Allylation of aldehydes with potassium allyltrifluoroborate catalyzed by Amberlyst A-15

Article abstract of DOI:10.1016/j.tet.2013.06.050

The use of the commercially available resin Amberlyst-15 as catalyst for allylation of aldehydes by potassium allyltrifluoroborate is described. The method features the use of a commercially available catalyst, aqueous media, and the products were obtained in high yields, short reaction times, at room temperature and no further purification. The catalyst was recovered and reused up to six times in further allylation reactions without significant yield losses. ¹¹B NMR experiments were conducted in order to evaluate the possible mechanism pathway. The formation of tricoordinate boron species was not observed.

Full text of DOI:10.1016/j.tet.2013.06.050

Tetrahedron 69 (2013) 7006e7010
Contents lists available at SciVerse ScienceDirect
Tetrahedron
journal homepage: www.elsevier.com/locate/tet
Allylation of aldehydes with potassium allyltrifluoroborate catalyzed
by Amberlyst A-15
T uꢀ lio R. Couto, Juliano C.R. Freitas, Italo H. Cavalcanti, Roberta A. Oliveira,
*
Paulo H. Menezes
Departamento de Química, Universidade Federal de Pernambuco, Av. Jornalista Anibal Fernandes s/n, 50670-901 Recife, PE, Brazil
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 25 April 2013
Received in revised form 11 June 2013
Accepted 13 June 2013
Available online 21 June 2013
The use of the commercially available resin Amberlyst-15 as catalyst for allylation of aldehydes by po-
tassium allyltrifluoroborate is described. The method features the use of a commercially available cat-
alyst, aqueous media, and the products were obtained in high yields, short reaction times, at room
temperature and no further purification. The catalyst was recovered and reused up to six times in further
allylation reactions without significant yield losses. 11B NMR experiments were conducted in order to
evaluate the possible mechanism pathway. The formation of tricoordinate boron species was not
observed.
Keywords:
Allylation
Potassium allyltrifluoroborate
Amberlyst A-15
Ó 2013 Elsevier Ltd. All rights reserved.
1
. Introduction
arrangement requires a synclinal orientation of reacting p sys-
8
tems. The Type II allyl reactions usually requires an external acti-
vation of the carbonyl group by an appropriate Lewis or Brønsted
acid, to give open transition structures.
The addition of allylic organometallics to carbonyl compounds is
1
one of the most important methods used for CeC bond formation.
The reaction can be compared to the aldol reaction while the ob-
tained product, a homoallylic alcohol can be further converted into
Type I mechanism appears to be the best choice because an
external promoter, such as a Lewis or Brønsted acid would compete
2
4b
the corresponding aldol.
with the boron atom for the basic aldehyde oxygen. In this con-
3
9
10
Several approaches based on the use of allylic organometallic
text, the addition of allylic boronates, 1,3,2-dioxaborolidines,
4
11
or organometalloid reagents, as well as electrochemical based
trifluoroborates to aldehydes promoted by a variety of Lewis or
methods5 were developed. However, some of these reagents are
expensive and difficult to handle due to its Lewis base character and
because of competing Wurtz coupling reactions.
Brønsted acid were already described. However, allylic boranes are
12
not subjected to this catalytic effect.
The development and the application of methods based on the
use of heterogeneous catalysts is of a great interest, as these cata-
lysts can be recovered, recycled and sometimes used in aqueous
Alternative protocols based on the Barbier reaction avoids the
6
previous preparation of the allylic organometallic, but the use of
13
zero valent metals can cause metal oxide (or hydroxide) pre-
cipitation and Rieke metals are sensitive to the reaction media.
Allyl boron reagents have proved to be very useful in the ally-
lation of carbonyl compounds because of easy formation and sta-
bility and due to date, several methods for the allylation of carbonyl
compounds based on the use of allyl boron compounds were
developed.7
and non-aqueous media. In the past decade, the use of Amberlyst
A-15, a commercially available and non-expensive resin, in organic
synthesis experienced a rapid development mainly due to its mild
14
and highly selective properties.
Herein, we wish to describe an environmentally benign reaction
for the synthesis of homoallylic alcohols based on the reaction of
potassium allyltrifluoroborate and aldehydes containing different
functional groups in aqueous media catalyzed by a recyclable and
inexpensive catalyst Amberlyst A-15.
Mechanistically, allyl boron reagents can be classified in Type I
or Type II reactions. Type I reactions proceed through a six-
membered cyclic transition state characterized by the internal ac-
7
tivation of the carbonyl group by the boron atom. This
2. Results and discussion
In the course of developing an optimal set for reaction condi-
tions, we first examined different types of heterogeneous catalysts.
