SnCl2·2H2O-mediated Barbier-type allylation: A comparative evaluation of the catalytic performance of CuI and Pd(OAc) 2

Article abstract of DOI:10.1016/j.crci.2013.02.012

A systematic investigation has been carried out for the allylation of carbonyl compounds under SnCl₂·2H₂O-mediated Barbier-type conditions, using CuI and Pd(OAc)₂ as catalysts. Ketones, which are not reactive under the influence of CuI, however, could be activated by using Pd(OAc)₂ as a catalyst.

Full text of DOI:10.1016/j.crci.2013.02.012

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CRAS2C-3718; No. of Pages 8
C. R. Chimie xxx (2013) xxx–xxx
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Full paper/Memoire
SnCl2Á2H2O-mediated Barbier-type allylation: A comparative evaluation
of the catalytic performance of CuI and Pd(OAc)2
*
Pabitra Kumar Kalita, Prodeep Phukan
Department of Chemistry, Gauhati University, Gopinath Bordoloi Nagar, Guwahati, 781014 Assam, India
A R T I C L E I N F O
A B S T R A C T
Article history:
A systematic investigation has been carried out for the allylation of carbonyl compounds
under SnCl2Á2H2O-mediated Barbier-type conditions, using CuI and Pd(OAc)2 as catalysts.
Ketones, which are not reactive under the influence of CuI, however, could be activated by
using Pd(OAc)2 as a catalyst.
Received 24 November 2012
Accepted after revision 11 February 2013
Available online xxx
´
ß 2013 Academie des sciences. Published by Elsevier Masson SAS. All rights reserved.
Keywords:
Homoallylation
Barbier
SnCl2Á2H2O
CuI
Pd(OAc)2
1. Introduction
or a reducing salt [14]. Some other methods, such as
ultrasonic irradiation [15], the use of ionic liquids [16] have
Allylation of carbonyl compounds, using allylic metal
reagents, is an important class of carbon–carbon bond-
forming reactions, as it gives rise to synthetically useful
homoallylic alcohols [1]. The homoallylic alcohol products
are often obtained with high stereoselectivity and can
further be manipulated to access synthetically valuable
also been developed to promote this particular reaction.
Nokami et al. first reported the coupling reaction of allyl
bromide with carbonyl compounds in aqueous medium
mediated by tin and aluminum in the presence of an acid,
such as HBr or acetic acid [17]. Gambaro et al. [18] reported
a method for the synthesis of allylbromodichlorotin from
allyl bromide and tin(II) chloride for allylation of acetone in
tetrahydrofuran. However, this method was studied for
acetone only, where the corresponding homoallyl alcohol
was obtained in low yield (30%) after 24 h of reaction under
reflux temperature. In the same year, Mukaiyama et al. [19]
reported that allylation of ketones can be achieved using
allyl iodide at room temperature in 1,2-dimethylimidazole
(DMI) as the solvent. However, this method uses expensive
solvent as well as the allylating agent. Moreover, DMI is
highly toxic. Very recently, Cuerva et al. [20] developed a
new Barbier-type [1c] allylation reaction of carbonyl
compounds, using allylic carboxylates in the presence of
intermediates, such as
b-hydroxy carbonyl compounds.
These compounds can be easily converted into various
building blocks useful for the synthesis of natural-like
products [2]. A number of methods have been developed
for allylation reaction involving various metals, such as
zinc [3], tin [4], indium [5], bismuth [6], manganese [7],
magnesium [8], antimony [9], scandium [10], cobalt [11],
cerium [12], and silver [7b]. Masuyama et al. [13]
developed a new approach for synthesizing homoallyl
alcohol in one-pot via an umpolung of
p-palladium
complexes, using SnCl2 as a reducing reagent. Allylation
of carbonyl compounds from allylic acetate requires the
use of palladium as a catalyst, in addition to another metal
a
Ti/Ni-based multi-metallic catalyst. This procedure
requires high amounts of toxic chlorotrimethylsilane
(TMSCl), Mn dust and 2,4,6-collidine as the activator and
four equivalents of the allylating agent.
*
Corresponding author.
E-mail address: pphukan@yahoo.com (P. Phukan).
1631-0748/$ – see front matter ß 2013 Acade´mie des sciences. Published by Elsevier Masson SAS. All rights reserved.
http://dx.doi.org/10.1016/j.crci.2013.02.012
Please cite this article in press as: Kalita PK, Phukan P. SnCl2Á2H2O-mediated Barbier-type allylation: A comparative
evaluation of the catalytic performance of CuI and Pd(OAc)2. C. R. Chimie (2013), http://dx.doi.org/10.1016/
j.crci.2013.02.012

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OH
R2 = H
R1
10 mol% CuI
O
SnCl2.2H2O
Br
+
R1 R2
DMF/cat/rt
OH
R2
R2 = H, Me, cyclic
3 mol% Pd(OAc)2
R1 = Ph, aryl, aliphatic
R1
Scheme 1.
