An easy access to styrenes: Trans aryl 1,3-, 1,4- and 1,5-dienes, and 1,3,5-trienes by Hiyama cross-coupling catalyzed by palladium nanoparticles

Article abstract of DOI:10.1039/c0nj01019g

A convenient and efficient procedure has been developed for the vinylation of aryl-, styrenyl-, cinnamyl- and dienyl-halides by a Pd(0) nanoparticle-catalyzed Hiyama cross-coupling to provide the corresponding dienes and trienes in high yields. The reaction does not require any ligand or co-catalyst, and is carried out using PdCl₂ and tetrabutyl ammonium fluoride (TBAF) in THF. Pd nanoparticles are generated in situ and are the active catalytic species in this reaction. A wide range of functionalized styrenes, trans aryl 1,3-, 1,4- and 1,5- dienes, 1,2-, 1-3 and 1,4-bis(1,3-dienes), and 1,3,5-trienes can be obtained by this procedure. The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2011.

Full text of DOI:10.1039/c0nj01019g

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PAPER
An easy access to styrenes: trans aryl 1,3-, 1,4- and 1,5-dienes, and
1,3,5-trienes by Hiyama cross-coupling catalyzed by palladium
nanoparticlesw
Tanmay Chatterjee, Raju Dey and Brindaban C. Ranu*
Received (in Montpellier, France) 24th December 2010, Accepted 21st February 2011
DOI: 10.1039/c0nj01019g
A convenient and efficient procedure has been developed for the vinylation of aryl-, styrenyl-,
cinnamyl- and dienyl-halides by a Pd(0) nanoparticle-catalyzed Hiyama cross-coupling to provide
the corresponding dienes and trienes in high yields. The reaction does not require any ligand or
co-catalyst, and is carried out using PdCl2 and tetrabutyl ammonium fluoride (TBAF) in THF.
Pd nanoparticles are generated in situ and are the active catalytic species in this reaction.
A wide range of functionalized styrenes, trans aryl 1,3-, 1,4- and 1,5- dienes, 1,2-, 1-3 and
1,4-bis(1,3-dienes), and 1,3,5-trienes can be obtained by this procedure.
volume ratio of nanoparticles provides larger number of active
Introduction
sites per unit area compared to their heterogeneous counter-
parts. As part of our continuing program8 to explore catalysis
Styrenes, dienes, trienes and polyenes are useful intermediates
in organic synthesis.1 They are also present as sub-units
by metal nanoparticles for the synthesis of useful molecules,
in a wide range of biologically active compounds, including
we report a convenient procedure for the synthesis of styrenes,
terpenoids, pheromones and polyketides.2 Moreover, functio-
aryl 1,3-, 1,4- and 1,5-dienes, and 1,3,5-trienes by the Hiyama
nalized 1,3-dienes are of much importance in the cycloaddition
coupling of appropriate aryl halides and triethoxyvinylsilane
reactions that have been widely used in the construction of
under the catalysis of Pd(0) nanoparticles (Scheme 1).
complex frameworks.3
Several methods have been reported for the synthesis of
Results and discussion
these compounds. The Wittig olefination of a carbonyl com-
pound is one of the commonly used methods for the synthesis
of dienes.4 However, the Wittig reaction entails an enormous
amount of triphenyl phosphonium waste and, in addition, the
purification of the product is often tedious. Besides, the
stereoselectivity of formation of the product is usually not
very good. Subsequently, various modified procedures using
alkyl-substituted phosphines have been developed to provide a
higher stereoselectivity.5
To determine the optimum reaction conditions for an efficient
coupling, a representative reaction of 4-methoxyphenyl iodide
and triethoxyvinylsilane was studied by the variation of the
reaction parameters such as solvent, temperature and additive.
