Synthesis of (E)-stilbenes and (E,E)-1,4-diphenylbuta-1,3-diene promoted by boron trifluoride-diethyl ether complex

Article abstract of DOI:10.1055/s-0029-1217010

An efficient, simple, and practical method has been de-veloped to regioselectively synthesize (E)-stilbenes and (E,E)-1,4diphenylbuta-1,3-diene in good to excellent yields in the presence of boron trifluoride-diethyl ether complex as a catalyst in a short reaction (30-60 s) at room temperature. Georg Thieme Verlag Stuttgart.

Full text of DOI:10.1055/s-0029-1217010

PAPER
3791
Synthesis of (E)-Stilbenes and (E,E)-1,4-Diphenylbuta-1,3-diene Promoted by
Boron Trifluoride–Diethyl Ether Complex
Synthesis of
(
E
)
.
-Stilbenes
a
n
N
d (
E
,
E
)-1,4-Diphe
a
nylbuta-1,
r
3-diene ender,* K. Papi Reddy, G. Madhur
Medicinal and Process Chemistry Division, Central Drug Research Institute, Lucknow 226 001, U.P., India
Fax +91(522)2623405; E-mail: t_narendra@cdri.res.in
Received 4 May 2009; revised 8 July 2009
of 1,2-diphenylacetylenes,10 dehydrogenation of 1,2-
Abstract: An efficient, simple, and practical method has been de-
veloped to regioselectively synthesize (E)-stilbenes and (E,E)-1,4-
diphenylbuta-1,3-diene in good to excellent yields in the presence
of boron trifluoride–diethyl ether complex as a catalyst in a short re-
action (30–60 s) at room temperature.
diphenylethanes,11 or dehydration of 1-hydroxy-1,2-
diphenylethanes12 lead to the formation of stilbenes with-
out the formation of a new C–C bond. The methods for the
synthesis of stilbenes through formation of a new C–C
bond are coupling reactions such as Meerwein arylation,13
the Heck-type reactions also known as Mizoroki–Heck
reactions14,15 of aryl halides and styrenes, Suzuki cross-
coupling of organotellurides with potassium organic tri-
fluoroborate salts,16 and condensation reactions such as
Knoevenagel-type, Wittig, and Wittig–Horner reac-
tions.17 Other reactions that have appeared in the literature
include the following: reactions of aldehyde tosylhydra-
zones with benzotriazole-stabilized carbanions,18 tri-
methylborate/lithium tert-butoxide, trialkylboranes, and
alkylboron chlorides;19 reactions of organozinc halides
with carbonyl compounds in the presence of a catalytic
amount of [PdCl2(PPh3)]2 or [NiCl2(PPh3)]2 complex-
es;20,21 reductive coupling of ketones (McMurry reac-
tion);22 conversion of a-halo sulfones into alkenes
(Ramberg–Bäcklund reaction);23 condensation of meth-
ylated aromatic nuclei with benzalaniline (Siegrist reac-
tion);24 reductive ArCHBr2 dimerization;25 and sequential
cross-coupling reactions.26
Key words: boron trifluoride–diethyl ether complex, (E)-stilbenes,
(E,E)-1,4-diphenylbuta-1,3-diene, ketones, regioselectivity
Stilbene derivatives (stilbenoids) are present in plants and
show a wide range of biological activities and potential
therapeutic value (Figure 1).1 For example, resveratrol ex-
hibits a variety of useful bioactivities including cancer
chemopreventive, antiplatelet aggregation, antioxidative,
antibacterial, anti-inflammatory, and antidyslipidemic ac-
tivities.2 Pterostilbene acts as an effective PPAR-a
agonist2b and hypolipidemic agent, and in vivo studies
demonstrated that it also possesses lipid- and glucose-
lowering effects. Pinosylvin is a constituent of heartwood
of pine and exhibits antifungal and antibacterial activity.3