Copper [21] and palladium [22] compounds have
attracted the attention as catalysts in numerous C–C
bond-forming reactions. To our knowledge, there are only
a very few reports of SnCl2-mediated, one-pot, Barbier-
type allylations using an allyl halide, where Pd(II) [23] or
Pd(0) [24] compounds were used as catalysts. But, in both
cases, either a high amount of the catalyst or long reaction
time is necessary to achieve good yield of homoallyl
alcohols. Guo et al. reported a method for the allylation of
carbonyl compound using copper powder [25]. This
method requires two molar equivalents of copper powder
to accomplish the allylation. As a continuation of our
investigation on various allylation reactions [26], we
present, herein, the results of a systematic study of
Barbier-type allylation of carbonyl compounds under the
influence of SnCl2Á2H2O in the presence of CuI and
Pd(OAc)2 as the catalyst (Scheme 1). While no detailed
investigations on the catalytic activity of both catalysts for
Barbier-type allylation reaction have been reported so far,
such study may be useful in developing an effective
protocol for various homoallylation reactions.
(1 mmol) and CuI (5 mol%) were added to a mixture of
allylbromide (1 mmol) and benzaldehyde (1 mmol) in N,N-
dimethylformamide (DMF) (1 mL) at room temperature.
The reaction was monitored by thin-layer chromatography
(TLC). The results are presented in Table 1.
Initial experiment, without CuI, failed to produce any
product. Another experiment without SnCl2Á2H2O also
produced a negative result after 24 h of reaction at room
temperature. Next, we examined the reaction using
10 mol% of CuI, which could improve the yield up to 60%
after 10 h of reaction (Table 1, entry 4). The reaction with a
larger amount of allyl bromide could not improve the yield
significantly. However, the reaction rate as well as the yield
of the product increased significantly, when the concen-
tration of SnCl2Á2H2O was doubled. In this case, the
reaction produced the corresponding homoallylic alcohol
in 86% yield just after 3 h of reaction. An improvement in
the yield up to 90% was observed when the amount of
allylating agent was increased from 1 to 1.1 equiv (Table 1,
entry 8). Further increase of catalyst concentration upto
15 mol% could not improve the result. The reaction was
also examined using different solvents, such as H2O,
dimethyl sulfoxide (DMSO), toluene, DMF, CH2Cl2, and
CH3CN. While the use of CH3CN and CH2Cl2 produced low
yield, the reaction was found inactive in water, DMSO, and
toluene. However, DMF was found to be the solvent of
choice. Finally, the use of 10 mol% of CuI, 1.1 equiv of allyl
2. Results and discussion
The aim of this study is to evaluate the catalytic
efficiency of CuI and Pd(OAc)2 for Barbier-type allylation of
carbonyl compounds. In a typical reaction, SnCl2Á2H2O
Table 1
Synthesis of homoallylic alcohols from benzaldehydes using CuI as a catalyst.
Entry
Benzaldehyde (mmol)
Solvent
Allylbromide (mmol)
SnCl2Á2H2O (mmol)
Catalyst (mmol)
Time (h)
Yielda (%)
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
DMF
1
1
–
1
1
1
1.5
2
2
2
2
2
2
2
2
2
2
2
–
24
24
10
10
10
10
3
0
0
2
DMF
1
CuI (0.05)
CuI (0.05)
CuI (0.10)
CuI (0.10)
CuI (0.10)
CuI (0.10)
CuI (0.10)
CuI (0.15)
CuI (0.10)
CuI (0.10)
CuI (0.10)
CuI (0.10)
CuI (0.10)
Pd(OAc)2 (0.02)
Pd(OAc)2 (0.03)
Pd(OAc)2 (0.05)
3
DMF
1
50
60
65
72
86
90
90
22
0
4
DMF
1
5
DMF
1.1
1.1
1
6
DMF
7
DMF
8
DMF
1.1
1.1
1.1
1.1
1.1
1.1
1.1
1.1
1.1
1.1
3
9
DMF
3
10
11
12
13
14
15
16
17
CH3CN
H2O
24
24
24
24
24
3
CH2Cl2
Toluene
DMSO
DMF
10
0
0
82
92
91
DMF
1
DMF
0.5
a
Isolated yield after chromatographic purification.
Please cite this article in press as: Kalita PK, Phukan P. SnCl2Á2H2O-mediated Barbier-type allylation: A comparative
evaluation of the catalytic performance of CuI and Pd(OAc)2. C. R. Chimie (2013), http://dx.doi.org/10.1016/
j.crci.2013.02.012

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3
Table 2
SnCl2Á2H2O-mediated and CuI or Pd(OAc)2-catalyzed allylation of aldehydesa.
