J.; Yamaguchi, M. Tetrahedron Lett.
1986, 27, 1195.
(5) Araki, S.; Kamei, T.; Yamamura, H.; Kawai, M. Org. Lett.
2000, 2, 847.
(6) Qiu, W.; Wang, Z. J. Chem. Soc., Chem. Commun. 1989,
356.
1-Phenylhexa-1,5-dien-3-ol (17)
By a similar procedure to that described for the synthesis of 1, stir-
ring trans-cinnamaldehyde (1.32 g, 10 mmol) with allylic acetate
(1.1 mL, 10 mmol) for 72 h afforded 17. The residue was purified
by column chromatography on silica gel with pentane–Et2O (95:5)
as eluent to give 17 in 57% (0.99 g) yield.
(7) Tsuji, Y.; Mukai, T.; Kondo, T.; Watanabe, Y. J.
Organomet. Chem. 1989, 369, C51.
(8) (a) Gomes, P.; Gosmini, C.; Nédélec, J.-Y.; Périchon, J.
Tetrahedron Lett. 2002, 43, 5901. (b) Gomes, P.; Fillon, H.;
Gosmini, C.; Labbé, E.; Périchon, J. Tetrahedron 2002, 58,
8417.
(9) Gomes, P.; Gosmini, C.; Périchon, J. Patent application
France, 01/08808, 2001.
(10) Buriez, O.; Labbé, E.; Périchon, J. J. Electroanal. Chem.
2003, 543, 143.
IR (film): 3420, 2940 cm–1.
1H NMR: = 7.48–7.11 (m, 5 H), 6.58–6.40 (m, 1 H), 6.13–5.61
(m, 2 H), 5.09–4.95 (m, 2 H), 4.09–3.95 (m, 2 H), 2.44–2.24 (m, 1
H), 1.98 (s, 1 H).
13C NMR: = 136.7, 134.6, 132.7, 130.4, 128.5, 126.5, 125.6,
116.9, 96.5, 40.7.
MS: m/z (%) = 156 (100), 155 (51), 153 (39), 141 (63), 128 (47),
115 (39), 91 (26).
(11) Durandetti, M.; Nédélec, J. Y.; Périchon, J. J. Org. Chem.
1996, 61, 1748.
(12) Schuetz, H. J. Am. Chem. Soc. 1955, 77, 1839.
(13) Majee, A.; Das, A. R.; Ranu, B. C. Indian J. Chem., Sect. B
1998, 37, 731.
1-(2-Furyl)but-3-en-1-ol (18)
By a similar procedure to that described for the synthesis of 1, the
stirring of 2-furaldehyde (0.96 g, 10 mmol) with allylic acetate (1.1
mL, 10 mmol) for 20 h afforded 18. The residue was purified by col-
umn chromatography on silica gel with pentane–Et2O (95:5) as elu-
ent to give 18 in 75% (1.04 g) yield.
Synthesis 2003, No. 12, 1909–1915 © Thieme Stuttgart · New York