Palladium/Imidazolium salt as a versatile catalyst for sequential coupling reactions of aryl dihalides to unsymmetrically substituted arenes

Article abstract of DOI:10.1016/j.tet.2009.12.043

A simple method for one-pot sequential Heck/Suzuki coupling reactions of a range of substituted aryl dihalides has been described. The Pd(OAc)₂/imidazolium system catalyzed double coupling reactions proceed without isolation of the intermediates giving unsymmetrically polysubstituted biphenyls in good to excellent yields. Further couplings of the resultant products bearing additional C-Cl bonds with substituted arylboronic acids or amines lead to unsymmetrical terphenyls and aminobiphenyl derivatives.

Full text of DOI:10.1016/j.tet.2009.12.043

Tetrahedron 66 (2010) 1188–1195
Contents lists available at ScienceDirect
Tetrahedron
journal homepage: www.elsevier.com/locate/tet
Palladium/Imidazolium salt as a versatile catalyst for sequential coupling
reactions of aryl dihalides to unsymmetrically substituted arenes
,b,
Xiaoming Zhang a, Weilong Xie a, Wanzhi Chen a
*
a Department of Chemistry, Zhejiang University, Xixi Campus, Hangzhou 310028, PR China
b State Key Laboratory of Elemento-organic Chemistry, Nankai University, Tianjing, PR China
a r t i c l e i n f o
a b s t r a c t
Article history:
A simple method for one-pot sequential Heck/Suzuki coupling reactions of a range of substituted aryl di-
halides has been described. The Pd(OAc)2/imidazolium system catalyzed double coupling reactions pro-
ceed without isolation of the intermediates giving unsymmetrically polysubstituted biphenyls in good to
excellent yields. Further couplings of the resultant products bearing additional C–Cl bonds with substituted
arylboronic acids or amines lead to unsymmetrical terphenyls and aminobiphenyl derivatives.
Ó 2009 Elsevier Ltd. All rights reserved.
Received 13 November 2009
Received in revised form 13 December 2009
Accepted 21 December 2009
Available online 28 December 2009
Keywords:
Palladium
Imidazolium
Double coupling
Dihaloarene
1. Introduction
was described. The sequential integration of Heck coupling and
Hiyama coupling afforded multisubstituted olefins, which are
Palladium-catalyzed cross-coupling involving aryl halides with
olefins, organomagnesium, organoboron, or organosilicon reagents
etc., is an important protocol for the construction of carbon–carbon
bonds. Such coupling reactions have found versatile applications in
pharmaceutical, fungicide, and material industries.1 Combination
of two or more coupling reactions into a single vessel using a single
catalyst is of practical importance for the manufacture of valuable
structures, because it generates less waste and also obviates the
tedious separation and purification of the intermediate products. A
successful one-pot sequential reaction requires that the catalyst is
highly efficient and chemoselective toward the first coupling re-
action and maintains its catalytic activity in the subsequent cou-
pling reaction. Therefore, only a few successful examples have been
reported so far.2 For example, the sequential double Hiyama pro-
cess could be realized by the use of the dienylsilanol bearing
a benzyldimethylsilyl or 2-thienyldimethylsilyl unit at one end with
overall excellent yields of the unsymmetrical 1,4-diaryl-1,3-buta-
dienes.2a Recently, a one-pot, simultaneous Suzuki–Miyaura cross-
coupling of two different arylboronic acids with symmetrical aryl
dibromides and heterocyclic dibromides substrates giving the un-
symmetrical disubstituted tri(hetero)aryl derivatives has been
reported.2b A novel strategy for the synthesis of multisubstituted
olefins using 2-pyridyldimethyl(vinyl)silane as a versatile platform
regioselective and stereoselective.2d A catalytic one-pot triarylation
on the C]C core of vinylboronate pinacol ester has been described
to give extended
p-systems based on a multisubstituted olefin
structure very rapidly.2e
N-Heterocyclic carbenes (NHCs) have been playing more and
more important role in C–C and C–N formation reactions.3 Either
structurally characterized metal–NHC complexes4 or metal/imida-
zolium salts systems5 can be used. In this context, we have recently
reported the one-pot sequential double couplings of aryl dihalides
by using a well defined Pd–NHC complex, [Pd(3-(2,4-dimethyl-1,8-
naphthyrid-7-yl)-1-picolylimidazolylidene)2](PF6)2, as a catalyst.6
However, the special catalyst has to be pre-prepared, and the
substrates are limited to 3- and 4-bromoiodobenzene. As an ex-
tension of our studies on the organometallic chemistry of func-
tionalized NHCs,7 here we report a one-pot sequential Heck/Suzuki
coupling protocol, which is applicable to
a wide range of
substituted aryl dialyzes to give unsymmetrical substituted arenes
and terphenyls using a Pd/imidazolium catalytic system.