O
OH
SnCl2.2H2O
Br
+
R
H
R
Cat./DMF/RT
2
1a-q
3a-q
Productb
Entry
1
Carbonyl compound
CHO
Catalyst
Time (h)
Yield (%)c
CuI
3
1
90
92
OH
Pd(OAc)2
3a
2
3
4
CuI
3
92
91
OH
Cl
CHO
Pd(OAc)2
1.5
Cl
3b
Cl OH
CuI
3
92
93
Cl
Pd(OAc)2
1.2
CHO
3c
CuI
3
90
92
OH
CHO
Pd(OAc)2
1.5
Cl
Cl
3d
5
CuI
3
85
88
OH
CHO
Pd(OAc)2
1.5
MeO
MeO
OMe OH
3e
6
7
CuI
3.5
2
80
83
OMe
Pd(OAc)2
CHO
3f
CuI
4
2
78
82
OH
CHO
Pd(OAc)2
Br
Br
3g
8
9
CuI
10
4
65
79
CHO
OH
Pd(OAc)2
O2N
O2N
3h
OH
CuI
9
4
64
74
O
Pd(OAc)2
H
NO2
CHO
NO2
3i
10
11
CuI
2
95
94
OH
Pd(OAc)2
1.2
3j
CuI
7
77
80
OH
CHO
Pd(OAc)2
3.5
F
F
3k
Please cite this article in press as: Kalita PK, Phukan P. SnCl2Á2H2O-mediated Barbier-type allylation: A comparative
evaluation of the catalytic performance of CuI and Pd(OAc)2. C. R. Chimie (2013), http://dx.doi.org/10.1016/
j.crci.2013.02.012

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Table 2 (Continued )
O
OH
SnCl2.2H2O
Br
+
R
H
R
Cat./DMF/RT
2
1a-q
3a-q
Entry
12
Carbonyl compound
Productb
Catalyst
Time (h)
Yield (%)c
CuI
3
82
84
Cl
OH
Cl
Pd(OAc)2
1.5
CHO
Cl
Cl
3l
13
14
CuI
2.5
1.3
87
85
OH
CHO
Pd(OAc)2
3m
CuI
3
83
88
OH
MeO
MeO
CHO
Pd(OAc)2
1.5
MeO
MeO
3n
15
16
CuI
3.5
1.5
78
75
Br OH
Br
Pd(OAc)2
CHO
3o
CuI
5
3
88
82
OH
CHO
Pd(OAc)2
3p
17
18
CuI
5
88
80
OH
CHO
Pd(OAc)2
1.5
3q
CuI
4.5
2
92
85
OH
CHO
Pd(OAc)2
3r
19
CuI
5
88
83
OH
O
H
Pd(OAc)2
2.5
H
3s
a
Reaction condition: aldehydes, 1 mmol; allylbromide, 1.1 mmol; SnCl2Á2H2O, 2 mmol; CuI, 10 mol%; Pd(OAc)2, 3 mol%.
b
c
All products were characterized by IR, 1H-NMR and 13C-NMR.
Isolated yield after chromatographic purification.
bromide and 2 equiv of SnCl2Á2H2O was found to be
excellent yield. Aromatic substrates, bearing –Cl, –Br, –
CH3, –OMe and aliphatic aldehydes reacted very success-
fully, irrespective of the substituent position in the
aromatic ring. The presence of –NO2 and –F groups on
the aromatic ring in both aldehydes and ketones not only
lowers the yield, but also takes long time.
The success of the homoallylation of the aldehydes
encouraged us to extend the reaction to ketones (Table 3).
The initial reaction with acetophenone using CuI as the
catalyst under the same reaction conditions failed to
produce the corresponding homoallyl alcohol. However,
the use of 3 mol% of Pd(OAc)2 could drive the reaction
forward to produce homoallylic alcohols in 85% yield after
3 h of reaction. The reaction was further extended to a
optimum to realize the best yield of the product. Next, we
examined the catalytic efficiency of Pd(OAc)2 under the
same reaction conditions. Initial experiment, using 2 mol%
of Pd(OAc)2 as a catalyst produced 82% of the product in 3 h
of reaction. Thereafter, we studied the reaction using
3 mol% and 5 mol% of the catalyst. Finally, the use of 3 mol%
of Pd(OAc)2 was found to be the optimum in terms of yield
and reaction time.
After finding the optimum conditions, the procedure
was extended to a variety of aldehydes. The results are
summarized in Table 2. In general, this procedure works
well for a variety of aromatic as well as aliphatic aldehydes
to produce the corresponding homoallylic alcohols in
Please cite this article in press as: Kalita PK, Phukan P. SnCl2Á2H2O-mediated Barbier-type allylation: A comparative
evaluation of the catalytic performance of CuI and Pd(OAc)2. C. R. Chimie (2013), http://dx.doi.org/10.1016/
j.crci.2013.02.012

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5
Table 3
SnCl2Á2H2O-mediated and Pd(OAc)2-catalyzed allylation of ketonesa.
