Efficient synthesis of substituted styrenes and biaryls (or heteroaryls) with regioselective reactions of ortho -, meta -, and para-bromobenzyl bromide

Article abstract of DOI:10.1055/s-0031-1290987

Regio- and stereoselective reactions of ortho-, meta-, and para-bromobenzyl bromide under Stille and (or) Suzuki cross-coupling reactions are described that provided substituted styrene monomers and biaryls in two steps. By controlling the experimental conditions, the first coupling provided access to allylarene or diarylmethane intermediates, and the second reaction led to the desired styrenes and biaryls, substituted by a spacer arm in the ortho, meta or para position depending on the starting material. Georg Thieme Verlag Stuttgart · New York.

Full text of DOI:10.1055/s-0031-1290987

PAPER
▌2023
paper
Efficient Synthesis of Substituted Styrenes and Biaryls (or Heteroaryls) with
Regioselective Reactions of ortho-, meta-, and para-Bromobenzyl Bromide
Synthesis of Substituted Styrenes and Biaryls
Elsa Anselmi,a Mohamed Abarbri,a Alain Duchêne,a Sandrine Langle-Lamandé,*b Jérôme Thibonnet*a
a
Laboratoire d’Infectiologie et Santé Publique (UMR UFR/INRA 1282), Equipe ‘Recherche et Innovation en Chimie Médicinale’ Université
François Rabelais, Faculté des Sciences, Parc de Grandmont, 37200 Tours, France
E-mail: jerome.thibonnet@univ-tours.fr
b
Groupe S.U.C.R.E.S – UMR 7565 Nancy Université – CNRS, BP 70239, 54506 Nancy Vandoeuvre, France
Received: 24.02.2012; Accepted after revision: 06.04.2012
Abstract: Regio- and stereoselective reactions of ortho-, meta-,
and para-bromobenzyl bromide under Stille and (or) Suzuki cross-
coupling reactions are described that provided substituted styrene
monomers and biaryls in two steps. By controlling the experimental
conditions, the first coupling provided access to allylarene or diaryl-
methane intermediates, and the second reaction led to the desired
styrenes and biaryls, substituted by a spacer arm in the ortho, meta
or para position depending on the starting material.
R
R
Br
Br
cross-
coupling
cross-
coupling
styrenes
Ar
Br
R
Key words: Stille reaction, palladium, regioselectivity, organome-
tallic reagents, biaryls
biaryls
Scheme 1 Preparation of styrene and biaryl compounds
Styrenes and biaryls are useful building blocks for fine
chemical synthesis.1,2 Biaryl moieties with important
physical or biological properties are widely represented in
organic molecules.3 As pharmacophores, they are found
in many medicinally important compounds such as antibi-
otic, anti-inflammatory, antihypertensive, and anticancer
drugs, among others. Di- or triaromatic rings are the back-
bone of some of the most efficient and selective ligands
for asymmetric catalysis, especially when atropoisomer-
ism is possible.4
The first coupling permitted regioselective access to allyl-
arene or diarylmethane intermediates I and II, and the sec-
ond reaction allowed the synthesis of styrenes and biaryls.
Synthesis of Intermediates I and II
Using 0.95 to 1 equivalents of an organometallic reagent
and starting from o-, m- or p-bromobenzyl bromides, we
were able to substitute benzylic bromide, rather than aryl-
ic bromide, regioselectively by Stille or Suzuki cross-cou-
pling reactions in the presence of a palladium salt. The
regioselective reaction of these two types of bromide has
already been demonstrated by other reactions (e.g., nu-
cleophilic or metallic substitution), however few reports
have investigated this regioselectivity by cross-coupling
catalysis.6,9 We accessed bromo-substituted allylarenes
1a–j (intermediates I) or brominated diarylmethanes 1k–
r (intermediates II) depending on the type of palladium
catalysis and the organometallic reagent used.
Styrenes are of particular interest as monomers in the
polymer industry,5 conferring different properties on the
polymers depending on the nature of the substituents pres-
ent on the derivatives. The development of efficient, se-
lective, and high-yielding methods for the preparation of
these molecules will, therefore, continue well into the fu-
ture.
In continuation of our previous studies on the different re-
actions of the two bromine atoms of bromobenzyl
bromide6 by cross-coupling reactions and recognizing that
a chemoselective reaction could be valuable, we have de-
veloped an efficient and versatile method to synthesize a
wide range of styrenes and biaryls very easily and selec-
tively. We have investigated the selective substitution re-
action under two successive Stille7 and Suzuki7g,8 cross-
coupling reactions with o-, m-, and p-bromobenzyl bro-
mides (Scheme 1).
The reaction conditions were classical (Table 1), but the
temperature of the reaction should not exceed 80 °C, oth-
erwise partial isomerization of the double bond of the allyl
group occurred with the Stille reaction. The starting vin-
yltin compounds bearing a trialkylsilyl, trialkylgermyl, or
triphenylgermyl, or a tributylstannyl group at the β posi-
tion were obtained by hydrostannation of the correspond-
ing alkynes.10 For Suzuki cross-coupling, the temperature
of the reaction depended on the boronic acid used. With
some boronic acids, higher temperatures led to loss of re-
gioselectivity.
SYNTHESIS 2012, 44, 2023–2040
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DOI: 10.1055/s-0031-1290987; Art ID: SS-2012-Z0195-OP
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Table 1 Synthesis of Intermediates I 1a–j and II 1k–ra,b
Br
Br
Stille[a] or Suzuki[b]
R1-M
+
R1
=
Br
R1 = aryl, alkenyl
M = SnBu3, or B(OH)2
1a–r
25–85%
intermediates I R1
intermediates II R1 = Ar
R2
Entry
1
R-M reagent
Product
Yieldc (%)
Br
SnBu3
SnBu3
SnBu3
SnBu3
SnBu3
SnBu3
SnBu3
SnBu3
1a
78
Me3Si
Me3Si
Me3Si
Et3Ge
Et3Ge
Et3Ge
Ph3Ge
Bu3Sn
SiMe3
Br
2
3
4
5
6
7
8
1b
1c
1d
1e
1f
71
72
80
67
66
67
25
SiMe3
SiMe3
GeEt3
Br
Br
Br
GeEt3
GeEt3
Br
Br
1g
1hd
GePh3
SnBu3
Br
Br
B(OH)2
B(OH)2
9
1i
71
t-Bu
t-Bu
t-Bu
Br
10
11
1j
69
84
t-Bu
Br
Br
1ke
B(OH)2
1le
83
B(OH)2
12
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Synthesis of Substituted Styrenes and Biaryls
2025
Table 1 Synthesis of Intermediates I 1a–j and II 1k–ra,b (continued)
Br
Br
Stille[a] or Suzuki[b]
R1-M
+
R1
=
Br
R1 = aryl, alkenyl
M = SnBu3, or B(OH)2
1a–r
25–85%
intermediates I R1
intermediates II R1 = Ar
R2
Entry
13
R-M reagent
Product
Yieldc (%)
Br
1me
85
B(OH)2
Br
Br
1nf
1of
1pf
71
59
61
F
B(OH)2
14
15
16
F
S
S
B(OH)2
S
Br
Br
B(OH)2
S
O
H
B(OH)2
17
18
1qg
66
65
CHO
Br
O
H
1rg
B(OH)2
CHO
a Stille conditions: bromobenzyl bromide (12 mmol, 1 equiv), organotin (11.5 mmol, 0.95 equiv), Pd(PPh3)4 (3 mol%), toluene, 80 °C, 15 h.
b Suzuki conditions: bromobenzyl bromide (12 mmol, 1 equiv), boronic acid (12 mmol, 1 equiv), Pd(PPh3)4 (3 mol%), EtOH–toluene–H2O, 1
M Na2CO3, 50 °C, 15 h.
c Yield of isolated product after chromatographic purification.
d 50% of double-coupling reaction was observed by GC.
e 80 °C.
f r.t., 24 h.
g 40 °C, 20 h.
As seen from the results in Table 1, these Stille and Suzuki diarylmethane 1k–r or (E)-allylarenes 1a–j very simply
cross-coupling reactions were completely regio- and and in good yields, depending on the organometallic re-
stereoselective, and only the benzylic bromide was substi- agent used, substituted by an o-, m-, or p-bromo-substitut-
tuted. No bis-coupling products were obtained and no ed aryl group. It is noted that the reaction with (E)-1,2-
isomerization of allylic compounds occurred. The config- bis(tributylstannyl)ethene (entry 8) provide a poor yield
uration of the double bond was conserved. We accessed of 1h, even when the reaction mixture was diluted and
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E. Anselmi et al.
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heated at only 70 °C. This was due to the inevitable for-
mation of 50% of the product resulting from a double-
coupling reaction.
Synthesis of ‘Symmetrical’ Dimetaled Styrenes and
Biaryls
Using 2.2 or 2.5 equivalents of an organometallic reagent
under the same conditions as described above, a clean
double cross-coupling reaction occurred, providing ‘sym-
metrical’ dimetaled styrenes 2a–d and biaryls 2e–i in one
step in good yields (Table 2). The products obtained were
substituted in the ortho, meta, or para position according
to the starting bromobenzyl bromide.
Allylarenes 1a–h bear 14th Group metals, this will be
valuable in the synthesis of styrenes, because the poly-
mers would have different properties after polymerization
depending on the metal. Diarylmethanes are used in the
synthesis of macrocycles, catenanes, and rotaxanes.11
Moreover, they often appear in the constitution of natural
products or advanced materials with important biological
and medical properties.12 The wide range of diarylmeth-
anes thus synthesized could be of interest to modulate
their pharmacological properties.