2. Results and discussion
As shown in Scheme 1, the one-pot sequential Heck/Suzuki
reaction was conducted in a stepwise way starting from 4-bro-
moiodobenzene in order to introduce two different groups. Initially,
we examined the efficiency of Pd(OAc)2/IPr$HCl (IPr¼1,3-bis(2,6-
* Corresponding author. Tel./fax: þ86 571 8827 3314.
E-mail address: chenwzz@zju.edu.cn (W. Chen).
diisopropylphenyl)imidazolylidene)
and
Pd(OAc)2/IMes$HCl
0040-4020/$ – see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2009.12.043

X. Zhang et al. / Tetrahedron 66 (2010) 1188–1195
1189
Table 1
(Imes¼1,3-bis(2,4,6-trimethylphenyl)imidazolylidene)
systems,
which have proven to be excellent catalysts in various coupling
reactions.8 We found that the chemoselectivity is high and the yield
of the mono-coupled product of Heck reaction is nearly quantita-
tive. However, both catalysts could not accomplish the Suzuki
coupling reaction due to generation of palladium black in the
course of the Heck coupling. Addition of catalytic amount of pyri-
dine or PPh3 could efficiently prohibit the generation of palladium
black, however, the Suzuki coupling reaction still did not occur and
only n-butyl 4-bromophenylacrylate could be obtained.
Sequential Heck/Suzuki reaction of 4-bromoiodobenzene with different Pd/L
systemsa
Entry
Ligand
Pd/L
ratio
Time of Heck
reaction (h)
Yieldb
(%)
Time of Suzuki
reaction (h)
Yieldc
(%)
1
2
3
4
5
6d
7
8
9
L1
L2
L3
L4
L5
L5
L5
L6
L6
1/2
1/2
1/2
1/2
1/2
1/2
1/1
1/2
1/1
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
92/6
92/6
94/5
92/6
96/4
95/5
93/6
93/6
94/5
5
5
5
5
2
2
2
2
2
24
28
35
25
92
90
86
87
85
L·HCl
N
N
N
R
a
Reaction conditions: Heck conditions. 4-bromoiodobenzene 1.0 mmol, n-butyl
acrylate 1.05 mmol, NaOAc 1.2 mmol, Pd(OAc)2 1.0 mol %, L$HCl 2.0 mol %, DMF
5 mL, 120 ꢀC. Suzuki conditions: PhB(OH)2 1.5 mmol, Cs2CO3 1.2 mmol, 80 ꢀC.
N
Cl
b
GC yield of mono-/double Heck coupling product.
Overall yields of double coupling product.
Pd2(dba)3 0.5 mol % was used.
c
O
O
Pd/L·HCl, NaOAc
DMF, 120 °C
d
Br
I
Br
OBu
O
BuO
intermediate
We found that all these Pd(OAc)2/L$HCl catalytic systems are
very active in the Heck reaction. The Heck coupling could be
completed within 1.5 h at 120 ꢀC regardless of which ligand was
employed. The reaction is highly chemoselective giving 4-bro-
mophenylacrylate ester in 92–96% yields. The double Heck cou-
pling product, 1,4-phenylenediacrylate ester, was obtained in not
more than 5% yield as determined by GC analysis. However, the
catalytic activities the Pd/imidazolium systems differ from each
other in the Suzuki coupling reaction. The Heck coupling is nearly
quantitative for all ligands, and thus the overall yield depends on
the Suzuki coupling. The carbene ligand with a bulky substituted
group is much more active (Table 1, entries 5–9) than those car-
bene ligands with small substituted groups (Table 1, entries 1–4).