O
OH
SnCl2.2H2O
Br
+
R
R
R'
4a-j
Pd(OAc) /DMF/RT
R'
5a-j
2
2
Entry
1
Carbonyl Compound
Productb
Catalyst
Time (h)
Yield (%)c
CuI
12
5
0
OH
O
Pd(OAc)2
85
5a
2
3
4
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
6
5
8
77
81
68
OH OH
OH
O
5b
OH
O
5c
O
OH
F
F
5d
5
6
Pd(OAc)2
Pd(OAc)2
7
8
79
72
HO
O
5e
O
HO
5f
7
8
Pd(OAc)2
Pd(OAc)2
5
7
71
69
O
O
HO
HO
5g
5h
9
Pd(OAc)2
Pd(OAc)2
6
6
75
77
O
OH
5i
10
O
OH
5j
a
Reaction conditions: ketones, 1 mmol; allylbromide, 1.1 mmol; SnCl2Á2H2O, 2 mmol; CuI, 10 mol%; Pd(OAc)2, 3 mol%.
All products were characterized by IR, 1H-NMR and 13C-NMR.
b
c
Isolated yield after chromatographic purification.
Please cite this article in press as: Kalita PK, Phukan P. SnCl2Á2H2O-mediated Barbier-type allylation: A comparative
evaluation of the catalytic performance of CuI and Pd(OAc)2. C. R. Chimie (2013), http://dx.doi.org/10.1016/
j.crci.2013.02.012

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P.K. Kalita, P. Phukan / C. R. Chimie xxx (2013) xxx–xxx
variety of ketones and the results are summarized in Table
3.
5.78–5.65 (m, 1H), 5.14–5.06 (m, 2H), 4.64 (dd,
J1 = 4.83 Hz, J2 = 7.88 Hz, 1H), 2.49–2.33 (m, 2H), 1.91 (s,
1H); 13C-NMR (75 MHz, CDCl3):
d 145.9, 134.3, 133.8,
It can be seen from Table 3 that a variety of ketones
undergo homoallylation in the presence of 3 mol% of
Pd(OAc)2 to give the product in high yield. Literature
search revealed that SnCl2-mediated allylation of ketones,
aliphatic ketones, in particular, needs long reaction times
to achieve good yields [4a,4b,5a,5c,11,13,16,23]. In the
present investigation, the reaction completes in much
shorter time with high yield. However, we observed that 4-
fluoroacetophenone (Table 3, entry 4) and 4-methylcyclo-
hexanone (Table 3, entry 8) produced slightly low yield of
the product.
129.6, 127.6, 126.0, 123.9, 119.0, 72.5, 43.8.
5e
1-(2-Chlorophenyl)but-3-en-1-ol,4b,
(3c). IR (y/
cmÀ1): 3419, 3074, 2927, 1709, 1641, 1574, 1429, 1196;
1H-NMR (300 MHz, CDCl3):
d 7.57 (d, J = 7.18 Hz, 1H), 7.48–
7.15 (m, 3H), 6.02–5.76 (m, 1H), 5.35–5.07 (m, 3H), 2.76–
2.54 (m, 1H), 2.51–2.31 (m, 1H), 2.26 (s, 1H); 13C-NMR
(75 MHz, CDCl3):
118.8, 69.6, 42.0.
d
141.1, 134.3, 131.6, 129.4, 128.4, 127.0,
1-(4-Chlorophenyl)but3-en-1-ol,10,
(3d). IR (y/
5e
cmÀ1): 3374, 3077, 2980, 2908, 1642, 1597, 1490, 1411,
1091; 1H-NMR (300 MHz, CDCl3):
7.47–7.14 (m, 4H),
d
5.87–5.61 (m, 1H), 5.25–4.99 (m, 2H), 4.63 (t, J = 6.42 Hz,
1H), 2.75 (s, 1H), 2.58–2.32 (m, 2H); 13C-NMR (75 MHz,
3. Conclusions
CDCl3):
43.6.
d 142.2, 133.9, 132.9, 128.3, 127.1, 118.4, 72.5,
In summary, a comparative study on the Barbier-type
allylation reactions of aldehyde- and ketone-mediated by
SnCl2Á2H2O, using CuI and Pd(OAc)2 as the catalyst have
been reported. Although both the catalysts are very
effective for aldehydes, CuI failed to catalyse the allylation
reaction of ketones under this particular reaction condi-
tion. In the presence of Pd(OAc)2, allylation of ketones
proceeds smoothly. The best results are obtained when the
reaction was carried out using 1 equiv of carbonyl
compound, 1.1 equiv of allyl bromide and 2 equiv of
SnCl2Á2H2O in DMF at room temperature.
1-(4-Methoxyphenyl)but-3-en-1-ol,5e (3e). IR
(y/
cmÀ1): 3398, 3072, 2932, 1886, 1611, 1512, 1456, 1247,
1036; 1H-NMR (300 MHz, CDCl3):
7.20 (d, J = 8.69 Hz, 2H),
6.82 (d, J = 8.69 Hz, 2H), 5.81–5.65 (m, 1H), 5.12–5.00 (m,
2H), 4.56 (t, J = 6.42 Hz, 1H), 3.72 (s, 3H), 3.41 (s, 1H), 2.53–
2.34 (m, 2H); 13C-NMR (75 MHz, CDCl3):
134.6, 127.0, 117.4, 113.4, 72.9, 54.9, 43.4.