Table 2 Synthesis of Symmetrical Styrenes and Biaryls by Double Cross-Couplinga,b
MR3
SnBu3
R3M
Stille[a]
Br
MR3
2a–d
64–73%
Br
R
RB(OH)2
Suzuki[b]
R
2e–i
59–91%
Entry
1
R-M reagent
Product
Yieldc (%)
73
Me3Si
SnBu3
SnBu3
2a
2b
Me3Si
Me3Si
SiMe3
SiMe3
SiMe3
2
3
72
70
SiMe3
SnBu3
SnBu3
2c
Me3Si
Et3Ge
SiMe3
GeEt3
GeEt3
4
5
2dd
2e
64
91
B(OH)2
F
F
B(OH)2
6
2f
79
F
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Synthesis of Substituted Styrenes and Biaryls
2027
Table 2 Synthesis of Symmetrical Styrenes and Biaryls by Double Cross-Couplinga,b (continued)
MR3
SnBu3
R3M
Stille[a]
Br
MR3
2a–d
64–73%
Br
R
RB(OH)2
Suzuki[b]
R
2e–i
59–91%
Entry
R-M reagent
Product
Yieldc (%)
7
2g
87
59
71
B(OH)2
S
S
8
B(OH)2
2hd
S
CHO
O
H
2id
B(OH)2
9
CHO
a Stille conditions: bromobenzyl bromide (12 mmol, 1 equiv), organotin (30 mmol, 2.5 equiv), Pd(PPh3)4 (3 mol%), toluene, 80 °C, 18 h.
b Suzuki conditions: bromobenzyl bromide (12 mmol, 1 equiv), boronic acid (26.4 mmol, 2.2 equiv), Pd(PPh3)4 (3 mol%), EtOH–toluene–H2O,
1 M Na2CO3, 50 °C, 18 h.
c Yield of isolated product after chromatographic purification.
d 24 h.
renes) or with a diarylmethane (type II styrenes)
depending on the intermediates.
Synthesis of Substituted Styrenes (Types I and II):
Cross-Coupling with Aryl Bromides
The different type I styrenes were substituted by a three-
carbon spacer between the phenyl group and a Group 14
metal. This type of monomer was required for polymer-
ization in order to test the physical properties of the co-
polymers obtained, varying according to the nature of the
metal. The polymers were tested in order to constitute one
part of the target in the internal cavity of the laser mega-
joule (LMJ).18 As can be seen in Table 2, vinyltin and vi-
nylboronic acid reagents were good candidates for such
The synthesis of styrenes has been widely described in the
literature, and several methods can be used, including pal-
ladium cross-coupling13 such as Heck,14 Hiyama,15
Stille,7,16 or Suzuki17 reactions. A Stille or Suzuki reaction
with vinylic reagents seemed to be the most efficient
method by which to obtain the desired styrenes. These
methods allowed us to synthesize various styrenes substi-
tuted with an allyl arm that could be metaled (type I sty-
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E. Anselmi et al.
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synthesis and proved their efficiency as tools for the trans- the desired styrenes 3a–m. This Stille reaction was run in
fer of a vinyl unit, with high tolerance of numerous func- classical coupling arylic halide conditions with vinyltin in
tions both on the substrate and on the reagent.19 The final toluene at 90 °C for 18 hours, with a small excess of vin-
styrenes 3a–m were synthesized in large quantities to test yltin for optimal reaction progress. The Suzuki cross-cou-
the polymerization; conventional methods for the synthe- pling reaction was performed with (E)-3,3-dimethylbut-2-
sis of vinyltin compounds by exchange between magne- enylboronic acid in slight excess at 80 °C for 18 hours.
sium chloride and tributyltin are sometimes tedious. The Metaled or bis-metaled new styrene monomers were ob-
organotins used in Stille cross-coupling were prepared by tained in good yields with a three carbon spacer in ortho,
sonochemistry.20 Stille and Suzuki palladium cross-cou- meta, or para position. The results are presented in Table
pling was performed on the arylic bromide of previously 3.
prepared (E)-allylarene intermediates I 1a–h,j to obtain
Table 3 Synthesis of Type I Styrenesa,b
Br
Stille[a] or Suzuki[b]
M
+
R
R
1a–h,j
3a–m
52–75%
R = SiMe3, SnBu3, GeEt3, GePh3, t-Bu
M = SnBu3, B(OH)2
Entry
1
Intermediate I R-M reagent
Product
Yieldc (%)
75
1a
3a
SnBu3
SnBu3
SnBu3
SiMe3
SnBu3
GeEt3
2
3
1h
1d
3b
3c
64
71
4
1a
3d
69
SnBu3
SnBu3
SiMe3
5
6
1g
1d
3e
3f
60
64
GePh3
Me3Si
SnBu3
SnBu3
Me3Si
Me3Si
GeEt3
SiMe3
7
1f
3g
70
GeEt3
SiMe3
SnBu3
SnBu3
8
9
1j
3h
3i
73
52
Me3Si
t-Bu
Bu3Sn
1a
Bu3Sn
SiMe3
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Synthesis of Substituted Styrenes and Biaryls
2029
Table 3 Synthesis of Type I Styrenesa,b (continued)
Br
Stille[a] or Suzuki[b]
M
+
R
R
1a–h,j
3a–m
52–75%
R = SiMe3, SnBu3, GeEt3, GePh3, t-Bu
M = SnBu3, B(OH)2
Entry
10
Intermediate I R-M reagent
Product
Yieldc (%)
65
SnBu3
SnBu3
1b
3j
SiMe3
11
12
1e
1c
3k
62
63
GeEt3
SnBu3
3l
SiMe3
t-Bu
B(OH)2
13
1c
3m
74
t-Bu
SiMe3
a Stille conditions: intermediates 1a–h,j (4 mmol, 1 equiv), organotin (5.2 mmol, 1.3 equiv), Pd(PPh3)4 (3 mol%), toluene, 90 °C, 18 h.
b Suzuki conditions: intermediate 1c (4 mmol, 1 equiv), boronic acid (4.8 mmol, 1.2 equiv), Pd(PPh3)4 (3 mol%), EtOH–toluene–H2O, 1 M
Na2CO3, 80 °C, 18 h.
c Yield of isolated product after chromatographic purification.
Another clean second substitution by the Stille or Suzuki- this coupling reaction on the two types of intermediates I
type reaction was also possible, providing diarylmethane- and II in order to synthesize biaryls that were substituted
substituted type II styrenes. New substituted styrenes with an allyl or a diarylmethane group, depending on the
(metaled or unmetaled) with a one carbon spacer between intermediate used. The reaction conditions were the same
the two aromatic groups were prepared by reaction of ar- as previously described, various biaryls 5a–o were also
ylic bromides 1k–p,r. Using the same conditions as previ- obtained very efficiently in good yields bearing either a
ously used for the synthesis of type I styrenes, various diarylmethane or an allyl group in the ortho, meta, or para
arylstyrenes 4a–j were also obtained in good yields, as position, as shown in Table 5.
presented in Table 4.
Double Coupling in One-Pot Reaction
Synthesis of Substituted Biaryls: Cross-Coupling
In order to synthesize differently disubstituted styrenes
and biaryls, we performed two one-pot cross-coupling re-
with Aryl Bromides
Cross-coupling catalysis, in particular the Suzuki reaction actions without isolating the intermediate. A Suzuki
is the most versatile and often used reaction for the syn- cross-coupling reaction was performed on two different
thesis of biaryl-containing molecules.21 We decided to use boronic acids (Scheme 2) to test this strategy.
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Table 4 Synthesis of Type II Styrenes
Br
Stille[a] or Suzuki[b]
M
+
Ar
Ar
1k–p,r
4a–j
51–77%
M = SnBu3, B(OH)2
Entry
Intermediate II R-M reagent
Product
Yieldc (%)
1
2
1n
4a
4b
72
SnBu3
F
1m
67
SnBu3
3
4
1p
1k
4c
63
77
SnBu3
S
Me3Si
SnBu3
4d
Me3Si
SnBu3
5
1r
4e
64
Ph
CHO
Me3Ge
Bu3Sn
SnBu3
6
7
1o
1l
4f
58
51
Me3Ge
Bu3Sn
S
SnBu3
4g
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Synthesis of Substituted Styrenes and Biaryls
2031
Table 4 Synthesis of Type II Styrenes (continued)
Br
Stille[a] or Suzuki[b]
M
+
Ar
Ar
1k–p,r
4a–j
51–77%
M = SnBu3, B(OH)2
Entry
Intermediate II R-M reagent
Product
Yieldc (%)
t-Bu
B(OH)2
8
1r
4h
76
t-Bu
CHO
9
1n
1r
4i
70
75
B(OH)2
F
10
4j
B(OH)2
CHO
a Stille conditions: intermediates 1l–p,r (4 mmol, 1 equiv), organotin (5.2 mmol, 1.3 equiv), Pd(PPh3)4 (3 mol%), toluene, 90 °C, 18 h.
b Suzuki conditions: intermediates 1n,r (4 mmol, 1 equiv), boronic acid (4.8 mmol, 1.2 equiv), Pd(PPh3)4 (3 mol%), EtOH–toluene–H2O, 1 M
Na2CO3, 80 °C, 18 h.
c Yield of isolated product after chromatographic purification.
Table 5 Synthesis of Substituted Biarylsa
Ar
Br
Suzuki[a]
Ar-B(OH)2
+
R
R
1a,b,e–k,m–o,q
5a–o
58–86%
R = aryl, alkenyl
Entry
1
Intermediate
Boronic acids
Product
Yieldb (%)
67
1h
5a
B(OH)2
SnBu3
B(OH)2
2
3
1b
1a
5b
5c
77
77
SiMe3
B(OH)2
SiMe3
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Table 5 Synthesis of Substituted Biarylsa (continued)
Ar
Br
Suzuki[a]
Ar-B(OH)2
+
R
R
1a,b,e–k,m–o,q
5a–o
58–86%
R = aryl, alkenyl
Entry
4
Intermediate
Boronic acids
Product
Yieldb (%)
62
1g
5d
5e
B(OH)2
B(OH)2
GePh3
5
6
7
1e
1j
78
83
77
GeEt3
B(OH)2
5f
t-Bu
B(OH)2
1o
5g
S
B(OH)2
8
1q
5h
82
CHO
F
F
B(OH)2
9
1a
1f
5i
5j
69
73
SiMe3
CHO
O
H
B(OH)2
10
GeEt3
CHO
O
H
B(OH)2
11
12
1i
5k
5l
73
60
t-Bu
B(OH)2
S
S
1k
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Synthesis of Substituted Styrenes and Biaryls
2033
Table 5 Synthesis of Substituted Biarylsa (continued)
Ar
Br
Suzuki[a]
Ar-B(OH)2
+
R
R
1a,b,e–k,m–o,q
5a–o
58–86%
R = aryl, alkenyl
Entry
13
Intermediate
Boronic acids
Product
Yieldb (%)
S
B(OH)2
S
1n
5m
58
F
O2N
O2N
14
15
1k
5n
5o
75
86
B(OH)2
OMe
MeO
B(OH)2
1m
a Suzuki conditions: intermediates 1a,b,e–k,m–o,q (4 mmol, 1 equiv), boronic acid (4.8 mmol, 1.2 equiv), Pd(PPh3)4 (3 mol%), EtOH–toluene–
H2O, 1 M Na2CO3, 80 °C, 18 h.
b Yield of isolated product after chromatographic purification.
vided a very simple and efficient access to differently di-
substituted styrenes and biaryls (heteroaryls).