The results are summarized in Table 1. It was found that the
reaction proceeded best in THF using PdCl2 and tetrabutyl-
ammonium fluoride (TBAF) at 65 1C. The amount of PdCl2
was optimized to 2 mol%. Nevertheless, Pd nanoparticles were
formed in situ in the reaction mixture by the reduction of PdCl2
with vinylsilane.9 TBAF activated the vinylsilane towards
coupling and also acted as a stabilizer for the Pd nanoparticles.10
Interestingly, in other solvents, such as water, N,N-dimethyl-
formamide (DMF) and N-methylpyrrolidone (NMP), the
reaction did not proceed at all under similar reaction condi-
tions. In toluene, the progress of the reaction was marginal. The
replacement of TBAF with NaOH6k did not initiate this
reaction under these experimental conditions at 65 1C. No
reaction occurred in the absence of PdCl2 or TBAF. Thus, in
a typical experimental procedure, a mixture of aryl (phenyl/
styryl/cinnamyl) halide and triethoxyvinylsilane in THF was
stirred at 65 1C in the presence of PdCl2 and TBAF for the
required period of time (TLC). A standard work-up and
purification by column chromatography provided the product.
A variety of metal-catalyzed cross-coupling reactions involving
Suzuki, Hiyama, Stille and Negishi protocols have also been
used for the synthesis of dienes and trienes.6 Among these, the
Hiyama reaction, involving aryl halides and organosilanes, is a
better alternative because of the ease of preparation and low
toxicity of organosilane reagents.6c,e,k,l
The use of metal nanoparticles as efficient catalysts in
organic reactions has attracted considerable interest in the
context of green chemistry because of their benign character
and ease of preparation.7 In addition, the high surface to
Department of Organic Chemistry, Indian Association for the
Cultivation of Science, Jadavpur, Kolkata-700 032, India.
E-mail: ocbcr@iacs.res.in; Fax: +91 3324732805
w Electronic supplementary information (ESI) available. See DOI:
10.1039/c0nj01019g
c
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stereoselectivity. Phenyl-1,3-butenyl bromide upon vinylation
furnished the corresponding 1,3,5-triene. Thus, this protocol
is of potential for use in the synthesis of polyenes by appro-
priate manipulation. Another elegant application of this
protocol lies in an easy access to phenyl 1,2-, 1,3- and 1,4-
bis-(1,3)-dienes (Table 4), which are of much potential in
organic synthesis.11
Scheme 1 Cross-coupling of aryl halides with vinylsiloxanes.
To find the active catalytic species in the reaction, an extract
from the reaction mixture of 4-methoxyphenyl iodide and
triethoxyvinylsilane in presence of PdCl2 and TBAF after
4 h showed the presence of nanoparticles (2–3 nm) in a
TEM (transmission electron microscope) image (Fig. 1). The
identity of the nanoparticles as being of palladium was estab-
lished by EDX (energy dispersive X-ray) spectroscopy (Fig. 2).
These Pd(0) nanoparticles undergo oxidative addition with
aryl halides to form Pd(II) species during the progress of the
reaction.
Following the same procedure, aryl 1,4- and 1,5-dienes were
obtained by the reaction of cinnamyl bromides with vinyl-
siloxane (Table 5) and cinnamyl bromides with allyltrimethyl-
silane (Table 6), respectively.
The reactions are, in general, clean and high yielding.
The compatibility of base-sensitive functionalities such as
carboxylic ester, amide, anilide, etc. in this procedure is an
advantage over those using NaOH in Hiyama vinylation
reactions.6k This reaction does not require any phosphorus
or nitrogen ligands, unlike several other procedures using
these.6f,h,i The use of TBAF is vital as it stabilizes the Pd
nanoparticles, involving the tetrabutylammonium cations, and
also activates the siloxane. Our attempts to recycle the Pd
nanoparticles were not very successful as after the first cycle
the nanoparticles grew bigger (10–15 nm), leading to lower
yields and being less efficient.
Several substituted phenyl iodides and bromides underwent
vinylation by triethoxyvinylsilane in this procedure to produce
the corresponding styrenes. The results are reported in
Table 2. A variety of electron-withdrawing and -donating
substituents, such as NO2, COMe, CO2Et, CN, CHO,
CONHPh, OCH3 and Br, were compatible with this reaction.