*
Corresponding author. Tel.: þ55 81 2126 7473; fax: þ55 81 2126 8402; e-mail
addresses: pmenezes@ufpe.br, paulo.menezes@pq.cnpq.br (P.H. Menezes).
0
040-4020/$ e see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.tet.2013.06.050

T.R. Couto et al. / Tetrahedron 69 (2013) 7006e7010
7007
Thus, 2-naphtaldehyde, 1a (1 mmol) and potassium allyltri-
fluoroborate, 2 (1.1 mmol) were treated at room temperature with
catalyst (100% m/m) using a mixture of CH Cl :H O (1:1) and the
2 2 2
times were required to promote the reaction (Table 3, entries 2, 3,
5). The small differences in the isolated yields are more likely to be
due to the solubilities of reactants and products.
progress of the reaction was monitored by TLC. The results are
presented in Table 1, and all reported yields in this and other tables
are isolated yields.
Table 3
Effect of CH
allyltrifluoroborate 2 at room temperature
2 2 2
Cl :H O ratio on the allylation of 2-naphthaldehyde 1a by potassium
Table 1
Effect of the catalyst on the allylation of 2-naphthaldehyde 1a by potassium allyl-
ꢀ
trifluoroborate 2 in 1:1 CH
2
Cl
2
:H
2
O at 25
C
2
H O
CH
2
Cl
2
Time (min)
3a (%)
1
2
3
4
5
6
0
1
0.9
0.75
0.5
0.25
0
300
270
20
15
30
95
82
88
93
85
87
0.1
0.25
0.5
0.75
1
Catalyst
Time (min)
3a (%)
1
2
3
4
5
d
15
15
30
45
45
10
93
95
93
95
Amberlyst A-15
Amberlyst A-26
Montmorillonite K-10
Montmorillonite KSF
90
The optimized reaction conditions, namely, CH
2
Cl
2
:H
2
O (1:1)
and Amberlyst A-15 (100% m/m), were then applied in the allyla-
tion reaction of different aldehydes (Table 4). The method tolerates
When the reaction was performed without the use of a catalyst,
the corresponding product 3a was obtained in small yield after
5 min. When different types of catalysts were used, the yield was
a wide range of functional groups and aliphatic, aromatic, a,b-un-
saturated, and heterocyclic aldehydes were efficiently allylated in
moderate to high yields.
1
considerably increased in all cases, indicating their effective action
as a catalyst (Table 1, entries 2e4). The best result was found when
Amberlyst A-15 was used as the catalyst where 3a was obtained in
Table 4
9
3% yield after 15 min (Table 1, entry 2).
Next we investigated the effect of the amount of catalyst to
Allylation of various aldehydes 1 with potassium allyltrifluoroborate 2 catalyzed by
Amberlyst A-15 (100% m/m)
promote the reaction. The catalytic load of Amberlyst A-15 was
varied from 50 to 500 % m/m (Table 2). It was observed that the
reaction yield did not change appreciably when the amount of the
catalyst varied from 50 to 200 % m/m (Table 2, entries 1e3)
however, lower amounts of the catalyst required longer reaction
times. Further increase in the catalyst amount resulted in lower
yield.
RCHO
Product
Time (min)
15
Yield (%)
93
1
2
3
4
1a
3a
Table 2
Effect of Amberlyst A-15 amount on the allylation of 2-naphthaldehyde 1a by po-
tassium allyltrifluoroborate 2 in 1:1 CH
2
2
Cl :H
2
O at room temperature
20
18
20
94
82
95
1b
3b
1c
3c
1d
3d
A-15 (% m/m)
Time (min)
3a (%)
1
2
3
4
50
100
200
500
25
15
15
10
90
93
92
80
5
15
90
1e
3e
6
7
8
25
20
20
95
95
95
1
f
The effect of the solvent in the reaction using different
Cl :H O ratio was also investigated. The use of only CH Cl in
3f
CH
2
2
2
2
2
the allylation reaction required a longer reaction time, probably
due to the low solubility of the potassium allyltrifluoroborate in this
solvent (Table 3, entry 1). A similar behavior was observed when
water was used as the reaction solvent again due to the low solu-
bility of the aldehyde in water (Table 3, entry 6). When a 1:1
1g
3g
2 2 2
mixture of CH Cl :H O was used as the reaction solvent, 3a was
obtained in a good yield and short reaction time (Table 3, entry 4).