Br
Br
R
i
ii
In conclusion, we have developed a novel method to syn-
thesize a wide range of differently disubstituted and/or
functionalized styrenes and biaryls. They were obtained in
good yields by a double cross-coupling reaction with very
simple conditions. The first regio- and stereoselective
coupling reaction allowed the substitution of only benzyl-
ic bromide using the Stille or Suzuki condition. The sec-
ond cross-coupling reaction permitted clean substitution
of the aryl bromide in good yields, providing a variety of
styrenes and biaryls. A double one-pot Suzuki reaction is
also possible, styrenes and biaryls also being obtained in
only one step.
Br
6a R = Ph, 52%
6b R = (E)-3,3-dimethylbutenyl, 48%
Scheme 2 Double cross-coupling. Reagents and conditions: (i) p-
TolB(OH)2, Pd(PPh3)4, Na2CO3, EtOH–toluene–H2O, 80 °C, 15 h; (ii)
PhB(OH)2 or (E)-t-BuCH=CHB(OH)2, Pd(PPh3)4, 80 °C, 15 h.
We first performed the substitution of m-benzylic bro-
mide by addition of one equivalent of p-tolylboronic acid.
The reaction was followed by 1H NMR to verify the dis-
appearance of the boronic acid; after 15 hours we intro-
duced the second boronic acid [phenyl- or (E)-3,3-
dimethylbut-2-enylboronic acid]. The reaction was stirred
for a further 15 hours, and we then isolated the differently
disubstituted products (48% yield for styrene 6b and 52%
for biaryl 6a). The symmetrical disubstituted product 4–
6% was found with the first boronic acid. The yields were
not as good as previously, but the products were obtained
in one step which reduced the preparation time. This pro-
1H NMR spectra were recorded on a Bruker AC 200 (200 MHz) us-
ing CDCl3 as solvent. The results, reported using the residual proton
resonance of CDCl3 (δ = 7.26 ppm) as the internal reference. 13C
NMR spectra were recorded at 50.3 MHz on the same instrument
using the CDCl3 solvent peak at δ = 77.0 as reference. 19F NMR
were recorded at 188 MHz in CDCl3 using C6F6 as an external ref-
erence (δ = –164.9 ppm). Mass spectra were obtained on a Hewlett
Packard (engine 5989A) in GC–MS (70 eV) mode. The isotopic
patterns are given for 120Sn (isotopic abundance: 33%) in orga-
nostannyl fragments and for 74Ge (isotopic abundance: 36.6%) in
organogermyl fragments. This means that the reported abundances
(values in brackets) for organostannyl or organogermyl fragments
© Georg Thieme Verlag Stuttgart · New York
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E. Anselmi et al.
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are roughly only one-third of the correct value, taking into account
the 10 isotopes of tin and the five isotopes of germanium compared
with those of the organic fragment. IR spectra were recorded on a
Perkin–Elmer 781 Infrared Spectrophotometer or on a Perkin-
Elmer Spectrum-One. Standard column chromatography was per-
formed on Merck silica gel (60 Å, 230–400 mesh silica gel) or on
neutral alumina. DMF was dried by distillation over CaH2, THF
over Na/benzophenone, and toluene was dried by distillation over
Na prior to use. Compound 1k was commercially available, while
the following are known compounds: 1a,6a 1b,22 1d,6a 1g,6a 1g,6a
1h,6a 1i,6a 1l,23 1m,24 1n,25 1o,26 1p,27 1q,6a 2a,6a 2e,6a 2i,6a 3a,6a 3b,6a
3c,6a 3d,6a 3e,6a 3f,6a 3i,6a 4a,6a 5m.6b
MS (EI, 70 eV): m/z = 329 (M+• – Et, 66), 327 (M+• – Et, 100), 301
(29), 299 (41), 273 (14), 271 (21), 116 (11), 115 (25), 105 (11), 103
(15).
Compounds 1i–r by Suzuki Reaction; General Procedure 2
An oven-dried Schlenk flask equipped with a condenser was evac-
uated and back-filled with argon and charged with EtOH (19 mL),
H2O (5.3 mL), toluene (23 mL), bromobenzyl bromide (3 g, 12
mmol, 1 equiv), and boronic acid (12 mmol, 1 equiv). The flask was
evacuated and back-filled with argon and then 1 M Na2CO3 (13.5
mL) and Pd(PPh3)4 (0.36 mmol, 3 mol%) were added. The mixture
was stirred at the desired temperature until completion of the reac-
tion at the benzylic position. The soln was filtered through Celite
and the solvents were evaporated under reduced pressure. The resi-
due was extracted with Et2O, washed with brine, and dried
(MgSO4). After purification by flash chromatography (silica gel)
the products were characterized.
Compounds 1a–h by Stille Reaction; General Procedure 1
A mixture of bromobenzyl bromide (3 g, 12 mmol, 1 equiv) and
Pd(PPh3)4 (0.36 mmol, 3 mol%) in anhyd toluene (15 mL) was
placed in a dry round-bottomed three-necked flask (50 mL)
equipped with a condenser flushed with argon. Organotin com-
pound (11.5 mmol, 0.95 equiv) was added after stirring for 15 min
at r.t. The mixture was stirred at 80 °C for the recommended time.
After cooling, the mixture was filtered through a Celite, and toluene
was evaporated under reduced pressure. The residue was then treat-
ed with 1 M KF soln and EtOAc to eliminate the Bu3SnF thus
formed. The aqueous layer was extracted with Et2O. The organic
layer was washed with brine and dried (MgSO4). After evaporation
of the solvents, the crude product was purified by column chroma-
tography (silica gel, 100% petroleum ether, previously neutralized
with Et3N).
(E)-1-(3-Bromophenyl)-4,4-dimethylpent-2-ene (1j)
Colorless oil; yield: 2.09 g (69%).
IR (NaCl): 3059, 3024, 1668, 1593, 1568 cm–1.
1H NMR (200 MHz, CDCl3): δ = 1.03 (s, 9 H), 3.30 (d, J = 6.3 Hz,
2 H), 5.43 (dt, J = 15.4, 6.3 Hz, 1 H), 5.59 (d, J = 15.4 Hz, 1 H),
7.09–7.34 (m, 4 H).
13C NMR (50.3 MHz, CDCl3): δ = 30.3 (3 C), 33.5, 39.3, 123.1,
123.1, 127.6, 129.6, 130.4, 132.1, 144.1, 144.4.
MS (EI, 70 eV): m/z = 254 (M+•, 5), 252 (M+•, 5), 239 (2), 237 (2),
211 (3), 209 (3), 115 (12), 83 (100), 70 (15), 57 (25), 41 (30), 39
(17).
(E)-3-(3-Bromophenyl)-1-(trimethylsilyl)prop-1-ene (1c)
Yellow oil; yield: 2.22 g (72%).
Anal. Calcd for C13H17Br: C, 61.67; H, 6.77. Found: C, 61.75; H,
6.73.
IR (NaCl): 3060, 1614, 1595, 1569 cm–1.
1H NMR (200 MHz, CDCl3): δ = 0.07 (s, 9 H), 3.42 (dd, J = 6.1, 1.5
Hz, 2 H), 5.71 (dt, J = 18.4, 1.5 Hz, 1 H), 6.11 (dt, J = 18.4, 6.1 Hz,
1 H), 7.09–7.37 (m, 4 H).
4-(3-Bromobenzyl)benzaldehyde (1r)
White solid; yield: 2.14 g (65%); mp 33–35 °C.
IR (KBr): 3056, 2827, 2736, 1698, 1606, 1595, 1567 cm–1.
13C NMR (50.3 MHz, CDCl3): δ = –0.8 (3 C), 45.2, 122.9, 127.8,
1H NMR (200 MHz, CDCl3): δ = 4.04 (s, 2 H), 7.10–7.41 (m, 6 H),
7.84 (d, J = 8.2 Hz, 2 H), 10.0 (s, 1 H).
13C NMR (50.3 MHz, CDCl3): δ = 42.0, 123.2, 128.1, 130.0 (2 C),
129.5, 130.3, 132.2, 132.8, 142.8, 144.5.
MS (EI, 70 eV): m/z = 270 (M+•, 8), 268 (M+•, 8), 255 (54), 253 (52),
159 (13), 145 (11), 139 (14), 137 (14), 115 (22), 99 (22), 90 (12), 89
(13), 73 (100), 59 (86), 58 (14), 45 (22), 43 (25).
130.1, 130.6 (2 C), 130.7, 132.4, 135.3, 142.6, 147.8, 192.2.
MS (EI, 70 eV): m/z = 276 (M+•, 39), 274 (M+•, 40), 247 (11), 245
(11), 195 (40), 167 (50), 166 (68), 165 (100), 152 (23), 91 (13), 90
(18), 89 (26), 82 (29), 63 (30), 51 (22), 50 (26), 39 (26).
Anal. Calcd for C12H17BrSi: C, 53.53; H, 6.36. Found: C, 53.59; H,
6.30.
(E)-3-(2-Bromophenyl)-1-(triethylgermyl)prop-1-ene (1e)
Yellow oil; yield: 2.74 g (67%).
IR (NaCl): 3060, 1611, 1592, 1568 cm–1.
Anal. Calcd for C14H11BrO: C, 61.11; H, 4.03. Found: C, 61.18; H,
4.10.