The heteroaryl iodides 3-pyridyl iodide, (Table 2, entry 9) and
5-acetyl-2-thiophenyl bromide (Table 2, entry 16) also parti-
cipated in this reaction. Aryl iodides are more reactive than
aryl bromides and thus a selective reaction with the iodo group
occurred in the presence of a bromo group (Table 2, entry 4).
This chemoselectivity of the iodo over the bromo functionality
has been utilised for the synthesis of a variety of useful
functionalized arenes and biaryls involving Heck, Suzuki
and Hiyama couplings, as illustrated in Scheme 2.
To gain a better understanding of the catalytic cycle, a
representative reaction of iodobenzene and triethoxyvinyl-
silane was studied by UV (THF) spectroscopy. A solution of
PdCl2 in THF showed an absorbance at 348 nm. UV spectra
of the reaction mixture after 1 min, 30 min, 1 h, 2 h, 2.5 h, 3 h
and 8 h showed the absence of the corresponding peak for
PdCl2 at 348 nm, and a new peak at 365 nm appeared after
30 min, becoming maximum after 2.5 h (Fig. 3). This peak
remained even after 3 h but completely disappeared after 8 h.
The new peak at 365 nm was possibly due to aryl Pd(II)
intermediate species formed during the progress of the reac-
tion, and this peak disappeared after reductive elimination
upon completion of the reaction, indicating the formation of
Pd(0). It is thus suggested that Pd(II) was reduced by triethoxy-
vinylsilane to Pd(0), which then catalyzes the reaction.
It is proposed that the reaction proceeds via the pathway
outlined in Scheme 3. As Pd(0) nanoparticles are the active
A series of substituted phenyl vinyl bromides underwent
coupling with triethoxyvinylsilane via this procedure to
provide the corresponding aryl 1,3-dienes. The results are
reported in Table 3. Interestingly, both cis- and trans-vinyl
bromides produced trans-1,3-dienes only. The stereochemistry
was determined by the coupling constants in the 1H NMR
spectroscopic data of the corresponding compound in
comparison to reported values for an authentic compound
(see the references in Table 3).
The electron-withdrawing and electron-donating behavior
of the substituents on the aromatic ring did not influence the
Table 1 Standardization of the Hiyama cross-coupling reaction
Entry
Additiveb
Pd salt
Solvent
Temp./1C
Time/h
Yield (%)a
1
2
3
4
5
6
7
8
TBAF
TBAF
NaOH
NaOH
TBAF
TBAF
TBAF
TBAF
K2CO3
TBAF
TBAF
PdCl2
PdCl2
PdCl2
Pd(OAc)2
Pd(OAc)2
PdCl2
Toluene
H2O
H2O
110
100
100
100
65
65
65
65
65
12
12
12
12
12
12
9
12
12
12
12
20
—
8
H2O
12
70
78
78
68
—
—
—
THF
THF
THF
THF
THF
DMF
NMP
PdCl2
Pd(NO3)2ÁxH2O
9
10
11
PdCl2
PdCl2
PdCl2
100
100
a
A mixture of 4-methoxyiodobenzene (1 mmol), triethoxyvinylsilane (1.2 mmol), Pd catalyst (2 mol%) and additive (1.2 mmol) in solvent (3 mL)
b
were heated for the required time. 2.5 mmol of NaOH and K2CO3.
c
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Table 2 The Pd nanoparticle-catalyzed Hiyama cross-coupling of
aryl halides with triethoxyvinylsilanea
Entry
R
Time/h
Yield (%)b
Ref.
1
2
3
4
5
6
7
8
H
3-NO2
3-COMe
4-Br
4-OMe
2-COOEt
4-CONHPh
4-NHCOPh
8
7
7
8
9
8
8
9
77
82
78
80
78
77
80
68
6h
6h
6f
6b
6f
6n
9
8
71
6f
6l
Fig. 1 A TEM image of the Pd nanoparticles.