Piceatannol is found in red wine, and shows anti-inflam-
matory, immunomodulatory, and antiproliferative activi-
ties.4 The cis and trans isomers of combretastain A4 are
reported to have antitumor activity5 (Figure 1). Some of
the synthetic stilbenes are used as optical brighteners,6
phosphors,7 and scintillators.8
The currently available methods for the synthesis of stil-
benes have some limitations, such as (i) the need for mul-
tistep synthesis,27 (ii) the use of toxic metal complexes
such as Pd–NHC complexes,15 [Pd(O2CCF3],
[PdCl2(PPh3)]2, and [NiCl2(PPh3)],20 (iii) the requirement
to prepare special synthons such as organozinc arylha-
lides,20 aromatic boronic acids, aryl or vinyl tellurides,
aryl or vinyl trifluoroborate salts,16 etc., (iv) the lack of
stereoselectivity (cis and trans isomers),27 (v) long reac-
tion times,15,20,21 and (vi) harsh reaction conditions.10,16
The development of new and simple methods to form
such bonds by procedures devoid of the above-described
disadvantages i–vi is still a challenge for organic chem-
ists. Herein we show that (E)-stilbenes can be easily syn-
thesized by the reaction of 1-phenylpropan-2-one (1a), its
derivative 1b, and 1-(2,4-dimethoxyphenyl)-2-phenyleth-
anone (1c) with aryl aldehydes 2a–k in the presence of the
boron trifluoride–diethyl ether complex (Scheme 1,
Table 1).
R2
OH
R3O
MeO
MeO
MeO
R1
OMe
R3O
combretastatin A4 (CA4)
R1 = OH, R2, R3 = H resveratrol
R1 = OH, R2 = H, R3 = Me pterostilbene
R1, R2, R3 = H pinosylvin
R1,R2 = OH, R3 = H piceatannol
Figure 1 Biologically active stilbene derivatives
Several methods are available for the synthesis of stil-
benes.9 They can be synthesized either without formation
of a new C–C bond or with formation of a new C–C bond.
For example, controlled hydrogenation of the triple bond
SYNTHESIS 2009, No. 22, pp 3791–3796
x
x.
x
x
.
2
0
0
9
Advanced online publication: 23.09.2009
DOI: 10.1055/s-0029-1217010; Art ID: T09209SS
© Georg Thieme Verlag Stuttgart · New York

3792
T. Narender et al.
PAPER
R1
O
R1
H
R
1 = H
KOH
O
+
1,4-diphenylbut-3-en-2-one
R1
R2
O
BF3⋅OEt2
2a
OH
R1 = H, R2 = Me 1a
30–60 s, r.t.
+
R
R
1 = OMe, R2 = Me 1b
1 = H, R2 = 2,4-(MeO)2C6H3 1c
R2
O
R
1 = H 3a
R
1 = OMe 3e
Scheme 1 Synthesis of stilbenes 3a and 3e in the presence of the boron trifluoride–diethyl ether complex
Table 1 Synthesis of (E)-Stilbene Derivatives 3a–h and 3j–m and (E,E)-1,4-Diphenylbuta-1,3-diene 3i in the Presence of Boron Trifluoride–
Diethyl Ether Complex
Entry
1
Ketone
Aldehyde
Product
Yielda (%)
82
H
H
1a
2a
3a
O
O
O
2
3
1a
1a
2b
2c
3b
3c
80
70
Me
OH
Me
OH
H
H
O
O
4
1a
2d
3d
75
H
H
H
H
H
5
6
7
8
9
1a
1a
1a
1a
1a
2e
2f
3e
3f
72
74
69
66
73
O
O
O
O
O
OMe
OMe
O
O
O
O
2g
2h
2i
3g
3h
3i
Cl
F
Cl
F
F
F
Synthesis 2009, No. 22, 3791–3796 © Thieme Stuttgart · New York

PAPER
Synthesis of (E)-Stilbenes and (E,E)-1,4-Diphenylbuta-1,3-diene
3793
Table 1 Synthesis of (E)-Stilbene Derivatives 3a–h and 3j–m and (E,E)-1,4-Diphenylbuta-1,3-diene 3i in the Presence of Boron Trifluoride–
Diethyl Ether Complex (continued)
Entry
10
Ketone
Aldehyde
Product
Yielda (%)
72
H
1a
2j
3j
O
H
H
11
12
1a
1b
2k
2a
3k
3e
64
50
O
O
MeO
MeO
MeO
O
H
H
13
14
1b
1b
2b
2c
3l
49
42
O
O
Me
OH
Me
OH
MeO
3m
H
H
15b
16b
17
1c
1c
1d
2a
2e
2a
3a
3e
53
O
O
O
MeO
OMe
50
OMe
OMe
H
NIc
O
O
H
H
18
19
1a
1a
2l
NIc
NIc
O
O
O
2m
a Isolated yields.