1-(2-Methoxyphenyl)but-3-en-1-ol,8b (3f). IR
cmÀ1): 3412, 3072, 2938, 2837, 1640, 1596, 1462, 1240,
1045; 1H-NMR (300 MHz, CDCl3):
7.37 (d, J = 7.55 Hz, 1H),
d
d 158.6, 136.1,
(y/
d
7.31–7.21 (m, 1H), 6.98 (t, J = 7.18 Hz, 1H), 5.97–5.78 (m,
1H), 5.20–5.07 (m, 2H), 5.05–4.94 (m, 1H), 3.83 (s, 3H),
2.98 (s, 1H), 2.66–2.44 (m, 2H); 13C-NMR (75 MHz, CDCl3):
4. Experimental
4.1. General
d 156.1, 135.1, 131.7, 128.1, 126.6, 120.5, 117.2, 110.2,
69.2, 55.0, 41.7.
All the chemicals used are of analytical grade. IR spectra
were recorded by using a Perkin Elmer Spectrum RX I FT-IR
spectrometer. 1H and 13C-NMR spectra were obtained in
CDCl3 using Bruker 300 MHz instrument.
1-(4-Bromophenyl)but-3-en-1-ol,5e (3g). IR ( /cmÀ1):
y
3376, 3076, 2926, 2906, 1642, 1486, 1405, 1062, 1005; 1H-
NMR (300 MHz, CDCl3):
d 7.42 (d, J = 8.31 Hz, 2H), 7.14 (d,
J = 8.31 Hz, 2H), 5.81–5.61 (m, 1H), 5.21–5.01 (m, 2H), 4.58
(t, J = 6.04 Hz, 1H), 3.18 (s, 1H), 2.40 (t, J = 6.80 Hz, 2H); 13C-
4.2. Synthetic procedures
NMR (75 MHz, CDCl3):
d
142.7, 133.8, 131.2, 127.5, 121.0,
118.4, 72.5, 43.4.
To a solution of carbonyl compound (1 mmol) and
allylbromide (1.1 mmol) in DMF (1 ml), SnCl2Á2H2O
(2 mmol) and the catalyst, (CuI, 10 mol% or Pd(OAc)2, 3
mol%) were added successively at room temperature. After
stirring the reaction medium for an appropriate time (TLC)
at room temperature, water (10 mL) was added and the
reaction mixture was extracted with diethylether
(3 Â 10 mL). The combined organic extract was dried over
sodium sulphate, filtered and concentrated. The crude
product was purified by flash column chromatography
over silica gel (230–400 mesh) using ethylacetate-petro-
leum ether (5:95) as the eluent.
1-(4-Nitrophenyl)but-3-en-1-ol,5e (3h). IR ( /cmÀ1):
y
3551, 3389, 3055, 2931, 1631, 1523, 1429, 1169, 1048; 1H-
NMR (300 MHz, CDCl3): 8.13 (d, J = 8.65 Hz, 2H), 7.46 (d,
d
J = 8.39 Hz, 2H), 5.80–5.62 (m, 1H), 5.19–5.05 (m, 2H),
4.84–4.74 (m, 1H), 2.53–2.33 (m, 2H), 2.11 (s, 1H); 13C-
NMR (75 MHz, CDCl3):
120.1, 72.5, 44.3.
d
151.5, 147.6, 133.6, 126.9, 124.0,
1-(2-Nitrophenyl)but-3-en-1-ol,11 (3i). IR (
y
/cmÀ1):
3554, 3382, 3053, 2939, 1624, 1540, 1430, 1173, 1043; 1H-
NMR (300 MHz, CDCl3): 7.95 (d, J = 8.31 Hz, 1H), 7.84 (d,
d
J = 7.55 Hz, 1H), 7.66 (t, J = 7.18 Hz, 1H), 7.44 (t, J = 7.18 Hz,
1H), 6.04–5.80 (m, 1H), 5.42–5.13 (m, 3H), 2.58–2.27 (m,
1-Phenyl-but-3-en-1-ol,4b (3a). IR (
3073, 2907, 1641, 1493, 1445, 1043; 1H-NMR (300 MHz,
CDCl3): 7.43–7.23 (m, 5H), 5.91–5.72 (m, 1H), 5.24–5.11
y
/cmÀ1): 3372,
2H), 1.62 (s, 1H); 13C-NMR (75 MHz, CDCl3):
d
150.1, 139.0,
133.8, 133.3, 128.0, 127.9, 124.3, 119.0, 68.2, 42.7.