10
9
72
11
12
13
14
15
4-CHO
4-COOEt
4-COMe
4-CN
7
8
8
7
8
80
76
73
88
90
6f
6n
6f
6f
6f
4-NO2
16
8
9
65
67
6f
6f
17
a
b
Entries 1–10, X = 1; entries 11–17, X = Br. A mixture of iodo and
bromo arene (1 mmol), triethoxyvinylsilane (228 mg, 1.2 mmol), PdCl2
(4 mg, 1.2 mol%) and TBAF (1 M solution in THF; 1.2 mL, 1.2 mmol)
in THF (3 mL) was heated under reflux (65 1C) for the required time.
Yields refer to those of purified products characterized by spectro-
scopic data.
reaction of a cis vinyl bromide with PdCl2 and a drop of
vinylsiloxane to accelerate the formation of Pd(0) nano-
particle, no isomerization was observed after 8 h. This experi-
ment using pre-formed Pd nanoparticles21 also lead to no
isomerization. Thus path b is not considered. It should be
noted that the formation of a trans coupled product from cis
allyl acetate through isomerization during the reaction process
is well known.6e,24
Fig. 2 An EDX spectrum of the Pd nanoparticles on a Cu grid.
catalytic species, a cycle involving Pd(0) to Pd(II) is most likely.
The oxidative addition of the aryl halide to Pd(0) generates
arylpalladium complex 1, which undergoes transmetalation by
the vinylsiloxane in the presence of TBAF to produce inter-
mediate 2, which on reductive elimination provides the
product with the regeneration of Pd(0). This process operates
straightaway in case of aryl iodides, bromides and trans vinyl
bromides. However, for cis vinyl bromides, two alternative
routes may be considered. In path a, complex 1 may isomerize
to its trans isomer via 1a and 1b, which then couples with the
vinylsiloxane to form the same intermediate 2, eventually
leading to the trans product. Path b considers the possibility
of isomerization of the cis vinyl bromide to trans under the
reaction conditions, followed by reaction with the vinylsiloxane
to produce the trans product. To check the feasibility of this
isomerization, when a blank experiment was carried out by a
Conclusions
In conclusion, we have developed a simple and efficient route
to functionalised styrenes, trans aryl 1,3-, 1,4- and 1,5-dienes,
bis 1,2-, 1,3- and 1.4- (1,3-)dienes, and 1,3,5 trienes by the
Hiyama cross-coupling of an appropriate halide and triethoxy-
vinylsilane catalyzed by Pd(0) nanoparticles generated in situ
in the reaction mixture in presence of TBAF in THF. This
procedure offers significant advantages such as mild reaction
conditions without the requirement for a high pressure and
temperature,6k compatibility with base-sensitive functional
c
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groups (COOR, CONHPh, NHCOPh, CN), general appli-
cability for a wide range of aryl and heteroaryl halides, high
yields, and excellent stereoselectivity by providing only trans
products. To the best of our knowledge, we are not aware of a
protocol leading to the synthesis of such a wide range of aryl
trans dienes, bis dienes and trienes, and we believe that
this methodology will find useful applications in organic
synthesis.
Experimental
General comments
IR spectra were recorded neat on a Shimadzu 8300 FTIR
1
spectrometer. H NMR and 13C NMR spectra were collected
on a Bruker DPX-300 instrument at 300 or 500 and 75 or
125 MHz, respectively. HRMS were recorded on a Microtek
Qtof Micro YA263 spectrometer. A suspension of nano-
particles in THF was drop-cast onto a carbon-coated copper
grid, and a TEM image of a dry powder was taken using a
JEM-2011 (JEOL) microscope. All commercial reagents were
distilled before use.
Scheme 2 Chemoselective manipulation of 4-bromoiodobenzene.
Table 3 Pd nanoparticle-catalyzed Hiyama cross-coupling reactions of vinyl bromides with triethoxyvinylsilane
Entry
1
Substrate
Time/h
8
Product
Yield (%)a
Ref.
12
75
2
3
9
71
40
12
12
11
4
5
9
8
65
78
12
6
7
8
80
60
12
12
10
c
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Table 3 (continued )
Entry
8
Substrate
Time/h
8
Product
Yield (%)a
Ref.