However, with the variation in the amount of water, longer reaction
1h
3h
(continued on next page)

7008
T.R. Couto et al. / Tetrahedron 69 (2013) 7006e7010
Table 4 (continued )
Table 5
Amberlyst A-15 (100% m/m) recycling after successive runs after washing with
CH Cl and H
RCHO
Product
Time (min)
20
Yield (%)
93
2
2
2
O
9
1i
3i
Run
Time (min)
3a (%)
1
2
3
4
5
15
15
18
18
18
93
95
95
95
94
1
1
0
1
16
18
47
95
1j
3j
1
k
3
k
Table 6
1
1
1
2
3
5
15
18
15
71
95
86
Amberlyst A-15 (100% m/m) recycling after successive runs without catalyst
treatment
1
l
3
l
1
m
3
m
Run
Time (min)
3a (%)
1
2
3
4
5
15
25
25
30
30
93
94
93
92
91
1n
3n
1
1
6
7
25
10
90
95
1
o
3
o
1p
Previous reports dealing with the hydrolysis of some potassium
allyltrifluoroborates under buffered aqueous conditions suggested
the loss of KF as the rate-determining step, followed by a rapid
3p
16
1
8
40
50
exchange of F for OH to give the corresponding boronic acid. In
ꢁ
addition, when only water was used as solvent, the anions BF and
1q
3q
4
ꢁ
17
HOBF3 were detected.
11
Thus, analysis of B NMR spectrum of potassium allyltri-
fluoroborate, 2 in D
ꢀ
2
O at 25 C after 15 min revealed two signals at
d
6.32(q, J¼63Hz)corresponding to 2and
corresponding to deuteroxytrifluoroborate anion ðDOBF
A dramatic effect was observed when Amberlyst A-15 (100% m/
d
1.73(q, J¼15 Hz), probably
ꢁ
18
The electronic nature of the substituents in the aromatic alde-
3
Þ.
hydes has little influence on the reaction. For example, the ally-
lation of aromatic aldehydes containing electron-withdrawing or
electron donating groups gave the corresponding products in high
yields. Given the disparate electronic effects (o-, m- and p-sub-
stituents, aromatic and aliphatic groups) associated with the al-
dehydes, the small differences in the isolated yields are more likely
to be due to the solubilities of reactants and products. Additionally,
the reaction appears to be regioselective because only 1,2-addition
was observed for cinnamaldehyde (Table 4, entry 15). For aliphatic
aldehydes, the reaction also exhibited high efficiency (Table 4,
entry 16).
The recoverability and recyclability of the catalyst was in-
vestigated in two different situations. First, after each run, the
catalyst was separated from the reaction mixture, washed with
dichloromethane, water and reused. It was found that the catalyst
could be recovered and reused in further allylation reactions with
no significant differences in the yield and reaction time (Table 5).
However, when the catalyst was recycled without further
treatment, the conversion of the aldehyde 1a into the corre-
sponding homoallylic alcohol 3a required longer reaction times
after each run (Table 6).
m) was added to the solution of allyltrifluoroborate, 2 in D
2
O at
ꢀ
25 C. After 15 min, the two signals at
d
6.33 (q, J¼63 Hz) corre-
sponding to 2 and
d
1.66 (q, J¼14.7 Hz) were again observed, albeit
with 2 in low proportion.
Potassium organotrifluoroborates can be mild, and efficiently
converted into the corresponding boronic acids using silica gel and
1
9
H
2
O. Thus, following this procedure, a new experiment was
ꢀ
conducted, where 2 was dissolved in D
addition of SiO
the mixture indicated three distinct signals at
and
1.73 (q, J¼15 Hz), corresponding to 2 and DOBF
and a broad signal at 32.9 probably indicating the in situ forma-
2
O at 25 C followed by the
11
2
(10 equiv). After 15 min, the analysis of B NMR of
6.33 (q, J¼63 Hz)
d
-
d
3
, respectively,
d
tion of the corresponding allylboronic acid.
Although some groups have proposed that some organo-
trifluoroborates required acid catalysis to the hydrolysis into the
corresponding boronic acids and the addition of some tetra-
coordinate boron species to aldehydes promoted by Lewis acid
11
may proceed through the tricoordinate boron species, in all
11
conducted B experiments in this work, the presence of allyldi-
fluoroborane or allylboronic acid, as well as the formation of dis-
crete complexes between this compounds and the aldehyde were
not observed.
It is known from the literature that in aqueous medium some
potassium organotrifluoroborates suffer hydrolysis to yield the
corresponding boronic acids being the rates dependent on a num-
ber of variables, in special the organic moiety, resulting in complex
solvolytic profiles.15
Taking these results into consideration, Type II mechanism ap-
pears to be the best choice to explain the results, while the
Amberlyst A-15 would act as an external promoter by complexing

T.R. Couto et al. / Tetrahedron 69 (2013) 7006e7010
7009
to the basic aldehyde oxygen, leading to an open-chain Type II
mechanism.