23
d
1-(4-Methylphenyl)but-3-en-1-ol,4b,
cmÀ1): 3542, 3381, 3062, 2938, 1633, 1519, 1436, 1164,
1051; 1H-NMR (300 MHz, CDCl3):
7.26 (d, J = 7.93 Hz, 2H),
(3j). IR (y/
(m, 2H), 4.80–4.70 (m, 1H), 2.60–2.45 (m, 2H), 2.00 (s, 1H);
13C-NMR (75 MHz, CDCl3):
125.8, 118.5, 73.3, 43.8.
d
143.8, 134.4, 128.4, 127.5,
d
7.19 (d, J = 7.93 Hz, 2H), 5.92–5.71 (m, 1H), 5.27–5.07 (m,
2H), 4.67 (t, J = 6.42 Hz, 1H), 2.84 (s, 1H), 2.58–2.47 (m, 2H),
2.40 (s, 3H); 13C-NMR (75 MHz, CDCl3):
d 140.9, 136.9,
1-(3-Chlorophenyl)but-3-en-1-ol,5e (3b). IR (
y
/cmÀ1):
3377, 3075, 2927, 1709, 1641, 1574, 1429, 1196; 1H-NMR
(300 MHz, CDCl3): 7.31–7.28 (m, 1H), 7.24–7.12 (m, 3H),
d
134.6, 128.9, 125.7, 117.8, 73.1, 43.5, 20.9.
Please cite this article in press as: Kalita PK, Phukan P. SnCl2Á2H2O-mediated Barbier-type allylation: A comparative
evaluation of the catalytic performance of CuI and Pd(OAc)2. C. R. Chimie (2013), http://dx.doi.org/10.1016/
j.crci.2013.02.012

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P.K. Kalita, P. Phukan / C. R. Chimie xxx (2013) xxx–xxx
7
1-(4-Fluorophenyl)but-3-en-1-ol,5e (3k). IR (
3359, 3078, 2944, 2858,1845, 1640, 1487, 1370; 1H-NMR
(300 MHz, CDCl3): 7.40–7.17 (m, 2H), 7.13–6.92 (m,
2H), 5.89–5.60 (m, 1H), 5.26–4.99 (m, 2H), 4.74–4.52 (m,
1H), 3.22 (s, 1H), 2.58–2.31 (m, 2H); 13C-NMR (75 MHz,
y
/cmÀ1):
1.90 (s, 1H); 13C-NMR (75 MHz, CDCl3): 136.6, 134.0, 131.5,
130.4, 128.6, 127.7, 126.5, 118.6, 71.7, 42.0.
d
1-phenyl-1-methylbut-3-en-1-ol,5a (5a). IR ( /cmÀ1):
y
3440, 3069, 2977, 1641, 1444, 1371, 1068; 1H-NMR
(300 MHz, CDCl3): 7.47–7.23 (m, 5H), 5.72–5.62 (m,
d
CDCl3):
43.5.
d
160.2, 139.5, 134.0, 127.3, 118.0, 114.8, 72.6,
1H), 5.18–5.12 (m, 2H), 2.71 (dd, J1 = 13.6 Hz, J2 = 6.42 Hz,
1H), 2.55–2.48 (m, 1H), 1.57 (s, 3H, CH3); 13C-NMR
1-(2,4-Dichlorophenyl)but-3-en-1-ol,5e, 8b (3l). IR (
y
/
(75 MHz, CDCl3):
d 147.5, 133.5, 128.0, 126.6, 125.0,
cmÀ1): 3278, 3080, 2938, 1639,1470,1071, 1045; 1H-NMR
(300 MHz, CDCl3): 7.42 (d, J = 8.69 Hz, 1H), 7.37–7.17 (m,
2H), 5.93–5.68 (m, 1H), 5.32–4.94 (m, 3H), 2.91 (s, 1H),
2.66–2.44 (m, 1H), 2.41–2.19 (m, 1H); 13C-NMR (75 MHz,
119.3, 73.5, 48.3, 29.7.
d
1-(o-Hydroxyphenyl)-1-methylbut-3-en-ol,5a (5b). IR
(
y
/cmÀ1): 3439, 3072, 2975, 1645, 1441, 1377, 1071; 1H-
NMR (300 MHz, CDCl3):
d 9.26 (s, 1H), 7.19–6.81 (m, 4H),
CDCl3):
118.7, 68.9, 41.7.
d
139.6, 133.6, 133.2, 131.9, 128.8, 127.8, 127.1,
5.83–5.75 (m, 1H), 5.22–5.17 (m, 2H), 2.84–2.77 (m, 1H,),
2.59–2.52 (m, 1H,), 1.63 (s, 3H, CH3); 13C-NMR (75 MHz,
CDCl3): d 155.7, 132.9, 129.3, 128.8, 125.9, 120.3, 119.5,
1-(4-Ethylphenyl)but-3-en-1-ol,5f (3m). IR (
y
/cmÀ1):
3544, 3389, 3067, 2931, 1638, 1519, 1432, 1161, 1055; 1H-
117.5, 76.6, 46.5, 28.3.