Among these ligands, the pyrimidine functionalized imidazolium
salts bearing bulky 2,4,6-trimethylphenyl and 2,6-diisopropyl-
phenyl are most active in this sequential reaction. The employ-
ment of Pd2(dba)3 and Pd(OAc)2 as palladium sources did not
show any significant difference (Table 1, entry 6). Therefore,
Pd(OAc)2 was used for detailed investigation. The Pd/L ratio of 2
gave better overall yields and thus two equivalents of ligands were
used for further study. With respect to bases, NaOAc and Cs2CO3
have been previously found to be most suitable for Heck and
Suzuki coupling, respectively.6
After screening of the catalysts and the optimization of the re-
action conditions, we continued our investigation of the Heck/
Suzuki sequential couplings. We tried to extend the one-pot pro-
tocol to double coupling of other aryl dihalide derivatives with
various phenylboronic acids. As shown in Table 2, the coupling of 4-
bromoiodobenzene (1a) with n-butyl acrylate and subsequent
phenylboronic acid affording 2a in 85% yield (Table 2, entry 1).
When 4-chlorophenylboronic acid was employed as a coupling
partner, the C–Cl bond is inert under these conditions, and thus 2b
and 2c bearing additional chloride could be obtained in 67% and
73% yields, respectively (Table 2, entries 2 and 3). These products
offer opportunity for the construction of more complex structures
through further coupling reaction.
B(OH)2
BuO
Cs2CO3, 80 °C
Scheme 1. Sequential Heck/Suzuki reactions.
In our previous studies, we have shown that NHCs bearing one
or two heteroarene groups can efficiently increase the stability of
palladium catalysts.7a–c Therefore, we turned our study to func-
tionalized NHCs containing additional N-donors. We were pleased
to find that a series of imidazolium salts, L1$HCl–L6$HCl, combin-
ing pyrimidine functional group and carbene ligand moiety
(Chart 1) are quite suitable for the one-pot double coupling re-
actions. The detail of their catalytic behavior is given in Table 1.
These ligands could efficiently prohibit the generation of palladium
black in the Heck coupling reaction when heated at 120 ꢀC in DMF.
Furthermore, these Pd(OAc)2/imidazolium systems show excellent
catalytic activities in Heck coupling process and can also maintain
their activities in the subsequent Suzuki coupling reaction. After
completion of the Heck transformation at 120 ꢀC and cooling the
mixture to room temperature, PhB(OH)2 and Cs2CO3 were directly
added to the reaction vessel without isolation of the intermediate.
The Suzuki coupling was performed 80 ꢀC. The procedure gave the
desired double coupling products in different yields with the
ligands listed in Chart 1.
N
N
N
n
N
N
N
Bu
Me
N
N
Cl
Cl
L1·HCl
L2·HCl
N
N
N
N
N
N
N
N
N
Cl
Cl
We next examined the reactivities of the substituted aryl diha-
lides in order to understand the influence of substitutents. When
electron-deficient substrate, 2-fluoro-4-bromoiodobenzene (1c),
was employed as the reactant, the Heck reaction requires 3 h to
achieve a complete conversion. The chemoselectivity is also very
good, and the mono-coupled product could be obtained in more
than 90% as determined by GC chromatography. The Suzuki re-
actions could complete within another 3 h at 80 ꢀC. All the elec-
tron-rich and electron-deficient phenylboronic acid could give
good yields of biphenylacrylate esters (Table 2, entries 4–6). It is
L4·HCl
L3·HCl
N
N
N
N
N
N
N
N
Cl
Cl
L6·HCl
L5·HCl
Chart 1. Schematic illustration of the imidazolium salts.