4.3.1.2. 1-Phenyl-but-3-en-1-ol (3b). 1H NMR (300 MHz, CDCl
7.36e7.25 (m, 5H, HAryl), 5.88e5.74 (m, 1H, CH]CH ), 5.19e5.12
m, 2H, CH]CH
), 4.73 (dd, J¼7.5, 5.4 Hz, 1H, CHOH), 2.53e2.46 (m,
3
)
d
2
(
2
2
13
2 3
H, CHCH ), 2.00 (br s, 1H, OH); C NMR d (75 MHz, CDCl ) d 143.8,
3
. Conclusion
1
34.4, 128.2, 127.3, 125.7, 118.0, 73.2, 43.6. The data match with the
3
i
previously described compound.
In summary, we have shown that the commercially available
resin Amberlyst A-15 is an efficient catalyst for the allylation of
aldehydes by potassium allyltrifluoroborate. The method features
the use of a commercially available and recyclable catalyst, and
the products were obtained in short reaction times with high yield
and purity at room temperature. The methodology is simple, fast,
and efficient, uses water as co-solvent, and is synthetically useful
while it could be applied for the synthesis of more complex
compounds.
4
.3.1.3. 1-p-Tolyl-but-3-en-1-ol (3c). 1H NMR (300 MHz, CDCl
7.18 (d, J¼7.8 Hz, 2H, HAryl), 7.09 (d, J¼7.8 Hz, 2H, HAryl), 5.74 (ddd,
H, J¼17.1, 10.2, 6.6 Hz, CH]CH ), 5.13e5.04 (m, 2H, CH]CH ), 4.64
), 2.28 (s, 3H, CH ),
140.9, 137.2, 134.6,
3
)
d
1
(
1
2
2
t, J¼6.6 Hz, CHOH), 2.49e2.41 (m, 2H, CHCH
2
d
3
13
.69 (br s, 1H, OH); C NMR (75 MHz, CDCl
3
)
1
29.0, 125.7, 118.2, 73.1, 43.7, 21.1. The data match with the pre-
viously described compound.
3
i
4
.3.1.4. 1-(4-Nitrophenyl)but-3-en-1-ol (3d). 1H NMR (300 MHz,
CDCl
8.21 (d, J¼8.7 Hz, 2H, HAryl), 7.54 (d, J¼8.7 Hz, 2H, HAryl),
.86e5.72 (m, 1H, CH]CH ), 5.22e5.16 (m, 2H, CH]CH ), 4.87 (dd,
J¼7.8, 4.5 Hz, 1H, CHOH), 2.62e2.40 (m, 2H, CHCH ), 2.07 (br s, 1H,
151.1, 147.1, 133.1, 126.5, 123.5, 119.5,
4
4
. Experimental section
3
) d
5
2
2
.1. Materials
2
13
OH); C NMR (75 MHz, CDCl
3
) d
3
i
All reagents and solvents used were previously purified and
72.1, 43.8. The data match with the previously described compound.
2
0
dried in agreement with the literature. Aldehydes 1aeq were
purchased from Aldrich Chemical Co. and used as received. All
other commercially available reagents and solvents were used as
received. Reactions were monitored by thin-layer chromatogra-
phy on 0.25 mm E. Merck silica gel 60 plates (F254) using UV
light, vanillin and p-anisaldehyde as visualizing agents. Column
chromatography purification was performed using Silica Gel 60
4.3.1.5. 1-(3-Nitrophenyl)but-3-en-1-ol (3e). 1H NMR (300 MHz,
CDCl
8.24 (t, J¼1.5 Hz, 1H, HAryl), 8.13 (ddd, J¼8.1, 2.1, 0.9 Hz, 1H,
Aryl), 7.71 (d, J¼8.1 Hz, 1H, HAryl), 7.53 (t, J¼8.1 Hz, 1H, HAryl),
5.87e5.73 (m, 1H, CH]CH ), 5.22e5.16 (m, 2H, CH]CH ), 4.87 (dd,
J¼8.1, 5.1 Hz, 1H, CHOH), 2.63e2.43 (m, 2H, CHCH ), 2.19 (br s, 1H,
148.1, 145.9, 133.2, 131.9, 129.3,
122.4, 120.8, 119.6, 72.0, 43.9. The data match with the previously
3
) d
H
2
2
2
13
3
OH); C NMR (75 MHz, CDCl ) d
(
230e400 mesh) unless indicated otherwise. All compounds
3
i
purified by chromatography were sufficiently pure for use in
described compound.
further experiments, unless indicated otherwise.
4
.3.1.6. 1-(2-Nitrophenyl)but-3-en-1-ol (3f). 1H NMR (300 MHz,
CDCl 7.94 (dd, J¼8.1, 1.2 Hz, 1H, HAryl), 7.84 (dd, J¼8.1, 1.5 Hz, 1H,
Aryl), 7.65 (td, J¼8.1, 1.2 Hz, 1H, HAryl), 7.43 (td, J¼8.1, 1.2 Hz, 1H,
Aryl), 5.97e5.83 (m, 1H, CH]CH
), 5.32 (dd, J¼8.4, 3.6 Hz, 1H,
), 2.76e2.67 (m, 1H, CHCH ),
3
) d
4
.2. Instrumentation
H
H
1H NMR and 13C NMR data were recorded in CDCl
2
3
6
or DMSO-d .