1H NMR (200 MHz, CDCl3): δ = 0.79–1.14 (m, 15 H), 3.65 (dd, J =
5.9, 1.2 Hz, 2 H), 5.85 (dt, J = 18.3, 1.2 Hz, 1 H), 6.11 (dt, J = 18.3,
5.9 Hz, 1 H), 7.07–7.31 (m, 3 H), 7.60 (d, J = 7.6 Hz, 1 H).
Compounds 2a–d by Stille Reaction; General Procedure
Using the conditions of general procedure 1, but organostannane
(2.5 equiv) was used.
13C NMR (50.3 MHz, CDCl3): δ = 4.8 (3 C), 9.4 (3 C), 43.7, 125.2,
127.8, 128.1, 129.9, 130.9, 133.2, 140.1, 142.7.
MS (EI, 70 eV): m/z = 329 (M+• – Et, 65), 327 (M+• – Et, 98), 301
(28), 299 (41), 273 (11), 271 (15), 171 (14), 169 (14), 161 (34), 133
(15), 117 (71), 116 (38), 115 (100), 105 (26), 103 (51), 91 (22), 90
(29), 89 (45), 77 (13), 75 (24), 65 (12), 63 (23), 39 (17).
(1E)-1-(Trimethylsilyl)-3-{(E)-2-[2-(trimethylsilyl)vinyl]phe-
nyl}prop-1-ene (2b)
Yellow oil; yield: 2.50 g (72%).
IR (NaCl): 3065, 3017, 1613, 1568 cm–1.
1H NMR (200 MHz, CDCl3): δ = 0.12 (s, 9 H), 0.24 (s, 9 H), 3.62
(dd, J = 5.7, 1.5 Hz, 2 H), 5.72 (dt, J = 18.5, 1.5 Hz, 1 H), 6.21 (dt,
J = 18.5, 5.7 Hz, 1 H), 6.46 (d, J = 19 Hz, 1 H), 7.17–7.31 (m, 4 H),
7.61–7.66 (m, 1 H).
13C NMR (50.3 MHz, CDCl3): δ = –0.7 (6 C), 41.4, 126.0, 127.1,
128.4, 130.5, 131.7, 131.8, 137.4, 138.3, 141.8, 145.1.
(E)-3-(3-Bromophenyl)-1-(triethylgermyl)prop-1-ene (1f)
Colorless oil; yield: 2.70 g (66%).
IR (NaCl): 1639, 1613 cm–1.
1H NMR (200 MHz, CDCl3): δ = 0.73–1.08 (m, 15 H), 3.45 (d, J =
6.0 Hz, 2 H), 5.81 (d, J = 18.3 Hz, 1 H), 6.03 (dt, J = 18.3, 6.0 Hz,
1 H), 7.03–7.35 (m, 4 H).
MS (EI, 70 eV): m/z = 288 (M+•, 10), 214 (12), 141 (10), 73 (100),
72 (14), 59 (39), 45 (17), 43 (12).
13C NMR (50.3 MHz, CDCl3): δ = 4.8 (3 C), 9.4 (3 C), 43.3, 122.9,
127.7, 129.5, 130.0, 130.3, 132.2, 143.1, 143.8.
Anal. Calcd for C17H28Si2: C, 70.76; H, 9.78. Found: C, 70.82; H,
9.72.
Synthesis 2012, 44, 2023–2040
© Georg Thieme Verlag Stuttgart · New York

PAPER
Synthesis of Substituted Styrenes and Biaryls
2035
(1E)-1-(Trimethylsilyl)-3-{(E)-3-[2-(trimethylsilyl)vinyl]phe-
nyl}prop-1-ene (2c)
Anal. Calcd for C21H20: C, 92.60; H, 7.40. Found: C, 92.75; H, 7.34.
Colorless oil; yield: 2.42 g (70%).
2-[2-(Thiophen-2-yl)benzyl]thiophene (2h)
Colorless oil; yield: 1.81 g (59%).
IR (NaCl): 3104, 3067, 3018, 1599, 1532 cm–1.
1H NMR (200 MHz, CDCl3): δ = 4.26 (s, 2 H), 6.67 (dd, J = 3.4, 1.1
Hz, 1 H), 6.91 (dd, J = 5.1, 3.4 Hz, 1 H), 7.00 (dd, J = 3.5, 1.1 Hz,
1 H), 7.07 (dd, J = 5.1, 3.5 Hz, 1 H), 7.15 (dd, J = 5.1, 1.1 Hz, 1 H),
7.30–7.46 (m, 5 H).
13C NMR (50.3 MHz, CDCl3): δ = 34.4, 124.4, 125.7, 126.1, 127.3
(3 C), 127.7, 128.8, 130.9, 131.8, 134.6, 139.0, 142.7, 144.9.
IR (NaCl): 3057, 3022, 1611, 1579 cm–1.
1H NMR (200 MHz, CDCl3): δ = 0.07 (s, 9 H), 0.17 (s, 9 H), 3.45
(dd, J = 6.2, 1.5 Hz, 2 H), 5.71 (dt, J = 18.4, 1.5 Hz, 1 H), 6.16 (dt,
J = 18.4, 6.2 Hz, 1 H), 6.48 (d, J = 19.1 Hz, 1 H), 6.88 (d, J = 19.1
Hz, 1 H), 7.07–7.30 (m, 4 H).
13C NMR (50.3 MHz, CDCl3): δ = –0.8 (6 C), 43.6, 124.5, 127.2,
128.8, 129.0, 129.8, 132.0, 138.9, 140.7, 144.1, 145.5.
MS (EI, 70 eV): m/z = 288 (M+•, 26), 273 (31), 215 (17), 199 (10),
185 (13), 183 (23), 129 (11), 85 (18), 73 (100), 59 (66), 45 (18), 43
(10).
MS (EI, 70 eV): m/z = 256 (M+•, 100), 223 (88), 184 (26), 171 (28),
115 (10), 97 (17), 45 (22), 39 (10).
Anal. Calcd for C15H12S2: C, 70.27; H, 4.72. Found: C, 70.38; H,
4.60.
Anal. Calcd for C17H28Si2: C, 70.76; H, 9.78. Found: C, 70.86; H,
9.83.
Compounds 3a–l by Stille Reaction; General Procedure 3
A mixture of intermediate I 1a–h,j (4 mmol, 1 equiv) and Pd(PPh3)4
(0.12 mmol, 3 mol%) in anhyd toluene (5 mL) was placed in a dry
Schlenk equipped with a condenser flushed with argon. Organotin
compound (5.2 mmol, 1.3 equiv) was added after stirring for 15 min
at r.t. The mixture was stirred at 90 °C for 18 h. After cooling, the
mixture was filtered through Celite, and toluene was evaporated un-
der reduced pressure. The residue was then treated with 1 M KF
soln and EtOAc to eliminate the Bu3SnF thus formed. The aqueous
layer was extracted with Et2O. The organic layer was washed with
brine and dried (MgSO4). After evaporation of the solvents, the
crude product was purified by column chromatography (silica gel,
100% petroleum ether, previously neutralized with Et3N).
(1E)-1-(Triethylgermyl)-3-{(E)-2-[2-(triethylgermyl)vinyl]phe-
nyl}prop-1-ene (2d)
Colorless oil; yield: 3.54 g (64%).
IR (NaCl): 3063, 1609, 1565 cm–1.
1H NMR (200 MHz, CDCl3): δ = 0.73–1.13 (m, 30 H), 3.56 (dd, J =
5.7, 1.4 Hz, 2 H), 5.72 (dt, J = 18.3, 1.4 Hz, 1 H), 6.06 (dt, J = 18.3,
5.7 Hz, 1 H), 6.50 (d, J = 18.8 Hz, 1 H), 7.10 (d, J = 18.8 Hz, 1 H),
7.12–7.24 (m, 3 H), 7.55 (d, J = 8.9 Hz, 1 H).
13C NMR (50.3 MHz, CDCl3): δ = 4.7 (3 C), 4.9 (3 C), 9.4 (3 C), 9.5
(3 C), 41.2, 126.1, 126.9, 128.0, 128.6, 130.0, 130.3, 137.3, 138.4,
141.7, 144.4.
MS (EI, 70 eV): m/z = 435 (M+• – 29, 2), 303 (7), 302 (7), 301 (6),
273 (100), 245 (23), 217 (53), 161 (52), 133 (53), 105 (34), 103
(39).
(1E)-1-(Triethylgermyl)-3-{3-[(E)-2-(trimethylsilyl)vinyl]phe-
nyl}prop-1-ene (3g)
Colorless oil; yield: 1.05 g (70%).
IR (NaCl): 3055, 1608, 1578 cm–1.
1H NMR (200 MHz, CDCl3): δ = 0.19 (s, 9 H), 0.79–1.11 (m, 15 H),
3.50 (d, J = 6.1 Hz, 2 H), 5.82 (d, J = 18.2 Hz, 1 H), 6.09 (dt, J =
18.2, 6.2 Hz, 1 H), 6.49 (d, J = 19.2 Hz, 1 H), 6.90 (d, J = 19.2 Hz,
1 H), 7.10–7.30 (m, 4 H).
13C NMR (50.3 MHz, CDCl3): δ = –0.8 (3 C), 4.8 (3 C), 9.4 (3 C),
43.7, 124.6, 127.0, 128.8, 129.0, 129.1, 129.7, 138.9, 140.9, 144.1,
144.8.
Compounds 2e–i by Suzuki Reaction; General Procedure
Using the conditions of general procedure 2, but boronic acid (2.2
equiv) was used.
4-Fluoro-4′-(4-fluorobenzyl)biphenyl (2f)
White solid; yield: 2.65 g (79%); mp 64–66 °C.
IR (KBr): 3053, 1603, 1508 cm–1.
1H NMR (200 MHz, CDCl3): δ = 4.08 (s, 2 H), 7.04–7.35 (m, 8 H),
7.55–7.62 (m, 4 H).
2
13C NMR (50.3 MHz, CDCl3): δ = 41.2, 115.8 (d, JC-F = 21 Hz),
MS (EI, 70 eV): m/z = 376 (M+•, 6), 347 (100), 319 (18), 199 (14),
183 (26), 145 (11), 138 (20), 133 (12), 115 (13), 105 (23), 103 (24),
89 (10), 87 (15), 73 (67), 59 (52), 45 (13).