12
77
9
10
50
73
12
13
10
9
11
12
13
8
8
8
9
83
85
77
67
14
15
12
14
15
10
10
68
65
12
16
16
a
A mixture of styryl bromide (1 mmol), triethoxyvinylsilane (228 mg, 1.2 mmol), PdCl2 (4 mg, 2 mol%) and TBAF (1 M solution in THF; 1.2 mL,
1.2 mmol) in THF (3 mL) was heated under reflux (65 1C) for the required time period. Yields refer to those of purified products characterized by
spectroscopic data.
Representative procedure for the coupling of 4-methoxyiodo-
benzene and triethoxyvinylsilane (Table 2, entry 5). A mixture
of 4-methoxyiodobenzene (234 mg, 1 mmol), triethoxyvinyl-
silane (228 mg, 1.2 mmol), PdCl2 (4 mg, 2 mol%) and TBAF
(1 M solution in THF; 1.2 mL, 1.2 mmol) in THF (3 mL) was
heated under reflux (65 1C) for 9 h (TLC). The reaction
mixture was extracted with Et2O (3 Â 10 mL), the ether
extract washed with brine and water, and dried over Na2SO4.
Evaporation of the solvent left the crude product, which
was purified by column chromatography over silica gel
(hexane : ether = 98 : 2) to give 4-methoxystyrene as a colour-
less oil (104.5 mg, 78%). The spectroscopic data were in good
agreement with reported values.6f
This procedure was followed for all the reactions listed in
Tables 2–6. Known compounds were identified by comparison
of their spectra (1H NMR, 13C NMR) with those reported
previously (see the references in the Tables). New compounds
were properly characterized by their IR, 1H NMR, 13C NMR and
c
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Table 4 Pd nanoparticle-catalyzed Hiyama cross-coupling reactions
of benzene bis vinyl bromides with triethoxyvinylsilane
N-(4-Vinyl phenyl) benzamide [Table 2, entry 8]. Yellow
solid. mp 145–147 1C; IR (KBr): nmax/cmÀ1 3336, 1651,
1523, 1402, 1323, 1261, 898, 837, 715, 650, 497. 1H NMR
(500 MHz, CDCl3) d (ppm): 5.21 (d, J = 11 Hz, 1 H), 5.70
(d, J = 17 Hz, 1 H), 6.66–6.71 (m, 1 H), 7.39 (d, J = 8 Hz, 3 H),
7.45 (t, J = 7.5 Hz, 2 H), 7.53 (t, J = 7.5 Hz, 1 H), 7.62
(d, J = 8 Hz, 2 H), 7.85 (d, J = 8 Hz, 2 H), 8.02 (s, 1 H). 13C
(125 MHz, CDCl3) d (ppm): 113.2, 120.2 (2 C), 126.9 (2 C),
127.1 (2 C), 128.8 (2 C), 131.0, 134.9, 136.1, 137.6, 165.7.
HRMS calc. for C15H13NO [M + H]+: 224.1094; found:
224.1072.
Entry
Substrate
Time/h
Yield (%)a
Ref.
17
1
2
3
1,2-
1,3-
1,4-
8
7
7
62
66
73
18
a
Yields refer to those of purified products characterized by spectro-
scopic data.
1-((E)-Buta-1,3-dienyl)-4-(trifluoromethoxy) benzene [Table 3,
entry 5]. Colorless oil. IR (KBr): nmax/cmÀ1 2922, 2850, 1508,
1464, 1257, 1222, 1168, 991. 1H NMR (500 MHz, CDCl3)
d (ppm): 5.22 (d, J = 10 Hz, 1 H), 5.37 (d, J = 17 Hz, 1 H),
6.47–6.57 (m, 2 H), 6.73–6.79 (m, 1 H), 7.17 (d, J = 8 Hz,
2 H), 7.43 (d, J = 8.5 Hz, 2 H). 13C NMR (125 MHz, CDCl3)
d (ppm): 118.5, 121.2 (2 C), 121.6, 127.7 (2 C), 130.7, 131.3,
136.0, 136.9, 148.6. Anal calc. for C11H9OF3: C 61.68, H 4.24;
found: C 61.70, H 4.24%.