CHOH), 5.25e5.18 (m, 2H, CH]CH
2
2
The chemical shifts are reported as
d units in parts per million
13
2 3
2.48e2.37 (m, 2H, CHCH and OH); C NMR (75 MHz, CDCl )
(
ppm) relative to the solvent residual peak as the internal reference.
d
147.7, 139.2, 133.9, 133.4, 128.1, 128.0, 124.3, 119.0, 68.3, 42.8. The
11
19
B (128 MHz) and F (376 MHz) NMR spectra were recorded in
DMSO-d . Spectra were calibrated using BF $Et O (0.0 ppm) as
external reference in the case of B NMR and chemical shifts were
3
i
data match with the previously described compound.
6
3
2
11
4
.3.1.7. 1-(4-Methoxyphenyl)but-3-en-1-ol (3g). 1H NMR (300 M
Hz, CDCl
7.28 (d, J¼9.0 Hz, 2H, HAryl), 6.88 (d, J¼9.0 Hz, 2H, HAryl),
), 5.19e5.10 (m, 2H, CH]
), 4.68 (t, J¼6.6 Hz, CHOH), 3.80 (s, 3H, OMe), 2.52e2.47 (m, 2H,
19
3 2
referenced to external CF CO H (0.0 ppm) in the case of F NMR.
3
) d
Coupling constants (J) for all spectra are reported in Hertz (Hz).
High-resolution mass spectral analyses were performed on using
ESI method.
5
CH
CHCH
.79 (ddt, J¼16.8, 9.9, 6.6 Hz, 1H, CH]CH
2
2
13
2 3
), 2.01 (br s, 1H, OH); C NMR (75 MHz, CDCl ) d 158.9, 136.0,
1
34.6, 127.0, 118.2, 113.7, 72.9, 55.2, 43.7. The data match with the
3
i
4
.3. Typical procedure
previously described compound.
4.3.1. General procedure for the allylation of aldehydes (1aeq) with
4.3.1.8. 1-(3-Methoxyphenyl)but-3-en-1-ol (3h). 1H NMR (300 M
potassium allyltrifluoroborate (2) using Amberlyst A-15. To a solu-
tion of the appropriate aldehyde 1aeq (1.0 mmol) in CH Cl (3 mL)
was added potassium allyltrifluoroborate 2 (163 mg, 1.10 mmol)
followed by water (3 mL) and Amberlyst A-15 (100% m/m). The
biphasic mixture was stirred for the time indicated on Table 4 and
Hz, CDCl 7.18 (dd, J¼8.1, 7.8 Hz, 1H, HAryl), 6.86e6.84 (m, 2H,
Aryl), 6.74 (ddd, J¼8.1, 2.7, 1.2 Hz, 1H, HAryl), 5.73 (ddt, J¼17.1, 10.2,
7.5 Hz, 1H, CH]CH ), 5.12e5.04 (m, 2H, CH]CH
), 4.63 (dd, J¼7.5,
5.4 Hz, 1H, CHOH), 3.73 (s, 3H, OMe), 2.46e2.39 (m, 2H, CHCH ),
159.5, 145.6, 134.4,
129.3, 118.2, 118.0, 112.8, 111.2, 73.1, 55.1, 43.6. The data match with
3
) d
2
2
H
2
2
2
1
3
3
1.95 (br s, 1H, OH); C NMR (75 MHz, CDCl ) d
then diluted with CH
aqueous layer was extracted with CH
MgSO . The solvent was removed under reduced pressure to yield
aeq without the need of further purification.
2
Cl
2
(5 mL). The layers were separated and the
3
i
2
Cl
2
(3ꢂ5 mL) and dried over
the previously described compound.