116.1 (d, 2JC-F = 21 Hz), 127.6 (2 C), 129.0 (d, 3JC-F = 8 Hz), 129.8
(2 C), 130.9 (d, 3JC-F = 8 Hz), 137.2, 137.5, 138.7, 140.6, 162.0 (d,
1JC-F = 244 Hz), 162.9 (d, 1JC-F = 246 Hz).
(2E)-4,4-Dimethyl-1-{3-[(E)-(trimethylsilyl)vinyl]phenyl}pent-
2-ene (3h)
Yellow oil; yield: 0.79 g (73%).
IR (NaCl): 3029, 1607, 1599, 1579, 1534 cm–1.
1H NMR (200 MHz, CDCl3): δ = 0.20 (s, 9 H), 1.06 (s, 9 H), 3.36
(d, J = 5.8 Hz, 2 H), 5.42–5.66 (m, 2 H), 6.50 (d, J = 19.2 Hz, 1 H),
6.91 (d, J = 19.2 Hz, 1 H), 7.09–7.31 (m, 4 H).
19F NMR (188 MHz, CDCl3): δ = –116.4, –117.7.
MS (EI, 70 eV): m/z = 280 (M+•, 100), 279 (21), 185 (33), 184 (24),
183 (73), 170 (29), 165 (21), 133 (27), 109 (76), 107 (17), 83 (35),
75 (24), 63 (19), 57 (19), 39 (20).
Anal. Calcd for C19H14F2: C, 81.41; H, 5.03. Found: C, 81.47; H,
5.08.
13C NMR (50.3 MHz, CDCl3): δ = –0.8 (3 C), 30.2 (3 C), 33.4, 39.5,
123.8, 124.4, 127.0, 128.6, 128.9, 129.7, 138.8, 141.9, 143.6, 144.2.
4′-Methyl-2-(4-methylbenzyl)biphenyl (2g)
Colorless oil; yield: 2.84 g (87%).
MS (EI, 70 eV): m/z = (M+•, 35), 257 (28), 142 (10), 141 (60), 99
(10), 97 (57), 83 (32), 73 (67), 69 (25), 59 (52), 57 (17), 55 (100),
45 (12), 43 (18), 41 (22).
IR (NaCl): 3050, 3021, 1599, 1573, 1514 cm–1.
1H NMR (200 MHz, CDCl3): δ = 2.46 (s, 3 H), 2.55 (s, 3 H), 4.11
(s, 2 H), 7.09 (d, J = 7.9 Hz, 2 H), 7.21 (d, J = 7.9 Hz, 2 H), 7.36–
7.44 (m, 8 H).
13C NMR (50.3 MHz, CDCl3): δ = 21.6, 21.8, 39.1, 126.6, 127.9,
129.4 (4 C), 129.6 (2 C), 129.8 (2 C), 130.7, 130.8, 135.7, 137.0,
139.1 (2 C), 139.4, 142.7.
Anal. Calcd for C18H28Si: C, 79.34; H, 10.36. Found: C, 79.45; H,
10.28.
(1E)-3-{2-[(E)-2-Phenylvinyl]phenyl}-1-(trimethylsilyl)prop-1-
ene (3j)
MS (EI, 70 eV): m/z = 272 (M+•, 100), 257 (35), 242 (10), 180 (26),
179 (46), 178 (16), 166 (12), 165 (51).
Yellow oil; yield: 0.76 g (65%).
IR (NaCl): 3060, 3025, 1612, 1581 cm–1.
© Georg Thieme Verlag Stuttgart · New York
Synthesis 2012, 44, 2023–2040

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E. Anselmi et al.
PAPER
1H NMR (200 MHz, CDCl3): δ = 0.04 (s, 9 H), 3.61 (br dd, J = 5.7,
1.6 Hz, 2 H), 5.71 (dt, J = 18.5, 1.6 Hz, 1 H), 6.18 (dt, J = 18.5, 5.7
Hz, 1 H), 6.98 (d, J = 18.9 Hz, 1 H), 7.16–7.67 (m, 10 H).
13C NMR (50.3 MHz, CDCl3): δ = –0.7 (3 C), 41.6, 126.2, 127.0 (2
C), 127.2 (2 C), 128.1, 128.2, 129.2 (2 C), 130.5, 130.7, 132.2,
137.2, 138.0, 138.3, 145.1.
MS (EI, 70 eV): m/z = 272 (M+•, 27), 257 (13), 159 (25), 85 (19), 73
(100), 59 (54), 45 (11).
Anal. Calcd for C18H28Si: C, 79.34; H, 10.36. Found: C, 79.38; H,
10.41.
Compounds 4a–g by Stille Reaction; General Procedure
Using the conditions for general procedure 3, but using intermedi-
ates II 1k–p,r.
MS (EI, 70 eV): m/z = 292 (M+•, 11), 218 (26), 129 (18), 116 (16),
91 (10), 73 (100), 59 (24), 45 (13).
2-{[2-(4-Methylbenzyl)]phenyl}propene (4b)
Anal. Calcd for C20H24Si: C, 82.13; H, 8.27. Found: C, 82.19; H,
8.30.
Colorless oil; yield: 0.59 g (67%).
IR (NaCl): 3049, 3019, 1640, 1599, 1514 cm–1.
(1E)-3-{2-[(E)-2-Phenylvinyl]phenyl}-1-(triethylgermyl)prop-
1-ene (3k)
Colorless oil; yield: 0.94 g (62%).
IR (NaCl): 3026, 1609, 1589 cm–1.
1H NMR (200 MHz, CDCl3): δ = 0.69–1.03 (m, 15 H), 3.62 (dd, J =
5.6, 1.4 Hz, 2 H), 5.78 (dt, J = 18.4, 1.4 Hz, 1 H), 6.09 (dt, J = 18.4,
5.6 Hz, 1 H), 6.99 (d, J = 16.2 Hz, 1 H), 7.13–7.66 (m, 10 H).
13C NMR (50.3 MHz, CDCl3): δ = 4.9 (3 C), 9.5 (3 C), 41.7, 126.2,
127.1 (2 C), 127.2 (2 C), 128.1, 128.2, 129.2 (3 C), 130.5, 130.6,
137.2, 138.2, 138.3, 144.5.
1H NMR (200 MHz, CDCl3): δ = 1.99 (t, J = 1.2 Hz, 3 H), 2.33 (s,
3 H), 4.02 (s, 2 H), 4.85–4.87 (m, 1 H), 5.18–5.21 (m, 1 H), 7.01–
7.23 (m, 8 H).
13C NMR (50.3 MHz, CDCl3): δ = 21.5, 25.7, 38.7, 115.6, 126.4,
127.4, 128.6, 129.3 (2 C), 129.5 (2 C), 130.6, 135.7, 138.0, 139.0,
144.4, 145.9.
MS (EI, 70 eV): m/z = 222 (M+•, 21), 208 (18), 207 (100), 193 (16),
192 (89), 191 (14), 178 (10), 129 (10), 115 (16), 91 (8).
Anal. Calcd for C17H18: C, 91.84; H, 8.16. Found: C, 91.79; H, 8.19.
MS (EI, 70 eV): m/z = 380 (M+•, 9), 351 (49), 235 (28), 218 (65),
217 (100), 202 (19), 203 (20), 161 (23), 133 (28), 129 (46), 115
(23), 105 (33), 103 (37), 91 (76), 77 (10).
2-(2-Isopropenylbenzyl)thiophene (4c)
Colorless oil; yield: 0.54 g (63%).
IR (NaCl): 3069, 3011, 1640, 1601, 1533 cm–1.
1H NMR (200 MHz, CDCl3): δ = 2.12 (s, 3 H), 4.31 (s, 2 H), 4.99
(br s, 1 H), 5.33 (br s, 1 H), 6.83 (dd, J = 3.4, 1.1 Hz, 1 H), 7.00 (dd,
J = 5.1, 3.4 Hz, 1 H), 7.20–7.34 (m, 5 H).
(1E)-3-{3-[(E)-2-Phenylvinyl]phenyl}-1-(trimethylsilyl)prop-1-
ene (3l)
White solid; yield: 0.73 g (63%); mp 57–59 °C.
IR (KBr): 3081, 3030, 1613, 1601, 1582 cm–1.
13C NMR (50.3 MHz, CDCl3): δ = 25.8, 33.6, 115.9, 124.2, 125.6,
1H NMR (200 MHz, CDCl3): δ = 0.09 (s, 9 H), 3.49 (d, J = 6.1 Hz,
2 H), 5.75 (dt, J = 18.4, 1.5 Hz, 1 H), 6.19 (dt, J = 18.4, 6.2 Hz, 1
H), 7.11–7.13 (m, 2 H), 7.30–7.42 (m, 7 H), 7.54 (d, J = 8.1 Hz, 2
H).
13C NMR (50.3 MHz, CDCl3): δ = –0.6 (3 C), 43.7, 124.8, 127.0 (2
C), 127.5, 128.1, 128.7, 129.2 (2 C), 129.3 (3 C), 132.2, 137.9,
138.0, 140.9, 145.5.
127.0, 127.2, 127.6, 128.7, 130.4, 137.3, 144.1, 144.4, 145.5.
MS (EI, 70 eV): m/z = 214 (M+•, 42), 199 (15), 185 (100), 165 (22),
152 (10), 129 (13), 115 (28), 97 (12), 45 (11), 39 (13).
Anal. Calcd for C14H14S: C, 78.46; H, 6.58. Found: C, 78.34; H,
6.63.
(E)-[2-(4-Benzylphenyl)vinyl]trimethylsilane (4d)
Yellow oil; yield: 0.82 g (77%).
IR (NaCl): 3026, 1605, 1565, 1509 cm–1.
MS (EI, 70 eV): m/z = 292 (M+•, 100), 277 (29), 218 (22), 202 (10),
179 (13), 178 (17), 135 (14), 73 (99), 59 (55), 45 (14).
Anal. Calcd for C20H24Si: C, 82.13; H, 8.27. Found: C, 82.05; H,
8.25.
1H NMR (200 MHz, CDCl3): δ = 0.28 (s, 9 H), 4.07 (s, 2 H), 6.55
(d, J = 19.1 Hz, 1 H), 6.98 (d, J = 19.1 Hz, 1 H), 7.24–7.43 (m, 8 H),
7.48 (d, J = 8.1 Hz, 1 H).