HRMS spectroscopic data. These are provided below in order
of their entries in Tables 2–6 and Scheme 2.
N-Phenyl-4-vinyl benzamide [Table 2, entry 7]. Yellowish
solid. mp 163–165 1C; IR (KBr): nmax/cmÀ1 3355, 1651,
1597, 1529, 1506, 1438, 1325, 993, 908, 858, 750, 688, 509.
1H NMR (300 MHz, CDCl3) d (ppm): 5.35 (d, J = 11 Hz, 1 H),
5.82 (d, J = 17.5 Hz, 1 H), 6.67–6.77 (m, 1 H), 7.12 (t, J =
7.5 Hz, 1 H), 7.32 (t, J = 7.8 Hz, 2 H), 7.45 (d, J = 9 Hz, 2 H),
7.62 (d, J = 8 Hz, 2 H), 7.79 (d, J = 8 Hz, 2 H), 8.05 (s, 1 H).
13C NMR (75 MHz, CDCl3) d (ppm): 116.3, 120.5 (2 C), 124.6,
126.5 (2 C), 127.5 (2 C), 129.1 (2 C), 134.0, 135.9, 138.0, 141.1,
165.7. HRMS calc. for C15H13NO [M + H]+: 224.1094;
found: 224.1071.
4-((E)-Buta-1,3-dienyl) phenyl-4-methyl benzenesulfonate
[Table 3, entry 14]. Colouless oil. IR (KBr): nmax/cmÀ1 3070,
2924, 1597, 1500, 1337, 1197, 1093, 866. H NMR (500 MHz,
1
CDCl3) d (ppm): 2.22 (s, 3 H), 4.97 (d, J = 9.5 Hz, 1 H), 5.12
(d, J = 17 Hz, 1 H), 6.23–6.28 (m, 2 H), 6.48–6.52 (m, 1 H),
6.70 (d, J = 8 Hz, 2 H), 7.04–7.09 (m, 4 H), 7.48 (d, J = 8 Hz,
2 H). 13C NMR (125 MHz, CDCl3) d (ppm): 21.8, 118.6, 122.7
Table 5 Pd nanoparticle-catalyzed Hiyama cross-coupling reactions of allyl bromides with triethoxyvinylsilane
Entry
1
Substrate
Time/h
8
Product
Yield (%)a
Ref.
75
6j
2
3
4
9
8
65
70
6j
6e
7
9
76
68
6e
6e
5
a
Yields refer to those of purified products characterized by spectroscopic data.
c
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Table 6 Pd nanoparticle-catalyzed Hiyama cross-coupling reactions
of allyl bromides with allyltrimethylsilane
1001, 945, 895, 785, 692. 1H NMR (500 MHz, CDCl3)
d (ppm): 5.19 (d, J = 10 Hz, 2 H), 5.36 (d, J = 16 Hz,
2 H), 6.50–6.57 (m, 4 H), 6.80–6.83 (m, 2 H), 7.26–7.27
(m, 3H), 7.43 (s, 1 H). 13C NMR (125 MHz, CDCl3)
d (ppm): 117.9 (2 C), 124.7, 125.8 (2 C), 128.9, 130.0 (2 C),
132.7 (2 C), 137.2 (2 C), 137.6 (2 C). Anal calc. for C14H14:
C 92.26, H 7.74; found: C 92.24, H 7.76%.
Entry
R
Time/h
Yield (%)a
Ref.
1
2
3
H
4-CH3
4-Cl
8
7
7
71
65
73
19
20
1-Chloro-4-((E)-hexa-1,5-dienyl) benzene [Table 6, entry 3].