b Formation of 2,4-dimethoxybenzoic acid as a byproduct was confirmed by TLC with an authentic sample as comparison.
c NI = not isolated (mixture of several compounds due to side reactions).
Almost 128 years ago (1890) Miller and Rohde described ride–diethyl ether complex;29 however, they did not
stilbene syntheses using sulfuric acid and water (H2SO4– explore the synthesis of (E)-stilbenes and (E,E)-1,4-
H2O, 3:1).28 Kabalka and co-workers reported the synthe- diphenylbuta-1,3-dienes.
sis of only (E)-alkenes in the presence of boron trifluo-
Synthesis 2009, No. 22, 3791–3796 © Thieme Stuttgart · New York

3794
T. Narender et al.
PAPER
To investigate the scope and limitations of boron trifluo- similar conditions, and this supports the importance of
ride–diethyl ether complex as a catalyst for the synthesis benzylic hydrogens in the ketone. Kabalka and co-
of (E)-stilbenes and (E,E)-1,4-diphenylbuta-1,3-diene, workers29 used aliphatic ketones (except 1,3-diphenylace-
various aromatic aldehydes 2a–k, including cinnamalde- tone) during their studies, and this might be the reason
hyde (2i), on the one hand, and 1-phenylpropan-2-one why drastic reaction conditions were required to obtain
(1a), 1-(p-methoxyphenyl)propan-2-one (1b), 1-(2,4- the (E)-alkenes.
dimethoxyphenyl)-2-phenylethanone (1c), on the other
In summary, we developed an efficient, simple, and prac-
tical method for the synthesis of (E)-stilbenes and conju-
gated (E,E)-1,4-diphenylbuta-1,3-diene in good to
hand, were utilized as substrates (Scheme 1).30 The results
are summarized in Table 1.
The regioselective reaction between 1-phenylpropan-2- excellent yields from the reactions of 1-phenylpropan-2-
one (1a) and benzaldehyde (2a) in the presence of boron one (1a), its derivative 1b, and 1-(2,4-dimethoxyphenyl)-
trifluoride–diethyl ether complex resulted in the forma- 2-phenylethanone (1c) with aromatic aldehydes 2a–k, for
tion of (E)-stilbene (3a) in excellent yield (82%) after a the first time in the presence of boron trifluoride–diethyl
short duration of time (30–60 s).30 Further exploration ether complex. The advantages of this method are the fol-
with various substituted aldehydes 2b–k also provided the lowing: the reaction proceeds regioselectively to provide
(E)-stilbenes 3b–h and 3j,k. To study the reaction condi- (E)-stilbenes and (E,E)-1,4-diphenylbuta-1,3-diene, sim-
tions, we carried out the reaction between 1-(p-methoxy- ple experimental procedure, short duration of reaction
phenyl)propan-2-one (1b) and benzaldehydes 2a–c, time (30–60 s), mild reaction conditions (room tempera-
which provided (E)-stilbenes 3e, 3l, and 3m; however, the ture), solvent-free reaction in the case of at least one liquid
electron-releasing groups on ketone led to low yields reactant, low cost of catalyst, and tolerance of functional
(Table 1, entries 12–14). To demonstrate the wider appli- groups such as an ester, phenol, and ether. This method
cability of this reaction, we carried out the reactions be- might also be useful for the synthesis of diphenyl-substi-
tween 1-(2,4-dimethoxyphenyl)-2-phenylethanone (1c) tuted polyenes. Our reaction avoids the use of toxic metal
and 2a and 2e, which also afforded the (E)-stilbenes 3a complexes, multistep synthesis, the preparation of special
and 3e (entries 15 and 16). The trans nature of the double synthons, long reaction times, and harsh reaction condi-
bond of the synthesized stilbenes was confirmed by the tions.