Compound 3m by Suzuki Reaction; General Procedure 4
An oven-dried Schlenk flask equipped with a condenser was evac-
uated and back-filled with argon and charged with EtOH (6.3 mL),
H2O (1.8 mL), toluene (7.7 mL), intermediate I 1c (4 mmol, 1
equiv), and boronic acid (4.8 mmol, 1.2 equiv). The flask was evac-
uated and back-filled with argon and then 1 M Na2CO3 (4.5 mL) and
Pd(PPh3)4 (0.12 mmol, 3 mol%) were added. The mixture was
stirred at 80 °C for 18 h. The soln was filtered through a Celite path
and the solvents were evaporated under reduced. The residue was
extracted with Et2O, washed with brine, and dried (MgSO4). After
purification by flash chromatography (silica gel) the products were
characterized.
13C NMR (50.3 MHz, CDCl3): δ = –6.6 (3 C), 42.2, 126.6, 127.0 (2
C), 129.0 (2 C), 129.3, 129.4 (2 C), 129.7 (2 C), 136.9, 141.5, 141.6,
143.9.
MS (EI, 70 eV): m/z = 266 (M+•, 9), 175 (12), 135 (21), 91 (100), 59
(30), 45 (10).
Anal. Calcd for C18H22Si: C, 81.14; H, 8.32. Found: C, 81.03; H,
8.38.
4-{3-[(1E)-2-Phenylvinyl]benzyl}benzaldehyde (4e)
White solid; yield: 0.76 g (64%); mp 72–74 °C.
IR (KBr): 3054, 1701, 1601, 1574, 1167 cm–1.
1H NMR (200 MHz, CDCl3): δ = 4.10 (s, 2 H), 7.10–7.14 (m, 2 H),
7.30–7.57 (m, 11 H), 7.86 (d, J = 8.20 Hz, 2 H), 10.01 (s, 1 H).
13C NMR (50.3 MHz, CDCl3): δ = 42.5, 125.1, 127.0 (2 C), 127.7,
128.2, 128.8, 128.9, 129.1 (2 C), 129.4, 129.5, 130.0 (2 C), 130.5 (2
C), 135.2, 137.6, 138.2, 140.6, 148.7, 192.1.
MS (EI, 70 eV): m/z = 298 (M+•, 100), 191 (13), 189 (10), 180 (13),
179 (89), 178 (40), 165 (15), 152 (10), 115 (10), 91 (35), 77 (11), 51
(10), 39 (10).
(1E)-3,3-Dimethyl-1-{3-[(E)-3-(trimethylsilyl)prop-2-enyl]phe-
nyl}but-1-ene (3m)
Colorless oil; yield: 0.80 g (74%).
IR (NaCl): 3026, 1613, 1602, 1582, 1363 cm–1.
1H NMR (200 MHz, CDCl3): δ = 0.07 (s, 9 H), 1.14 (s, 9 H), 3.45
(d, J = 6.2 Hz, 2 H), 5.72 (d, J = 18.4 Hz, 1 H), 6.17 (dt, J = 18.4,
6.2 Hz, 1 H), 6.27–6.29 (m, 2 H), 7.01–7.28 (m, 4 H).
13C NMR (50.3 MHz, CDCl3): δ = –0.4 (3 C), 30.3 (3 C), 34.0, 43.9,
124.5, 125.4, 127.2, 127.9, 129.2, 132.0, 138.7, 140.7, 142.2, 144.5.
Anal. Calcd for C22H18O: C, 88.56; H, 6.08. Found: C, 88.48; H,
6.01.
Synthesis 2012, 44, 2023–2040
© Georg Thieme Verlag Stuttgart · New York

PAPER
Synthesis of Substituted Styrenes and Biaryls
2037
2-{4-[(E)-2-(Trimethylgermyl)vinyl]benzyl}thiophene (4f)
1H NMR (200 MHz, CDCl3): δ = 1.87 (dd, J = 7.1, 1.8 Hz, 3 H),
4.07 (s, 2 H), 5.79 (dq, J = 11.6, 7.1 Hz, 1 H), 6.41 (dq, J = 11.6, 1.8
Hz, 1 H), 7.03–7.40 (m, 6 H), 7.82 (d, J = 8.1 Hz, 2 H), 9.99 (s, 1 H).
13C NMR (50.3 MHz, CDCl3): δ = 15.1, 42.5, 127.5 (3 C), 128.9,
130.0 (3 C), 130.1, 130.5 (2 C), 135.2, 138.5, 140.1, 148.8, 192.3.
MS (EI, 70 eV): m/z = 236 (M+•, 100), 207 (11), 179 (24), 178 (25),
166 (10), 165 (28), 129 (12), 120 (69), 118 (11), 117 (87), 115 (43),
91 (43), 90 (14), 89 (26), 76 (10), 65 (13), 63 (10), 39 (15).
Colorless oil; yield: 0.73 g (58%).
IR (NaCl): 3078, 3047, 1604, 1565, 1509 cm–1.
1H NMR (200 MHz, CDCl3): δ = 0.39 (s, 9 H), 4.21 (s, 2 H), 6.73
(d, J = 19 Hz, 1 H), 6.87 (dd, J = 3.4, 1.2 Hz, 1 H), 6.91 (d, J = 19
Hz, 1 H), 7.00 (dd, J = 5.1, 3.4 Hz, 1 H), 7.22 (dd, J = 5.1, 1.2 Hz,
1 H), 7.29 (d, J = 8.1 Hz, 2 H), 7.46 (d, J = 8.1 Hz, 2 H).
13C NMR (50.3 MHz, CDCl3): δ = –1.12 (3 C), 36.3, 124.5, 125.7,
127 (2 C), 127.3, 129.4 (2 C), 131.2, 137.1, 140.5, 142.4, 144.6.
MS (EI, 70 eV): m/z = 318 (M+•, 8), 303 (M+• – 15, 7), 115 (6), 97
Anal. Calcd for C17H16O: C, 86.40; H, 6.82. Found: C, 86.45; H,
6.80.
(100).
Substituted Biaryls 5; General Procedure
Using the conditions for general procedure 4, but using intermedi-
ates I or II 1a,b,e–k,m–o,q.
1-(4-Methylbenzyl)-4-[(1E)-2-(tributylstannyl)vinyl]benzene
(4g)
Yellow oil; yield: 1.01 g (51%).
4-[(2E)-3-(Tributylstannyl)prop-2-enyl]biphenyl (5a)
Colorless oil; yield: 1.30 g (67%).
IR (NaCl): 1607, 1593, 1508 cm–1.
1H NMR (200 MHz, CDCl3): δ = 0.91 (t, J = 7.2 Hz, 9 H), 1.29–1.60
(m, 18 H), 2.33 (s, 3 H), 3.94 (s, 2 H), 6.82–8.84 (m, 2 H), 7.09–7.37
(m, 8 H).
1H NMR (200 MHz, CDCl3): δ = 0.92 (t, J = 7.1 Hz, 9 H), 1.28–1.61
(m, 18 H), 3.56 (d, 3J1H = 5.8 Hz, 2 H), 6.00–6.15 (m, 2 H), 7.23–
7.66 (m, 9 H).
13C NMR (50.3 MHz, CDCl3): δ = 10.2 (1JSn-C = 328–344 Hz, 3 C),
14.4 (3 C), 21.6, 27.9 (3JSn-C = 54 Hz, 3 C), 29.6 (2JSn-C = 21 Hz, 3
C), 41.8, 126.7 (2 C), 129.0, 129.4 (2 C), 129.6 (2 C), 129.7 (2 C),
136.0, 137.3, 138.6, 141.4, 146.5.
13C NMR (50.3 MHz, CDCl3): δ = 9.9 (1JSn-C = 345–389 Hz, 3 C),
14.2 (3 C), 27.8 (3JSn-C = 54 Hz, 3 C), 29.6 (2JSn-C = 21 Hz, 3 C),
44.6, 127.5 (2 C), 127.6 (2 C), 128.7, 129.2 (2 C), 129.5 (2 C),
130.2, 139.5, 139.9, 141.6, 145.1.
MS (EI, 70 eV): m/z = 441 (M+• – 57, 90), 385 (31), 325 (26), 191
(26), 179 (20), 177 (20), 165 (12), 163 (14), 121 (25), 105 (100), 91
(20), 57 (18), 41 (46), 39 (15).
119Sn NMR (74.2 MHz, CDCl3): δ = –47.2.
MS (EI, 70 eV): m/z = 427 (M+• – 57, 100), 371 (47), 315 (51), 193
(16), 178 (10), 167 (16), 157 (18), 41 (10).
Compounds 4h–j by Suzuki Reaction; General Procedure
Using the conditions for general procedure 4, but using intermedi-
ates II 1n,r.
2-[(2E)-3-(Trimethylsilyl)prop-2-enyl]biphenyl (5b)
Colorless oil; yield: 0.82 g (77%).
IR (NaCl): 3060, 3023, 1613, 1583, 1501 cm–1.
(E)-4-[3-(3,3-Dimethylbut-1-enyl)benzyl]benzaldehyde (4h)
Yellow oil; yield: 0.84 g (76%).
IR (NaCl): 1704, 1602, 1576 cm–1.
1H NMR (200 MHz, CDCl3): δ = 0.03 (s, 9 H), 3.41 (dd, J = 5.9, 1.6
Hz, 2 H), 5.50 (dt, J = 18.5, 1.6 Hz, 1 H), 6.06 (dt, J = 18.5, 5.9 Hz,
1 H), 7.25–7.44 (m, 9 H).
1H NMR (200 MHz, CDCl3): δ = 1.16 (s, 9 H), 4.06 (s, 2 H), 6.30–
6.32 (br s, 2 H), 7.01–7.06 (m, 1 H), 7.23–7.30 (m, 3 H), 7.38 (d, J =
8.1 Hz, 2 H), 7.83 (d, J = 8.1 Hz, 2 H), 10 (s, 1 H).
13C NMR (50.3 MHz, CDCl3): δ = –0.6 (3 C), 41.2, 126.7, 127.4,
128.0, 128.5 (2 C), 129.8 (2 C), 130.5, 130.6, 131.9, 137.8, 142.2,
142.7, 145.9.