5c
NMR (300 MHz, CDCl3):
d
7.30 (d, J = 7.93 Hz, 1H), 7.23 (d,
1-(p-Methylphenyl)-1-methylbut-3-en-1-ol,5a,
J = 7.93 Hz, 1H) 5.95–5.73 (m, 1H), 5.28–5.09 (m, 2H), 4.68
(t, J = 6.42 Hz, 1H), 3.03 (s, 1H), 2.72 (q, J = 7.5 Hz, 2H), 2.53
(t, J = 6.8 Hz, 2H), 1.42- 1.27 (m, 3H); 13C-NMR (75 MHz,
(5c). IR (
1062; 1H-NMR (300 MHz, CDCl3):
y
/cmÀ1): 3441, 3064, 2977, 1641, 1444, 1373,
d
7.37 (d, J = 7.93 Hz,
2H), 7.19 (d, J = 7.55 Hz, 2H), 5.71–5.62 (m, 1H), 5.19–5.13
(m, 2H), 2.71 (dd, J1 = 13.6 Hz, J2 = 6.42 Hz, 1H), 2.52 (dd,
J1 = 13.6 Hz, J2 = 8.31 Hz, 1H,), 2.38 (s, 3H, CH3), 1.56 (s, 3H,
CH3); 13C-NMR (75 MHz, CDCl3):
d 144.7, 136.2, 133.9,
CDCl3):
43.4, 28.3, 15.4.
d 143.1, 141.0, 134.5, 127.6, 125.7, 117.5, 73.1,
1-(3,4-Dimethoxyphenyl)but-3-en-1-ol,7b (3n). IR (
y
/
cmÀ1): 3545, 3381, 3069, 2937, 1620, 1509, 1433, 1182,
128.9, 124.8, 119.4, 73.6, 48.5, 29.9, 21.0.
1055; 1H-NMR (300 MHz, CDCl3):
d
6.92–6.69 (m, 3H),
1-(p-Fluorophenyl)-1-methylbut-3-en-ol,5a (5d). IR
5.84–5.63 (m, 1H), 5.17–4.97 (m, 2H), 4.67–4.51 (m, 1 H),
3.82 (s, 3H), 3.80 (s, 3H), 2.57 (s, 1H), 2.48–2.39 (m, 2H);
13C-NMR (75 MHz, CDCl3):
(y
/cmÀ1): 3445, 3062, 2971, 1639, 1440, 1372, 1062;
1H-NMR (300 MHz, CDCl3):
d 7.43–7.38 (m, 2H, ArH), 7.12–
d
148.6, 148.0, 136.4, 134.4,
6.99 (m, 2H, ArH), 5.66–5.57 (m, 1H), 5.16–5.11 (m, 2H),
117.8, 110.6, 108.7, 73.0, 55.6, 43.5.
2.66 (dd, J1 = 13.6 Hz, J2 = 6.42 Hz, 1H), 2.52–2.45 (m, 1H),
8b
1-(2-Bromophenyl)but-3-en-1-ol,5e,
(3o). IR (
y
/
1.54 (s, 3H, CH3); 13C-NMR (75 MHz, CDCl3):
d
163.2, 159.9,
143.3, 133.3, 126.4, 119.7, 114.6, 73.3, 48.4, 29.9.
1-Cyclohexylbut-3-en-1-ol,10, 5a, 5c (5e). IR (
3362, 3067, 2926, 2856,1828, 1640, 1452, 1376; 1H-NMR
(300 MHz, CDCl3): 5.95–5.81 (m, 1H), 5.16–5.13 (m, 2H),
2.23–2.20 (m,2H), 1.70–1.38 (m, 10H); 13C-NMR (75 MHz,
CDCl3): 138.8, 133.7, 122.7, 118.7, 70.9, 46.6, 37.3, 29.7,
25.5, 22.1.
1-Cycloheptylbut-3-en-1-ol,5a (5f). IR (
3068, 2936, 1621, 1505, 1185, 1056; 1H-NMR (300 MHz,
cmÀ1): 3297, 3070, 2933, 1640, 1498, 1465, 1433, 1065;
1H-NMR (300 MHz, CDCl3):
d
7.62–7.44 (m, 2H), 7.31 (t,
y
/cmÀ1):
J = 7.2 Hz, 1H), 7.22–7.04 (m, 1H), 6.00–5.70 (m, 1H), 5.31–
4.94 (m, 3H), 2.99 (s, 1H), 2.67–2.51(m, 1H), 2.43–2.27 (m,
d
1H); 13C-NMR (75 MHz, CDCl3):
d 142.6, 134.1, 132.4,
128.6, 127.4, 127.2, 121.6, 118.2, 71.7, 41.8.
d
1-(Naphthalen-2-yl)but-3-en-1-ol,26f,
(3p). IR (y/
12
cmÀ1): 3547, 3382, 3069, 2932, 1639, 1511, 1431, 1161,
y
/cmÀ1): 3550,
1056; 1H-NMR (300 MHz, CDCl3):
d 8.21–7.71 (m, 4H),
7.40–6.72 (m, 3H), 6.03–5.71 (m, 1H), 5.34–5.06 (m, 2H),
CDCl3) d 5.94–5.80 (m, 1H), 5.13–5.05 (m, 2H), 2.21–2.19
5.00–4.76 (m, 1H), 3.13 (s, 1H), 2.63 (t, J = 6.42 Hz, 2H); 13C-
(m, 2H), 1.65–1.54 (m, 12H); 13C-NMR (75 MHz, CDCl3)
134.0, 118.5, 74.8, 47.7, 41.4, 30.3, 22.2.
d
NMR (75 MHz, CDCl3):
127.5, 125.9, 125.6, 124.4, 117.9, 73.2, 43.3.