coupling constants (J = ca. 16 Hz) in the 1H NMR spectra
(see Supporting Information), and we did not observe
their respective cis isomers (cis-stilbenes) during our iso-
lation process.
Melting points were determined on a Buchi-530 capillary melting
point apparatus and are uncorrected. IR spectra were recorded on a
Perkin-Elmer AC-1 infrared spectrometer of samples prepared as
KBr pellets. NMR spectra were recorded of samples in CDCl3 (un-
less stated otherwise) on a Bruker Avance DPX 300, 200 MHz spec-
trometer. ESI-MS determinations were carried out on a Jeol SX
102/DA-6000 spectrometer. Column chromatography was per-
formed on silica gel (60–120 mesh).
The reaction between 4-phenylbutan-2-one (1d) and ben-
zaldehyde (2a) and between 1-phenylpropan-2-one (1a)
and aliphatic aldehyde 2l (propanal) or 2m (citral) did not
provide the desired alkenes (Table 1, entries 17–19),
whereas the reaction between 1-phenylpropan-2-one (1a)
and cinnamaldehyde (2i) proceeded smoothly (entry 9);
this indicates that benzylic hydrogens adjacent to the ke-
tone (1a, 1b, 1c) and an aldehyde functionality directly at-
tached to an aromatic ring (2a–h, 2j, 2k) or conjugated
with an aromatic ring (2i) are essential to form the (E)-stil-
benes (3a–h, 3j, 3k) or (E)-1,4-diphenylbuta-1,3-diene
(3i). It is noteworthy to mention here that under basic con-
ditions (KOH) the reaction between 1-phenylpropan-2-
one (1a) and benzaldehyde (2a) resulted in the synthesis
of 1,4-diphenylbut-3-en-2-one in our own studies, as de-
scribed by Southwick and co-workers31 (Scheme 1).
(E)-4-Styrylphenol (3c); Typical Procedure
BF3·OEt2 (0.14 mL, 1.1 mmol) was added gradually to a stirred soln
of 1-phenylpropan-2-one (1a; 500 mg, 3.7 mmol) and 4-hydroxy-
benzaldehyde (2c; 546 mg, 4.4 mmol) at r.t. The resultant soln was
stirred for 30–60 s. After dilution with Et2O (100 mL), the soln was
washed with H2O (3 × 30 mL) to decompose the BF3·OEt2 complex.
The organic soln obtained after extraction was dried (Na2SO4) and
filtered, and the solvent was evaporated under reduced pressure.
The crude mixture was purified by column chromatography (silica
gel, hexane–EtOAc); this afforded 3c.21
Yield: 510 mg (70%); mp 183–185 °C.
IR (KBr): 2965, 1613, 1476, 1368, 1229, 1047, 960, 737 cm–1.
1H NMR (300 MHz, CDCl3 + CD3OD): d = 7.46 (m, 2 H), 7.37 (d,
J = 8.4 Hz, 2 H), 7.30 (m, 2 H), 7.18 (m, 1 H), 7.04 (d, J = 16.1 Hz,
1 H), 6.93 (d, J = 16.1 Hz, 1 H), 6.80 (d, J = 8.4 Hz, 2 H).
13C NMR (75 MHz, CDCl3 + CD3OD): d = 156.7, 137.8, 129.1,
128.4, 128.3 (2 C), 127.6 (2 C), 126.8, 125.9 (2 C), 125.6, 115.3 (2
C).