4
3
4.3.1.9. 1-(2-Methoxyphenyl)but-3-en-1-ol (3i). 1H NMR (300 M
Hz, CDCl
7.34 (dd, J¼7.5, 1.8 Hz, 1H, HAryl), 7.25 (td, J¼7.5,
1.8 Hz, 1H, HAryl), 6.96 (td, J¼8.4, 1.2 Hz, 1H, HAryl), 6.88 (d,
J¼8.4 Hz, 1H, HAryl), 5.85 (ddt, J¼17.1, 10.2, 7.5 Hz, 1H, CH]CH ),
5.17e5.09 (m, 2H, CH]CH
), 4.96 (dd, J¼8.1, 5.1 Hz, 1H, CHOH),
3.84 (s, 3H, OMe), 2.64e2.44 (m, 2H, CHCH ), 2.41 (br s, 1H, OH);
156.2, 135.1, 131.7, 128.2, 126.7, 120.6,
3
) d
4
.3.1.1. 1-(Naphthalen-2-yl)but-3-en-1-ol (3a). 1H NMR (300 M
Hz, CDCl 7.84e7.79 (m, 4H, HAryl), 7.48e7.45 (m, 3H, HAryl), 5.82
), 5.20e5.12 (m, 2H, CH]CH ),
.88 (dd, J¼7.2, 5.1 Hz, 1H, CHOH), 2.56e2.61 (m, 2H, CHCH ), 2.08
141.2, 134.3, 133.2, 133.0,
28.1, 127.9, 127.6, 126.0, 125.8, 124.2, 123.9, 118.4, 73.3, 43.6. The
3
)
d
2
(
4
(
ddt, J¼17.1, 10.2, 7.5 Hz,1H, CH]CH
2
2
2
2
2
br s, 1H, OH); 13C NMR (75 MHz, CDCl
)
d
13
3
3
C NMR (75 MHz, CDCl ) d
1
117.4, 110.3, 69.5, 55.1, 41.8. The data match with the previously
11b
3i
data match with the previously described compound.
described compound.

7010
T.R. Couto et al. / Tetrahedron 69 (2013) 7006e7010
4
.3.1.10. 1-(4-Fluorophenyl)but-3-en-1-ol (3j). 1H NMR (300 M
Hz, CDCl
7.28e7.24 (m, 2H, HAryl), 6.96 (t, 2H, J¼8.4 Hz, HAryl),
.79e5.65 (m, 1H, CH]CH ), 5.13e5.06 (m, 2H, CH]CH ), 4.66 (dd,
H, J¼7.2, 5.7 Hz, CHOH), 2.49e2.38 (m, 2H, CHCH ), 1.82 (br s, 1H,
163.1,139.2,133.8,127.1,118.4,114.9,
2.3, 43.6. The data match with the previously described
MeOH:H
317.1494.
2
O) calcd for C20
H
22
O
2
Na [MþNa]þ 317.1517, found
3
) d
5
1
2
2
2
Acknowledgements
13
3
OH); C NMR d (75 MHz, CDCl ) d
7
We gratefully acknowledge CNPq (484778/2011-0), FACEPE
(APQ-1402-1.06/10), CAPES and inct-INAMI for financial support.
The authors are also thankful to CNPq for their fellowships.
11b
compound.
4
.3.1.11. 1-(2-Fluorophenyl)but-3-en-1-ol (3k). 1H NMR (300 M
Hz, CDCl 7.41 (t,1H, J¼7.6 Hz, HAryl), 7.22e7.15 (m,1H, HAryl), 7.09
3
)
d
Supplementary data
(
t, J¼7.6 Hz, 1H, HAryl), 6.99e6.92 (m, 1H, HAryl), 5.83e5.69 (m, 1H,
CH]CH
2
), 5.14e5.07 (m, 2H, CH]CH
), 2.03 (br s, 1H, OH); C NMR
160.9, 134.0, 130.8, 128.8, 127.2, 124.2, 118.7,
2
), 5.00 (dd, 1H, J¼7.6, 4.4 Hz,
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.tet.2013.06.050.
13
CHOH), 2.57e2.37 (m, 2H, CHCH
(75 MHz, CDCl
2
d
3
) d
1
15.3, 67.2, 42.6. The data match with the previously described
References and notes
3p
compound.
1
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Hz, CDCl 7.27e7.19 (m, 4H, HAryl), 5.78e5.64 (m, 1H, CH]
CH ), 5.13e5.05 (m, 2H, CH]CH
), 4.65 (dd, J¼7.5, 5.4 Hz, CHOH),
.49e2.32 (m, 2H, CHCH ), 2.04 (br s, 1H, OH); C NMR (75 MHz,
CDCl 142.2, 133.9, 131.1, 128.5, 127.2, 118.8, 72.5, 43.8. The data
match with the previously described compound.
(b) Denmark, S. E.; Fu, J. Chem. Rev. 2003, 103, 2763e2793.