1190
X. Zhang et al. / Tetrahedron 66 (2010) 1188–1195
Table 2
Table 2 (continued)
One-pot sequential Heck/Suzuki reactions of aryl dihalides and substituted aryl
dihalidesa
Yield
(%)b
Entry Substrate R2
R3
Product
R3
R3
B(OH)2
Br
Pd(OAc)2/L5·HCl, NaOAc
DMF, 120 °C
OBu
O
H3C
I
13
14
1e
1e
nBuOCO 4-Me
72
75
R2
Cs2CO3, 80 °C
R2
R1
R1
H3C
2m
Entry Substrate R2
R3
H
Product
Yield
(%)b
OBu
nBuOCO 3-MeO
MeO
H3C
O
OBu
O
Br
I
2n
1
2
nBuOCO
85
1a
2a
2b
OBu
O
Cl
15
1e
nBuOCO 4-Cl
66
H3C
Cl
OEt
O
1a
EtOCO 4-Cl
nBuOCO 4-Cl
67
73
2o
a
Reaction conditions: ary halide 1.0 mmol, olefin 1.05 mmol, NaOAc 1.2 mmol,
Pd(OAc)2 1.0 mol %, L5$HCl 2.0 mol %, DMF 5 mL, 120 ꢀC. After 2 h, arylboronic acid
1.5 mmol, and Cs2CO3 1.2 mmol were added and heated to 80 ꢀC.
Cl
Br
OBu
b
O
Isolated yield.
The (Z)-isomer was not isolated.
I
3
4
c
1b
2c
F
also found that the steric hindrance has little influence on the
reactions.
F
F3C
OBu
O
nBuOCO 4-CF3
81
Br
I
Although 2-methyl-4-bromoiodobenzene (1d) has a methyl
group neighboring to iodide, this reactant is quite reactive in the
Heck coupling reaction. The olefination reactions with various al-
kenes could be completed within 1 h giving mono-coupled product
in 94% yields. The Heck coupling of 2-methyl-4-bromoiodobenzene
is even more facile than those of unsubstituted bromoiodobenzene.
It seems that the observation is opposite to the commonly recog-
nized fact that the electron-deficient halobenzene has higher re-
activity in carbon–carbon formation reactions. Further Suzuki
couplings with substituted phenylboronic acids also proceeded
smoothly giving the double coupled products in 62–88% isolated
yields (Table 2, entries 7, 8, 10, and 11). However, when tert-butyl-
styrene was used, the desired product has a poor solubility in pe-
troleum ether and ethyl acetate causing some trouble in isolation,
and the total yield is comparatively low (Table 2, entry 9). For 3-
methyl-4-bromoiodobenzene containing a methyl group adjacent
to the bromide, the Heck coupling reaction is as reactive as 2-
methyl-4-bromoiodobenzene affording mono-coupled product in
94% yield. Further Suzuki coupling with the substituted phenyl-
boronic acids gave biphenylarylate esters in good yields (Table 2,
entries 12–15). Even in the case of sterically hindered 1-naph-
thalenylboronic acid, the overall yield is also good(Table 2, entry 12).
Terphenyls are a class of important compounds, which are fre-
quently found in nature,9 predominantly as p-terphenyl derivatives.
Synthetic terphenyls are known to possess biological activities in-
cluding potent immunosuppressant, neuroprotective, antith-
rombotic, anticoagulant, and cytotoxic activities.10 In addition,
terphenyls and polyphenyls are also important structural elements in
liquid crystals and fluorescent compounds.11 We are able to prepare
polysubstituted terphenyls via further coupling of the coupling
products bearing C–Cl bonds. Actually, the third step Suzuki coupling
reaction could be easily performed in one-flask by simply adding
another substituted arylboronic acid and Pd(OAc)2/IPr$HCl after the
second Suzuki coupling without isolation of chlorobiphenylacrylate
ester. However, the resultant products are complicated and the
overall isolated yields of desired terphenyls are not satisfactory.