The reaction mechanism appears to be an aldol–Grob re-
action sequence as proposed by Kabalka and co-work-
ers.29 The reaction conditions to obtain the optimum yield
of (E)-alkenes in Kabalka and co-workers’ studies29 con-
sisted of reflux temperature, suitable solvent, and 0.5–21
hours’ reaction time. The rapid reaction at room tempera-
ture with a catalytic amount of boron trifluoride–diethyl
ether in our studies might be due to the presence of ben-
zylic hydrogens adjacent to the ketone functionality (1a–
c). The reaction between 4-phenylbutan-2-one (1d) and
benzaldehyde (2a) did not produce the (E)-alkene under
ESI-MS: m/z = 197.2 [M + H]+.
(E)-1,2-Diphenylethene (3a)21
Yield: 82%; mp 122–124 °C.
1H NMR (200 MHz, CDCl3): d = 7.62–7.58 (m, 4 H), 7.48–7.30 (m,
6 H), 7.20 (br s, 2 H).
Synthesis 2009, No. 22, 3791–3796 © Thieme Stuttgart · New York

PAPER
Synthesis of (E)-Stilbenes and (E,E)-1,4-Diphenylbuta-1,3-diene
3795
(E)-1-Methyl-4-styrylbenzene (3b)16
Yield: 80%; mp 118–120 °C.
1H NMR (300 MHz, CDCl3): d = 7.61 (d, J = 7.3 Hz, 2 H), 7.52 (d,
J = 8.0 Hz, 2 H), 7.48–7.43 (m, 2 H), 7.36 (m, 1 H), 7.27 (d, J = 8.0
Hz, 2 H), 7.19 (m, 2 H), 2.46 (s, 3 H).
13C NMR (75 MHz, CDCl3): d = 137.7, 137.7, 134.8, 129.6 (2 C),
128.9 (2 C), 128.0, 127.6, 126.7 (2 C), 126.6 (2 C), 126.2, 21.5.
13C NMR (75 MHz, CDCl3): d = 137.6, 135.0, 133.7, 131.4, 128.8
(2 C), 128.7, 128.6, 128.1, 127.8, 126.7 (2 C), 126.5, 126.1, 125.9,
125.8, 125.7, 123.8.
(E)-1-Methoxy-4-(4-methylstyryl)benzene (3l)35
Yield: 49%; mp 208–210 °C.
1H NMR (300 MHz, CDCl3): d = 7.49–7.42 (m, 4 H), 7.20 (m, 2 H),
7.03 (d, J = 8.7 Hz, 2 H), 6.94 (d, J = 8.7 Hz, 2 H), 3.86 (s, 3 H),
2.39 (s, 3 H).
(E)-1-Isopropyl-4-styrylbenzene (3d)32
Yield: 75%; mp 86–88 °C.
(E)-4-(4-Methoxystyryl)phenol (3m)36
Yield: 42%; mp 202–204 °C.
1H NMR (300 MHz, CDCl3): d = 7.43–7.33 (m, 4 H), 6.90–6.79 (m,
6 H), 3.81 (s, 3 H).
1H NMR (300 MHz, CDCl3): d = 7.58 (m, 2 H), 7.52 (m, 2 H), 7.42
(m, 2 H), 7.31 (m, 3 H), 7.15 (m, 2 H), 2.99 (m, 1 H), 1.34 (d, J = 6.9
Hz, 6 H).
(E)-1-Methoxy-4-styrylbenzene (3e)21
Yield: 72%; mp 136–138 °C.