Undec-1-en-4-ol,11 (3q). IR ( /cmÀ1): 3363, 3074,
2927, 2857, 1828, 1641, 1458, 1377; 1H-NMR (300 MHz,
CDCl3): 5.96–5.66 (m, 1H), 5.24–5.03 (m, 2H), 3.96–3.73
(m, 1H), 3.17(s, 1H, OH), 2.41–2.14 (m, 2H), 1.55–1.09 (m,
15 H); 13C-NMR (75 MHz, CDCl3):
134.9, 117.8, 45.9, 31.6,
31.5, 30.9, 29.8, 29.4, 29.1, 26.1, 22.5, 21.2, 13.9.
1-Phenylhex-5-en-3-ol,10 (3r). IR /cmÀ1): 3367,
3064, 2931, 1632, 1517, 1432, 1162, 1051; 1H-NMR
(300 MHz, CDCl3): 7.51–7.12 (m, 5H), 6.00–5.76 (m,
d 141.1, 134.2, 132.9, 127.9, 127.8,
1-Cyclopentylbut-3-en-1-ol,5a (5g). IR ( /cmÀ1): 3360,
y
y
3072, 2919, 2845, 1826, 1640, 1457, 1376; 1H-NMR
(300 MHz, CDCl3): 5.94–5.85 (m, 1H), 5.16–5.12 (m,
2H), 2.35–2.32 (m,2H), 1.80–1.61 (m, 8H); 13C-NMR
(75 MHz, CDCl3): 134.6, 118.6, 81.3, 45.8, 38.4, 23.8.
1-(4-Methylcyclohexyl)but-3-en-1-ol,16, 5e (5h). IR (
cmÀ1): 3381, 3065, 2942, 1621, 1510, 1432, 1181, 1056;
1H-NMR (300 MHz, CDCl3):
5.14–5.07 (m, 2H), 2.37–2.34
(m, 2H), 1.38–1.25 (m, 12H); 13C-NMR (75 MHz, CDCl3):
d
d
d
d
y/
(
y
d
d
d
133.7, 118.6, 70.2, 48.4, 40.8, 34.7, 32.2, 31.1, 30.2, 22.3,
20.1.
1H), 5.33–5.08 (m, 2H), 3.87–3.64 (m, 1H), 2.99–2.61 (m,
2H), 2.55–2.16 (m, 3H), 2.01–1.71 (m, 2H); 13C-NMR
4-Methyl-hept-1-en-4-ol,5a, 16 (5i). IR ( /cmÀ1): 3542,
y
(75 MHz, CDCl3):
d
141.9, 134.5, 128.3, 128.2, 125.6, 117.9,
3067, 2932, 1508, 1183, 1056; 1H-NMR (300 MHz, CDCl3):
69.8, 41.8, 38.2, 31.8.
d 5.87–5.78 (m, 1H), 5.10–5.04 (m, 2H), 2.18 (d, J = 7.18 Hz,
1-Phenyl-hexa-1,5-dien-3-ol,26f (3s). IR
(
y
/cmÀ1):
2H), 1.41–0.91 (m, 10H); 13C-NMR (75 MHz, CDCl3):
134.2, 118.4, 72.2, 46.3, 44.1, 26.6, 17.2, 17.1.
d
3542, 3381, 3072, 2930, 1638, 1520, 1431, 1156; 1H-
NMR (300 MHz, CDCl3)
J = 15.86 Hz, 1H), 6.25 (dd, J1 = 6.42 Hz, J2 = 15.86 Hz, 1H),
6.00–5.75 (m, 1H), 5.33–5.06 (m, 2H), 2.59–2.28 (m, 2H),
d
: 7.62–7.14 (m, 5H), 6.62 (d,
4-Methyl-oct-1-en-4-ol,5d (5j). IR /cmÀ1): 3542,
(y
3072, 2940, 1620, 1510, 1431; 1H-NMR (300 MHz, CDCl3):
5.84–5.73 (m, 1H), 5.03–4.97 (m, 2H), 2.33 (t, J = 7.18 Hz,
d
Please cite this article in press as: Kalita PK, Phukan P. SnCl2Á2H2O-mediated Barbier-type allylation: A comparative
evaluation of the catalytic performance of CuI and Pd(OAc)2. C. R. Chimie (2013), http://dx.doi.org/10.1016/
j.crci.2013.02.012

G Model
CRAS2C-3718; No. of Pages 8
8
P.K. Kalita, P. Phukan / C. R. Chimie xxx (2013) xxx–xxx
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Acknowledgements
Financial support from DST (Grant No. SR/S1/OC-43/
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Please cite this article in press as: Kalita PK, Phukan P. SnCl2Á2H2O-mediated Barbier-type allylation: A comparative
evaluation of the catalytic performance of CuI and Pd(OAc)2. C. R. Chimie (2013), http://dx.doi.org/10.1016/
j.crci.2013.02.012