Therefore, the preparation of substituted terphenyls from the isolated
intermediate products bearing additional C–Cl bond is needed. As
shown in Table 3, starting from the isolated chlorobiphenylacrylate
esters various substituted terphenyls could be obtained via Suzuki
coupling reactions with additional substituted phenylboronic acids
by using Pd(OAc)2/IPr$HCl as a catalyst in DMF at 80 ꢀC. These
1c
2d
Me
F
OEt
5
6
1c
EtOCO 2-Me
EtOCO 4-Cl
78
75
O
2e
F
Cl
OEt
O
1c
2f
MeO
CH3
CH3
OBu
O
nBuOCO 3-MeO
I
88
71
Br
7
8
1d
2g
CH3
F3
C
OEt
O
1d
EtOCO 4-CF3
2h
CH3
tbutyl
4-Cl
51c
Cl
9
1d
phenyl
2i
CH3
10
11
1d
1d
nBuOCO
65
62
OBu
O
B(OH)2
2j
CH3
Cl
OBu
nBuOCO 4-Cl
O
2k
OBu
H3C
Br
O
nBuOCO
63
I
12
CH3
B(OH)2
1e
2l

X. Zhang et al. / Tetrahedron 66 (2010) 1188–1195
1191
Table 3
Preparation of terphenyl alkenesa
R4
Cl
R2
R4
Pd(OAc)2/IPr·HCl
B(OH)2
Cs2CO3, DMF, 80 °C
R1
R2
R1
Entry
Substrate
R4
Product
Yieldb (%)
BuO
Cl
O
OBu
O
MeO
1
3-MeO
88
2c
3a
3b
OEt
O
NC
Cl
OEt
O
2
4-CN
63
81
2b
MeO
OEt
O
3
2b
3-MeO
3c
F
F
F3C
OEt
O
Cl
OEt
4
4-CF3
80
78
O
3d
2f
F
OEt
O
5
2f
B(OH)2
3e
H3C
H3C
Cl
OBu
O
Me
OBu
6
4-Me
4-CF3
79
83
O
3f
2k
H3
C
F3
C
OBu
O
7
2k
3g
H3C
CH3
CH3
Cl
OBu
OBu
8
3-Me
85
O
O
2o
3h
a
Reaction conditions: chlorobiphenylacrylate ester 0.5 mmol, arylboronic acid 0.75 mmol, Cs2CO3 1.0 mmol, Pd(OAc)2 2.0 mol %, IPr$HCl 4.0 mol %, DMF 5 mL, 80 ꢀC, 3 h.
Isolated yield.
b
reactions could be completed within 3 h and are alsotolerant to many
3. Conclusions
functionalgroups. Theterphenylswithdifferentsubstituentscouldbe
obtained in ca. 80% isolated yields (Table 3, entries 1 to 8).
In summary, we described a convenient one-pot sequential
approach to prepare unsymmetrically substituted arenes by using
a Pd/imidazolium salt system. Two different carbon–carbon for-
mation reactions can be achieved in one pot by using a simple
catalyst. Pyrimidine group play important role in stabilizing the
catalyst and preventing the formation of palladium black. This
protocol is convenient and efficient for various combinations of
dihaloarene, olefin, and arylboronic acid. In addition, the biphenyl
products bearing chloride could be further converted to poly-
substituted terphenyls and aminobiphenyls via additional C–C and
C–N coupling reactions.
Through C–N coupling of the obtained chlorobiphenyl de-
rivatives we were also able to prepare aminobiphenyl derivatives.
Such nitrogen-containing moiety represents an important motif in
natural products and pharmaceutical and medicinal compounds,12
as well as in polymers and materials.13 The amination of substituted
chlorobiphenyls could also be simply conducted by using Pd2(dba)3/
IPr$HCl as catalyst in dioxane. As shown in Table 4, (E)-4-(40-(4-tert-
butylstyryl)-30-methylbiphenyl-4-yl)morpholine (4a) and (E)-40-(4-
tert-butylstyryl)-30-methyl-N-phenylbiphenyl-4-amine (4b) could
be obtained in 81% and 72% yields, respectively.