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4
2
3
)
d
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3
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Jiang, G.; List, B. Adv. Synth. Catal. 2011, 353, 1667e1670; (d) Bhuyan, B. K.; Borah,
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Ji, B.; Wang, L.; Fu, W. Tetrahedron Lett. 2010, 51, 5567e5570; (h) Huang, J.-M.;
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2
2
3
) d
11b
4
.3.1.13. 1-(4-Bromophenyl)but-3-en-1-ol (3m). 1H NMR (300 M
Hz, CDCl
7.41 (d, J¼8.7 Hz, 2H, HAryl), 7.17 (d, J¼8.7 Hz, 2H, HAryl),
.78e5.64 (m, 1H, CH]CH ), 5.13e5.06 (m, 2H, CH]CH ), 4.64 (dd,
J¼7.8, 5.4 Hz, CHOH), 2.49e2.32 (m, 2H, CHCH ), 1.99 (br s, 1H, OH);
142.8, 133.9, 131.4, 127.5, 121.2, 118.9,
2.5, 43.8. The data match with the previously described
3
) d
2
008, 5507e5510; (l) Guimar ~a es, R. L.; Lima, D. J. P.; Barros, M. E. S. B.; Cavalcanti,
L. N.; Hallwass, F.; Navarro, M.; Bieber, L. W.; Malvestiti, I. Molecules 2007, 12,
089e2105; (m) Li, G.-L.; Zhao, G. Org. Lett. 2006, 8, 633e636; (n) Chung, W.;
5
2
2
2
2
13
C NMR (75 MHz, CDCl
3
)
d
Higashiya, S.; Oba, Y.; Welch, J. T. Tetrahedron 2003, 59, 10031e10036; (o) Li, C.-J.;
Zhang, W.-C. J. Am. Chem. Soc. 1998, 120, 9102e9103; (p) Li, C.-J.; Meng, Y.; Yi,
X.-H.; Ma, J.; Chan, T.-H. J. Org. Chem. 1998, 63, 7498e7504; (q) Li, C.-J.; Meng, Y.;
Yi, X.-H.; Ma, J.; Chan, T.-H. J. Org. Chem. 1997, 62, 8632e8633; (r) Marton, D.;
Stivanello, D.; Tagliavini, G. J. Org. Chem.1996, 61, 2731e2737; (s) Petrier, C.; Luche,
J. L. J. Org. Chem.1985, 50, 910e912; (t) Iamamoto, T.; Kusumoto, T.; Tawarayama,
Y.; Sugiura, Y.; Mita, T.; Hatanaka, Y.; Yokoyama, M. J. Org. Chem. 1984, 49,
7
18
compound.
.3.1.14. (E)-1-Phenylhexa-1,5-dien-3-ol (3n). 1H NMR (300 M
Hz, CDCl
7.40e7.21 (m, 5H, HAryl), 6.61 (dd, J¼15.9, 1.2 Hz, 1H,
4
3
) d
3
904e3912; (u) Luche, J. L.; Damiano, J. C. J. Am. Chem. Soc.1980, 102, 7926e7927.
4. (a) Shimizu, H.; Igarashi, T.; Miura, T.; Murakami, M. Angew. Chem., Int. Ed. 2011, 50,
1465e11469;(b)Ramadhar, T. R.; Batey, R. A. Synthesis2011,1321e1346; (c)Massa,
A.; Acocella, M. R.; De Sio, V.; Villano, R.; Scettri, A. Tetrahedron: Asymmetry 2009,
0, 202e204;(d)Ito, S.;Yamaguchi, H.; Kubota, Y.;Asami, M. Tetrahedron Lett. 2009,
PhCH]CH), 6.24 (dd, J¼15.9, 6.3 Hz, 1H, PhCH]CH), 5.86 (ddt,
J¼17.1, 10.2, 6.9 Hz, 1H, CH]CH ), 5.22e5.14 (m, 2H, CH]CH ),
.40e4.33 (m, 1H, CHOH), 2.50e2.33 (m, 2H, CHCH ), 1.78 (br s, 1H,
136.5, 134.0, 131.5, 130.2, 128.5,
1
2
2
4
2
2
13
OH); C NMR (75 MHz, CDCl
3
)
d
50, 2967e2969; (e) Yang, M.-S.; Xu, L.-W.; Qiu, H.-Y.; Lai, G.-Q.; Jiang, J.-X.
Tetrahedron Lett. 2008, 49, 253e256; (f) Yang, M.-S.; Xu, L.-W.; Zhang, F.-B.;
Qiu, H.-Y.; Jiang, J.-X.; Lai, G.-Q. Appl. Organometal. Chem. 2008, 22, 177e180; (g)
Kennedy, J. W. J.; Hall, D. G. Angew. Chem., Int. Ed. 2003, 42, 4732e4739.
. (a) de Souza, R. F. M.; Areias, M. C. C.; Bieber, L. W.; Navarro, M. Green Chem.
2011, 13, 1118e1120.
1
27.6, 126.4, 118.3, 71.6, 41.9. The data match with the previously
3i
described compound.