Supporting Information for this article is available online at
1H NMR (200 MHz, CDCl3): d = 7.52–7.45 (m, 4 H), 7.35 (m, 2 H),
7.28–7.24 (m, 1 H), 7.10 (d, J = 16.4 Hz, 1 H), 7.04 (m, 1 H), 6.91
(d, J = 8.8 Hz, 2 H), 3.84 (s, 3 H).
http://www.thieme-connect.com/ejournals/toc/synthesis.
Acknowledgment
(E)-4-Styrylphenyl Acetate (3f)33
Yield: 74%; mp 148–150 °C.
1H NMR (200 MHz, CDCl3): d = 7.54 (m, 4 H), 7.42–7.24 (m, 3 H),
7.12–7.09 (m, 4 H), 2.30 (s, 3 H).
The authors are thankful to the Director, CDRI, for support with the
synthesis of natural product analogues, the SAIF Division of CDRI
for spectral data, and CSIR, New Delhi, for financial support. This
is CDRI communication No. 7562.
13C NMR (75 MHz, CDCl3): d = 169.5, 150.1, 137.2, 135.2, 129.0,
128.7 (2 C), 127.7, 127.6, 127.4 (2 C), 126.5 (2 C), 121.8 (2 C),
21.2.
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(E)-1-Chloro-4-styrylbenzene (3g)21
Yield: 69%; mp 125–127 °C.
1H NMR (300 MHz, CDCl3): d = 7.54 (m, 2 H), 7.47 (m, 2 H), 7.42–
7.31 (m, 5 H), 7.10 (m, 2 H).
13C NMR (75 MHz, CDCl3): d = 137.0, 135.9, 133.2, 129.4, 128.8
(2 C), 128.7 (2 C), 127.9, 127.7 (2 C), 127.4, 126.6 (2 C).
(E)-2,4-Difluoro-1-styrylbenzene (3h)34
Yield: 66%; mp 120–122 °C.
1H NMR (300 MHz, CDCl3): d = 7.63–7.54 (m, 3 H), 7.43–7.38 (m,
2 H), 7.34 (m, 1 H), 7.24 (d, J = 16.4 Hz, 1 H), 7.13 (d, J = 16.4 Hz,
1 H), 6.94–6.83 (m, 2 H).
(1E,3E)-1,4-Diphenylbuta-1,3-diene (3i)21
Yield: 73%; mp 149–151 °C.
1H NMR (300 MHz, CDCl3): d = 7.47 (m, 4 H), 7.36 (m, 4 H), 7.25
(m, 2 H), 7.01–6.96 (m, 2 H), 6.72–6.67 (m, 2 H).
13C NMR (75 MHz, CDCl3): d = 137.6 (2 C), 133.1 (2 C), 129.5 (2
C), 128.9 (4 C), 127.8 (2 C), 126.6 (4 C).
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(E)-2-Styrylnaphthalene (3j)20
Yield: 72%; mp 144–146 °C.
1H NMR (200 MHz, CDCl3): d = 7.88 (m, 4 H), 7.79 (m, 1 H), 7.61
(m, 2 H), 7.53–7.41 (m, 4 H), 7.30 (m, 3 H).
13C NMR (75 MHz, CDCl3): d = 137.8, 135.3, 134.2, 133.5, 129.5,
129.2, 129.1 (2 C), 128.7, 128.4, 128.1 (2 C), 127.1, 127.0 (2 C),
126.8, 126.3, 124.0.
(E)-1-Styrylnaphthalene (3k)16
Yield: 64%; mp 127–128 °C.
1H NMR (300 MHz, CDCl3): d = 7.96–7.90 (m, 2 H), 7.85 (m, 1 H),
7.65 (m, 2 H), 7.59–7.51 (m, 3 H), 7.47–7.40 (m, 3 H), 7.37–7.29
(m, 2 H), 7.25 (d, J = 16.2 Hz, 1 H).
Synthesis 2009, No. 22, 3791–3796 © Thieme Stuttgart · New York

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T. Narender et al.
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