13C NMR (50.3 MHz, CDCl3): δ = 30.1 (3 C), 33.9, 42.5, 124.6,
124.9, 127.3, 127.9, 129.3, 130.0 (2 C), 130.5 (2 C), 135.1, 138.9,
140.3, 142.5, 148.9, 192.4.
MS (EI, 70 eV): m/z = 266 (M+•, 23), 251 (28), 233 (29), 192 (43),
191 (21), 179 (18), 165 (27), 73 (100), 59 (45), 58 (12), 45 (16), 43
(15).
MS (EI, 70 eV): m/z = 278 (M+•, 52), 263 (21), 165 (11), 159 (46),
144 (18), 143 (20), 129 (17), 128 (15), 120 (19), 119 (92), 117 (17),
115 (12), 91 (100), 89 (13), 65 (10), 41 (21), 39 (11).
Anal. Calcd for C18H22Si: C, 81.14; H, 8.32. Found: C, 81.18; H,
8.34.
4-Methyl-4′-[(2E)-3-(trimethylsilyl)prop-2-enyl]biphenyl (5c)
Anal. Calcd for C20H22O: C, 86.29; H, 7.97. Found: C, 86.38; H,
8.06.
Yellow oil; yield: 0.86 g (77%).
IR (NaCl): 3024, 1609, 1561 cm–1.
(Z)-1-[4-(4-Fluorobenzyl)phenyl]prop-1-ene (4i)
Yellow oil; yield: 0.63 g (70%).
IR (NaCl): 3041, 1630, 1602, 1570, 1510 cm–1.
1H NMR (200 MHz, CDCl3): δ = 0.21 (s, 9 H), 2.50 (s, 3 H), 3.59
(d, J = 6.2 Hz, 2 H), 5.87 (d, J = 18.4 Hz, 1 H), 6.30 (dt, J = 18.4,
6.2 Hz, 1 H), 7.34 (d, J = 7.9 Hz, 4 H), 7.60 (d, J = 7.9 Hz, 4 H).
1H NMR (200 MHz, CDCl3): δ = 1.98 (dd, J = 7.2, 1.8 Hz, 3 H),
4.01 (s, 2 H), 5.85 (dq, J = 11.6, 1.8 Hz, 1 H), 6.50 (dq, J = 11.6, 1.8
Hz, 1 H), 7.01–7.31 (m, 6 H), 7.52 (d, J = 8.2 Hz, 2 H).
13C NMR (50.3 MHz, CDCl3): δ = –0.64 (3 C), 21.6, 43.4, 127.4 (2
C), 127.5 (2 C), 129.6 (2 C), 130.0 (2 C), 132.1, 137.2, 138.7, 139.3,
139.4, 145.6.
13C NMR (50.3 MHz, CDCl3): δ = 15.2, 41.3, 115.7 (d, 2JC-F = 21
Hz, 2 C), 125.8, 128.7 (2 C), 129.5 (2 C), 130.1, 130.8 (d, 3JC-F = 7.5
Hz, 2 C), 136.2, 137.3, 139.6, 162.0 (d, 1JC-F = 243 Hz).
MS (EI, 70 eV): m/z = (M+•, 100), 211 (47), 197 (30), 196 (23), 185
(13), 183 (21), 165 (11), 133 (11), 117 (54), 115 (34), 109 (39), 99
(21), 98 (14), 91 (18), 83 (14), 39 (13).
MS (EI, 70 eV): m/z = 280 (M+•, 12), 265 (4), 73 (100), 59 (45), 45
(13).
Anal. Calcd for C19H24Si: C, 81.36; H, 8.62. Found: C, 81.23; H,
8.68.
4-Methyl-4′-[(2E)-3-(triphenylgermyl)prop-2-enyl]biphenyl
(5d)
White solid; yield: 1.25 g (62%); mp 96–98 °C.
IR (KBr): 3068, 3048, 1607, 1584, 1570 cm–1.
Anal. Calcd for C16H15F: C, 84.92; H, 6.68. Found: C, 84.84; H,
6.75.
4-[(Z)-3-(Prop-1-enyl)benzyl]benzaldehyde (4j)
Yellow oil; yield: 0.70 g (75%).
1H NMR (200 MHz, CDCl3): δ = 2.47 (s, 3 H), 3.70 (d, J = 6.0 Hz,
2 H), 6.39–6.42 (m, 2 H), 7.30–7.63 (m, 23 H).
© Georg Thieme Verlag Stuttgart · New York
Synthesis 2012, 44, 2023–2040

2038
E. Anselmi et al.
PAPER
13C NMR (50.3 MHz, CDCl3): δ = 21.6, 43.2, 126.1, 127.3 (2 C),
127.5 (2 C), 128.7 (6 C), 129.5 (3 C), 129.6 (2 C), 130.0 (2 C), 137.6
(6 C), 137.1 (3 C), 137.3, 138.6, 138.8, 139.5, 148.9.
(E)-[3-(4′-Fluorobiphenyl-4-yl)prop-1-enyl]trimethylsilane (5i)
White solid; yield: 0.78 g (69%); mp 34–36 °C
IR (KBr): 3029, 1606 cm–1.
MS (EI, 70 eV): m/z = 512 (M+•, 8), 435 (11), 331 (36), 305 (55),
284 (29), 229 (69), 228 (100), 207 (24), 206 (24), 205 (17), 192
(46), 191 (29), 181 (27), 165 (43), 151 (74), 115 (33), 91 (38), 78
(12), 77 (15), 51 (18), 39 (10).
1H NMR (200 MHz, CDCl3): δ = 0.15 (s, 9 H), 3.55 (d, J = 6.1 Hz,
2 H), 5.82 (dt, J = 18.4, 1.5 Hz, 1 H), 6.26 (dt, J = 18.4, 6.1 Hz, 1
H), 7.17 (dd, JH-F = 8.7 Hz, 2 H), 7.31 (d, J = 8.3 Hz, 2 H), 7.51–
7.63 (m, 4 H).
13C NMR (50.3 MHz, CDCl3): δ = –0.7 (3 C), 43.3, 116.0 (d, 2JC-F
=
4′-Methyl-2-[(2E)-3-(triethylgermyl)prop-2-enyl]biphenyl (5e)
Yellow oil; yield: 1.14 g (78%).
21 Hz, 2 C), 127.5 (2 C), 129.0 (d, 3JC-F = 8 Hz, 2 C), 129.7 (2 C),
132.2, 137.6, 138.5, 139.6, 145.4, 162.8 (d, 1JC-F = 245 Hz).
19F NMR (188 MHz, CDCl3): δ = –116.5.
MS (EI, 70 eV): m/z = 284 (M+•, 12), 192 (12), 191 (16), 73 (100),
59 (64), 58 (12), 45 (23), 43 (19).
IR (NaCl): 3058, 3021, 1611, 1586, 1516 cm–1.
1H NMR (200 MHz, CDCl3): δ = 0.77–1.15 (m, 15 H), 2.49 (s, 3 H),
3.53 (dd, J = 5.9, 1.5 Hz, 2 H), 5.71 (dt, J = 18.3, 1.5 Hz, 1 H), 6.09
(dt, J = 18.3, 5.9 Hz, 1 H), 7.30–7.39 (m, 8 H).
13C NMR (50.3 MHz, CDCl3): δ = 4.8 (3 C), 9.4 (3 C), 21.7, 41.2,
126.5, 127.7, 128.7, 129.1 (2 C), 129.6 (2 C), 130.3, 130.6, 136.9,
137.9, 139.3, 142.5, 145.3.
MS (EI, 70 eV): m/z = 368 (M+•, 9), 339 (100), 311 (19), 283 (5),
281 (13), 207 (21), 206 (13), 205 (42), 192 (23), 191 (21), 179 (22),
178 (22), 165 (39), 133 (10), 105 (10), 103 (12).
Anal. Calcd for C18H21FSi: C, 76.01; H, 7.44. Found: C, 76.15; H,
7.48.
3′-[(E)-3-(Triethylgermyl)prop-2-enyl]biphenyl-4-carbalde-
hyde (5j)
Colorless oil; yield: 1.11 g (73%).
IR: 3058, 3027, 1703, 1604, 1567 cm–1.
1H NMR (200 MHz, CDCl3): δ = 0.78–1.09 (m, 15 H), 3.57 (d, J =
6.0 Hz, 2 H), 5.86 (dt, J = 18.3, 1.2 Hz, 1 H), 6.11 (dt, J = 18.3, 6.0
Hz, 1 H), 7.24–7.52 (m, 4 H), 7.76 (d, J = 8.2 Hz, 2 H), 7.96 (d, J =
8.2 Hz, 2 H), 10.07 (s, 1 H).
3-[(E)-4,4-Dimethylpent-2-enyl]-4′-methylbiphenyl (5f)
Yellow oil; yield: 0.87 g (83%).
1H NMR (200 MHz, CDCl3): δ = 1.11 (s, 9 H), 2.46 (s, 3 H), 3.46
(d, J = 5.6 Hz, 2 H), 5.53–5.73 (m, 2 H), 7.20–7.58 (m, 8 H)
13C NMR (50.3 MHz, CDCl3): δ = 4.8 (3 C), 9.3 (3 C), 43.7, 125.5,
128.1 (3 C), 129.3, 129.5, 129.6, 130.6 (2 C), 135.6, 140.2, 141.6,
144.4, 147.8, 192.3.
13C NMR (50.3 MHz, CDCl3): δ = 21.6, 30.2 (3 C), 33.4, 39.6,
123.8, 125.1, 127.5 (2 C), 127.6 (2 C), 129.1, 129.9 (2 C), 137.4,
139.0, 141.7, 142.2, 143.8.
MS (EI, 70 eV): m/z = 382 (M+•, 3), 353 (100), 325 (31), 297 (13),
219 (27), 207 (86), 205 (30), 191 (16), 189 (19), 178 (30), 165 (38),
152 (22), 148 (18), 147 (14), 133 (19), 115 (10), 105 (28), 103 (33),
77 (11), 75 (14).
MS (EI, 70 eV): m/z = 264 (M+•, 67), 221 (11), 208 (22), 207 (21),
194 (44), 193 (27), 192 (18), 191 (10), 182 (10), 179 (35), 178 (18),
166 (12), 165 (29), 83 (100), 57 (42), 55 (41), 43 (11), 41 (39), 39
(14).