1192
X. Zhang et al. / Tetrahedron 66 (2010) 1188–1195
Table 4
Amination of the substituted biphenyl chloridesa
Cl
R2
Pd2(dba)3/IPr·HCl, KOtBu
HNR5R6
R6R5N
dioxane, 80 °C
R1
R2
R1
Entry
1
Substrate
Amine
Product
Yieldb (%)
CH3
CH3
O
N
Cl
Morph-oline
81
2i
4a
CH3
HN
2
2i
PhNH2
72
4b
a
Reaction conditions. biphenyl chlorides, 0.5 mmol, amines 1.0 mmol, KOtBu 1.0 mmol, Pd2(dba)3 1.0 mol %, IPr$HCl 4.0 mol %, dioxane 5 mL, 80 ꢀC, 6 h.
Isolated yield.
b
4. Experimental
7.41 (d, J¼8.0, C6H4, 2H), 6.47 (d, J¼16.0, CH]CHCOOEt, 1H), 4.25–
4.30 (m, CH2, 2H), 1.35 (t, J¼7.2, CH3, 3H). 13C NMR (100 MHz,
4.1. General
CDCl3): d 166.9, 143.8, 141.6, 138.5, 133.9, 133.7, 129.0, 128.6, 128.1,
127.3, 118.3, 60.5, 14.3. HRMS (ESI) m/e calcd (MþþNa) 309.0653,
All the chemicals were obtained from commercial suppliers and
used without further purification. L$HCl salts were prepared
according to the known procedure.7g Elemental analyses were
performed on a Flash EA1112 instrument. 1H and 13C NMR spectra
were recorded on Bruker Avance-400 (400 MHz) spectrometer.
found 309.0655.
4.2.3. (E)-Butyl 3-(40-chlorobiphenyl-3-yl)acrylate (Table 2, Entry 3,
2c). White solid. 1H NMR (400 MHz, CDCl3).
d
7.73 (d, J¼16.0,
]CHCOOBu, 1H), 7.68 (s, aromatic, 1H), 7.50–7.57 (m, aromatic 4H),
7.41–7.48 (m, aromatic 3H), 6.50 (d, J¼16.0, CH]CHCOOBu, 1H),
4.23 (t, J¼6.4, CH2, 2H), 1.65–1.74 (m, CH2, 2H), 1.42–1.48 (m, CH2,
Chemical shifts (d) are expressed in part per million downfield to
TMS at
d
¼0 ppm and coupling constants (J) are expressed in hertz.
HRMS data were acquired with a FT-ICR mass spectrometer. Col-
umn chromatography was performed using silica gel (60 Å 200–
300 mesh).
2H), 0.97 (t, J¼8.0, CH3, 3H). 13C NMR (100 MHz, CDCl3):
d 166.8,
144.0, 140.5, 138.6, 134.9, 133.6, 129.2, 128.8, 128.6, 128.2, 126.9,
126.4, 118.6, 64.3, 30.5, 19.0, 13.6. Anal. calcd (%) for C19H19O2Cl. C,
72.49; H, 6.08. Found. C, 72.13; H, 6.13. EIMS m/z 314 [M]þ.
4.2. Typical procedure for one-pot Heck/Suzuki sequence
reaction
4.2.4. (E)-Butyl 3-(3-fluoro-40-(trifluoromethyl)biphenyl-4-yl)acry-
late (Table 2, Entry 4, 2d). White solid. 1H NMR (400 MHz, CDCl3):
To 5 mL of degassed DMF in a Schlenk tube were subsequently
added 4-bromoiodobenzene (283 mg, 1.0 mmol), n-butyl acrylate
(134 mg, 1.05 mmol), NaOAc (100 mg, 1.2 mmol), Pd(OAc)2 (2.2 mg,
1.0 mmol %), and L5$HCl (6.0 mg, 2.0 mmol %). The solution was
heated to 120 ꢀC under an atmosphere of N2 for 1.5 h. The reaction
mixture was then allowed to cool to room temperature and phe-
nylboronic acid (183 mg, 1.5 mmol), Cs2CO3 (400 mg, 1.2 mmol)
were added and heated to 80 ꢀC for another 3 h. The reaction
mixture was added to 20 mL of water and extracted with CH2Cl2
(3ꢁ20 mL). The combined organic layer was washed with water
(2ꢁ20 mL), dried over anhydrous MgSO4 and concentrated in
vacuo. The residue was purified by flash chromatography on silica
gel to give the desired product.