Colourless oil. IR (KBr): nmax/cmÀ1 3163, 2924, 2852, 1514,
1464, 1193, 833, 761, 669. 1H NMR (500 MHz, CDCl3)
d (ppm): 2.17–2.25 (m, 2 H), 2.29–2.36 (m, 2 H), 4.99–5.09
(m, 2 H), 5.82–5.90 (m, 1 H), 6.17–6.23 (m, 1 H), 6.35 (d, J =
16 Hz, 1 H), 7.24–7.28 (m, 4 H). 13C NMR (125 MHz, CDCl3)
d (ppm): 32.5, 33.5, 115.1, 127.3 (2 C), 128.7 (2 C), 129.2,
131.0, 132.6, 136.4, 138.0. Anal calc. for C12H13Cl: C 74.80,
H 6.80; found: C 74.82, H 6.75%.
a
Yields refer to those of purified products characterized by spectro-
scopic data.
(E)-Butyl-3-(4-vinyl phenyl) acrylate [Scheme 2, D]. Colour-
less oil. IR (KBr): nmax/cmÀ1 2958, 2931, 1714, 1635, 1510,
1309, 1276, 1205, 1170, 981, 835, 667. H NMR (500 MHz,
1
CDCl3) d (ppm): 0.95–0.98 (m, 3 H), 1.25–1.26 (m, 2 H),
1.41–1.46 (m, 2 H), 1.67–1.70 (m, 2 H), 4.21 (t, J = 6.5 Hz,
2 H), 5.31 (d, J = 11 Hz, 1 H), 5.80 (d, J = 18 Hz, 1 H), 6.42
(d, J = 16 Hz, 1 H), 6.68–6.74 (m, 1 H), 7.41(d, J = 8 Hz, 2 H),
7.48 (d, J = 8 Hz, 2 H), 7.66 (d, J = 16 Hz, 1 H). 13C NMR
(125 MHz, CDCl3) d (ppm): 13.8, 19.3, 30.9, 64.5, 115.3, 118.1,
126.7 (2 C), 128.4 (2 C), 134.0, 136.2, 139.6, 144.1, 167.2.
HRMS calc. for C15H18O2Na [M + Na]+: 253.1205; found:
253.1204.
Fig. 3 Reaction monitoring by UV spectroscopy.
1-(4-(4-Vinyl styryl) phenyl) ethanone [Scheme 2, B]. Yellow
solid. mp 150–153 1C. IR (KBr): nmax/cmÀ1 3335, 1674, 1595,
1410, 1357, 1273, 1182, 964, 840, 594, 515. 1H NMR
(300 MHz, CDCl3) d (ppm): 2.52 (s, 3 H), 5.19 (d, J = 11 Hz,
1 H), 5.70 (d, J = 17 Hz, 1 H), 6.60–6.69 (m, 1 H), 7.01–7.06
(m, 2 H), 7.34 (d, J = 8 Hz, 2 H), 7.42 (d, J = 8 Hz, 2 H), 7.50
(d, J = 8 Hz, 2 H), 7.87 (d, J = 8 Hz, 2 H). 13C NMR
(75 MHz, CDCl3) d (ppm): 26.6, 114.3, 126.6 (2 C), 126.7 (2 C),
127.1 (2 C), 127.4, 129.0 (2 C), 131.1, 136.0, 136.3, 136.4,
137.7, 142.1, 197.5. HRMS calc. for C18H16O [M + H]+:
249.1250; found: 249.1275. Compounds A and C in Scheme 2
are known and were identified by comparison of their spectro-
scopic data with those previously reported.22,23
Acknowledgements
We are pleased to acknowledge the financial support from the
Department of Science and Technology, New Delhi through
the award of a J. C. Bose National Fellowship to B. C. R.
(Grant no. SR/S2/JCB-11/2008). T. C. and R. D. thank the
Council of Scientific and Industrial Research, New Delhi for
their fellowships.
Scheme 3 A plausible mechanism.
(2 C), 127.5 (2 C), 128.6 (2 C), 129.9 (2 C), 130.7, 131.3, 132.4,
135.9, 136.9, 145.5, 148.9. HRMS calc. for C17H16O3SNa
[M + Na]+: 323.0718; found 323.0719.
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