Anal. Calcd for C20H24: C, 90.85; H, 9.15. Found: C, 90.79; H, 9.18.
(E)-2′-(4,4-Dimethylpent-2-enyl)biphenyl-4-carbaldehyde (5k)
White solid; yield: 0.81 g (73%); mp 54–56 °C.
2-[(4′-Methylbiphenyl-4-yl)methyl]thiophene (5g)
White solid; yield: 0.81 g (77%); mp 54–56 °C.
IR (KBr): 3057, 3024, 1704, 1607, 1564, 1510, 1265 cm–1.
1H NMR (200 MHz, CDCl3): δ = 0.98 (s, 9 H), 3.29 (d, J = 4.9 Hz,
2 H), 5.33–5.38 (m, 2 H), 7.22–7.39 (m, 4 H), 7.52 (d, J = 8.2 Hz, 2
H), 7.94 (d, J = 8.2 Hz, 2 H), 10.09 (s, 1 H).
13C NMR (50.3 MHz, CDCl3): δ = 30.0 (3 C), 33.3, 37.0, 123.7,
126.6, 128.6, 129.9 (2 C), 130.1, 130.3, 130.5 (2 C), 135.5, 138.7,
141.1, 143.7, 148.7, 192.3.
MS (EI, 70 eV): m/z = 278 (M+•, 16), 207 (20), 193 (27), 179 (58),
178 (32), 165 (51), 152 (14), 83 (100), 57 (12), 55 (47), 43 (14), 41
(60), 39 (17).
IR (KBr): 1647, 1597, 1514 cm–1.
1H NMR (200 MHz, CDCl3): δ = 2.40 (s, 3 H), 4.21 (s, 2 H), 6.86
(dd, J = 3.2, 1.1 Hz, 1 H), 6.96 (dd, J = 5.1, 3.2 Hz, 1 H), 7.18 (dd,
J = 5.1, 3.2 Hz, 1 H), 7.23–7.34 (m, 4 H), 7.48–7.56 (m, 4 H).
13C NMR (50.3 MHz, CDCl3): δ = 21.8, 36.3, 124.6, 125.9, 127.5
(2 C), 127.7, 129.6 (2 C), 130.1 (2 C), 137.5, 138.6, 139.8, 140.0,
144.6.
MS (EI, 70 eV): m/z = 264 (M+•, 100), 249 (18), 231 (22), 215 (22),
165 (49), 152 (21), 131 (19), 115 (20), 97 (92), 91 (19), 89 (18), 85
(15), 77 (12), 65 (22), 63 (26), 57 (12), 53 (28), 51 (23), 45 (67), 39
(57).
Anal. Calcd for C20H22O: C, 86.29; H, 7.97. Found: C, 86.24; H,
7.92.
Anal. Calcd for C18H16S: C, 81.77; H, 6.10. Found: C, 81.71; H,
6.18.
2-(4-Benzylphenyl)thiophene (5l)
White solid; yield: 0.60 g (60%); mp 68–70 °C.
IR (KBr): 3107, 3063, 3025, 1600, 1535, 1501 cm–1.
1H NMR (200 MHz, CDCl3): δ = 4.06 (s, 2 H), 7.12 (dd, J = 5.1, 3.6
4-[(4′-Methylbiphenyl-2-yl)methyl]benzaldehyde (5h)
Yellow oil; yield: 0.93 g (82%).
IR (NaCl): 3056, 3023, 1698, 1607, 1575, 1516 cm–1.
Hz, 1 H), 7.25–7.37 (m, 9 H), 7.55–7.65 (m, 2 H).
13C NMR (50.3 MHz, CDCl3): δ = 42.1, 123.3, 125.0, 126.6, 126.7,
128.5, 129.0, 129.4, 129.9, 132.8, 141.0, 141.4, 144.8.
1H NMR (200 MHz, CDCl3): δ = 2.46 (s, 3 H), 4.11 (s, 2 H), 7.17–
7.43 (m, 10 H), 7.78 (d, J = 8.0 Hz, 2 H), 10.0 (s, 1 H).
MS (EI, 70 eV): m/z = 250 (M+•, 100), 217 (16), 216 (10), 215 (23),
202 (13), 173 (23), 171 (12), 165 (21), 115 (17), 91 (19), 89 (17), 77
(12), 65 (22), 63 (22), 51 (77), 45 (31), 39 (35).
13C NMR (50.3 MHz, CDCl3): δ = 21.6, 39.8, 127.1, 127.9, 129.3,
129.5, 129.9, 130.2, 130.7, 130.9, 134.8, 137.2, 137.5, 138.8, 142.8,
149.4, 192.5.
MS (EI, 70 eV): m/z = 286 (M+•, 93), 271 (12), 241 (12), 239 (13),
215 (12), 180 (32), 179 (75), 178 (26), 166 (22), 165 (100), 152
(13), 115 (13), 107 (27), 91 (19), 79 (13), 65 (11), 51 (14), 39 (17).
Anal. Calcd for C17H14S: C, 81.56; H, 5.64. Found: C, 81.62; H,
5.65.
4′-Benzyl-3-nitrobiphenyl (5n)
White solid; yield: 0.86 g (75%); mp 57–59 °C.
Anal. Calcd for C21H18O: C, 88.08; H, 6.37. Found: C, 88.15; H,
6.39.
Synthesis 2012, 44, 2023–2040
© Georg Thieme Verlag Stuttgart · New York

PAPER
Synthesis of Substituted Styrenes and Biaryls
2039
IR (KBr): 3084, 3061, 3027, 1602, 1583, 1531, 1515 cm–1.
MS (EI, 70 eV): m/z = 264 (M+•, 27), 159 (26), 105 (100).
1H NMR (200 MHz, CDCl3): δ = 4.09 (s, 2 H), 7.24–7.38 (m, 7 H),
Anal. Calcd for C20H24: C, 90.85; H, 9.15. Found: C, 90.92; H, 9.18.
7.56–7.65 (m, 3 H), 7.89–8.46 (m, 3 H).
13C NMR (50.3 MHz, CDCl3): δ = 42.0, 122.2, 122.3, 126.8, 127.7
(2 C), 129.1 (2 C), 129.4 (2 C), 130.2 (3 C), 133.3, 136.9, 141.1,
142.3, 143.1, 149.2.
Acknowledgment
We thank the ‘Service d’analyse chimique du Vivant de Tours’ for
recording NMR and mass spectra.
MS (EI, 70 eV): m/z = (M+•, 100), 254 (14), 242 (38), 241 (21), 167
(19), 165 (34), 152 (16), 120 (13), 91 (78), 65 (18).
Anal. Calcd for C19H15NO2: C, 78.87; H, 5.23; N, 4.84. Found: C,
78.75; H, 5.18; N, 4.88.
References
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4′-Methoxy-2-(4-methylbenzyl)biphenyl (5o)
Yellow oil; yield: 1.00 g (86%).
IR (NaCl): 3019, 3008, 1612, 1578, 1514 cm–1.
1H NMR (200 MHz, CDCl3): δ = 2.31 (s, 3 H), 3.86 (s, 3 H), 3.94
(s, 2 H), 6.88–6.94 (m, 4 H), 7.05 (d, J = 7.9 Hz, 2 H), 7.17–7.28
(m, 6 H).
13C NMR (50.3 MHz, CDCl3): δ = 21.6, 39.1, 55.8, 114.0 (2 C),
126.6, 127.8, 129.3 (2 C), 129.5 (2 C), 130.8 (2 C), 130.9 (2 C),
134.6, 135.7, 139.1, 139.2, 142.4, 159.2.
MS (EI, 70 eV): m/z = 288 (M+•, 100), 273 (16), 257 (11), 256 (11),
195 (25), 181 (11), 165 (24), 152 (13).
Anal. Calcd for C21H20O: C, 87.46; H, 6.99. Found: C, 87.39; H,
6.91.
1-Substituted-3-(4-methylbenzyl)benzenes 6a,b by Double Cou-
pling in One Pot; General Procedure
An oven-dried Schlenk flask equipped with a condenser was evac-
uated and back-filled with argon and charged with EtOH (19 mL),
H2O (5.3 mL), toluene (23 mL), m-bromobenzyl bromide (3 g, 12
mmol, 1 equiv), and boronic acid (12 mmol, 1 equiv). The flask was
evacuated and back-filled with argon and then 1 M Na2CO3 (13.5
mL) and Pd(PPh3)4 (0.36 mmol, 3 mol%) were added. The mixture
was stirred at 80 °C until completion of reaction (15 h). The second
boronic acid (18 mmol, 1.5 equiv) and Pd(PPh3)4 (0.36 mmol, 3
mol%) were then introduced. The mixture was stirred at 80 °C for
15 h. The soln was filtered through a Celite path and the solvents
were evaporated under reduced. The residue was extracted with
Et2O, washed with brine, and dried (MgSO4). After purification by
flash chromatography (silica gel) the products were characterized.
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3-(4-Methylbenzyl)biphenyl (6a)
White oil; yield: 1.61 g (52%).
IR (NaCl): 3028, 1600, 1575, 1514 cm–1.
1H NMR (200 MHz, CDCl3): δ = 2.45 (s, 3 H), 4.14 (s, 2 H), 7.25–
7.72 (m, 13 H).
13C NMR (50.3 MHz, CDCl3): δ = 21.6, 42.2, 125.5, 127.8 (3 C),
128.1, 128.4, 129.2 (2 C), 129.4 (3 C), 130.0 (2 C), 136.1, 138.5,
141.8, 141.9, 142.4.
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166 (16), 165 (37), 104 (10), 91 (11).
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(E)-1-(3,3-Dimethylbut-1-enyl)-3-(4-methylbenzyl)benzene
(6b)
Colorless oil; yield: 1.52 g (48%).
IR (NaCl): 3023, 1648, 1602, 1583, 1514 cm–1.
1H NMR (200 MHz, CDCl3): δ = 1.26 (s, 9 H), 2.45 (s, 3 H), 4.06
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© Georg Thieme Verlag Stuttgart · New York
Synthesis 2012, 44, 2023–2040

2040
E. Anselmi et al.
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Synthesis 2012, 44, 2023–2040
© Georg Thieme Verlag Stuttgart · New York