5
6
4
.3.1.15. Non-1-en-4-ol (3o). 1
5.90e5.77 (m, 1H, CH]CH ), 5.17e5.10 (m, 2H, CH]CH
.69e3.50 (m, 1H, CHOH), 2.35e2.26 (m, 2H, CHCH ), 2.19e2.08 (m,
H, CHOH) 1.67 (br s, 1H, OH), 1.50e1.25 (m, 6H, CH CH CH CH ),
); C NMR (75 MHz, CDCl 134.9,
H
3
NMR (300 MHz, CDCl )
. (a) Preite, M. D.; Jorquera-Geroldi, H. A.; P eꢀ rez-Carvajal, A. Arkivoc 2011, 7,
d
2
2
),
380e388; (b) Dam, J. H.; Fristrup, P.; Madsen, R. J. Org. Chem. 2008, 73,
3
2
0
2
3228e3235; (c) Wada, M.; Fukuma, T.; Morioka, M.; Takahashi, T.; Miyoshi, N.
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3
2
2
2
1
3
.88 (t, J¼6.3 Hz, 6H, CH
3
CH
2
3
) d
8
9
1
18.0, 70.6, 41.9, 36.7, 31.8, 25.3, 22.6, 14.0. The data match with the
11b
previously described compound.
.3.1.16. 1-(Furan-2-yl)but-3-en-1-ol (3p). 1H NMR (300 MHz,
CDCl
7.38 (dd, J¼1.8, 0.9 Hz, 1H, HHet), 6.34 (dd, J¼2.1, 1.8 Hz,
1
0. Reilly, M. K.; Rychnovsky, S. D. Org. Lett. 2010, 12, 4892e4895.
11. (a) Freitas, J. C. R.; Couto, T. R.; Paulino, A. A. S.; Freitas Filho, J. R.; Malvestiti, I.;
Oliveira, R. A.; Menezes, P. H. Tetrahedron 2012, 68, 10611e10620; (b) Barbosa, F.
C. G.; Freitas, J. C. R.; Melo, C. F.; Menezes, P. H.; Oliveira, R. A. Molecules 2012, 17,
4
3
) d
1
2
(
4099e14110; (c) Nowrouzi, F.; Thadani, A. N.; Batey, R. A. Org. Lett. 2009, 11,
631e2634; (d) Matsuoka, H.; Kondo, K. Tetrahedron Lett. 2009, 50, 2320e2321;
e) Batey, R. A.; Thadani, A. N.; Smil, D. V.; Lough, A. J. Synthesis 2000, 990e998;
1
6
6
H, HHet), 6.26 (dd, J¼2.1, 0.9 Hz, 1H, HHet), 5.81 (ddt, J¼17.1, 10.2,
.9 Hz, 1H, CH]CH ), 5.23e5.13 (m, 2H, CH]CH
), 4.76 (dd, J¼6.6,
.3 Hz, 1H, CHOH), 2.66e2.60 (m, 2H, CHCH ), 2.05 (br s, 1H, OH);
155.9; 141.9; 133.6, 118.6, 110.1, 106.1,
6.9, 40.1. The data match with the previously described
2
2
2
(f) Batey, R. A.; Thadani, A. N.; Smil, D. V. Tetrahedron Lett. 1999, 40, 4289e4292.
12. Rauniyar, V.; Hall, D. G. J. Am. Chem. Soc. 2004, 126, 4518e4519.
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1
3
3
C NMR (75 MHz, CDCl ) d
1
1
6
3i
compound.
1
.3.1.17. 1,1 -([1,1 -Biphenyl]-4,4 -diyl)bis(but-3-en-1-ol) (3q). 1H
NMR (300 MHz, CDCl
7.50 (d, J¼7.8 Hz, 4H, HAryl), 7.35 (d,
), 5.15e5.07
), 4.71 (dd, J¼7.5, 5.1 Hz, 2H, CHOH), 2.53e2.40
0
0
0
75, 468e471; (b) Ting, R.; Harwig, C. W.; Lo, J.; Li, Y.; Adam, M. J.; Ruth, T. J.;
Perrin, D. M. J. Org. Chem. 2008, 73, 4662e4670.
7. Surya Prakash, G. K.; Pertusati, F.; Olah, A. G. Synthesis 2011, 292e302.
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Chem. 2009, 74, 7364e7369.
0. Perrin, D. D.; Armarego, W. L. F. Purification of Laboratory Chemicals; Pergamon:
Oxford, United Kingdom.
4
3
) d
1
J¼7.8 Hz, 4H, HAryl), 5.84e5.70 (m, 2H, CH]CH
2
1
(
(
m, 4H, CH]CH
m, 4H, CHCH ), 1.90 (br s, 2H, OH); C NMR (75 MHz, CDCl
143.1, 140.3, 134.6, 127.4, 126.5, 118.8, 73.28, 44.0; HRMS (ESI,
2
13
2
3
)
2
d