d
7.82 (d, J¼16.0,]CHCOOBu,1H), 7.72–7.67 (m, C6H4(CF3), 4H), 7.63
(t, J¼8.0, C6H3F, 1H), 7.41 (d, J¼8.0, C6H3F, 1H), 7.35 (d, JHF¼12.0,
C6H3F, 1H), 6.59 (d, J¼16.0, CH]CHCOOBu, 1H), 4.23 (t, J¼6.4, CH2,
2H), 1.72–1.67 (m, CH2, 2H), 1.48–1.42 (m, CH2, 2H), 0.97 (t, J¼7.2,
CH3, 3H). 13C NMR (100 MHz, CDCl3):
d 166.7, 162.7, 160.2, 143.1,
143.0, 142.3, 136.4, 136.3, 129.6, 129.5, 127.2, 125.9, 125.9, 125.8,
123.1, 123.0, 122.2, 122.1, 121.2, 121.1, 114.8, 114.6, 64.6, 30.7, 19.1,
13.6. HRMS (ESI) m/e calcd (MþþNa) 389.1141, found 389.1135.
4.2.5. (E)-Ethyl 3-(3-fluoro-20-methylbiphenyl-4-yl)acrylate (Table 2,
Entry 5, 2e). White solid. 1H NMR (400 MHz, CDCl3):
d 7.85 (d,
J¼16.0,]CHCOOBu, 1H), 7.55 (t, J¼8.0, 1H), 7.20–7.28 (m, aromatic,
4H), 7.12 (d, J¼8.0, aromatic, 1H), 7.08 (d, JHF¼12.0, C6H3F, 1H), 6.57
(d, J¼16.0, CH]CHCOOBu, 1H), 4.29 (m, CH2, 2H), 2.29 (s,
C6H4(CH3), 3H), 1.35 (t, J¼7.2, CH3, 3H). 13C NMR (100 MHz, CDCl3):
4.2.1. (E)-Butyl3-(biphenyl-4-yl)acrylate(Table 2,Entry1,2a). Colorless
oil. 1H NMR (400 MHz, CDCl3):
d
7.70 (d, J¼16.0,]CHCOOBu, 1H),
d 166.9, 162.2, 159.7, 146.0, 145.9, 139.9, 137.0, 136.9, 135.1, 130.6,
7.57–7.62 (m, C6H4þo-C6H5, 6H), 7.44 (t, J¼8.0, m-C6H5, 2H), 7.36 (t,
J¼8.0, p-C6H5, 1H), 6.46 (d, J¼16.0, –CH]CHCOOBu, 1H), 4.21 (t,
J¼6.4, CH2, 2H), 1.66–1.73 (m, CH2, 2H), 1.39–1.48 (m, CH2, 2H), 0.97
129.4, 128.7, 128.6, 128.0, 126.0, 125.5, 125.4, 121.0, 120.9, 120.7,
120.6, 117.0, 116.8, 60.6, 20.3, 14.3. HRMS (ESI) m/e calcd (MþþNa)
307.1105, found 307.1105.
(t, J¼8.0, CH3, 3H). 13C NMR (100 MHz, CDCl3):
d 167.1, 144.0, 142.9,
140.1, 133.4, 128.8, 128.5, 127.8, 127.5, 127.0, 118.1, 64.4, 30.7, 19.1,
4.2.6. (E)-Ethyl 3-(40-chloro-3-fluorobiphenyl-4-yl)acrylate (Table 2,
13.7. EIMS m/z 280 [M]þ.
Entry 6, 2f). White solid. 1H NMR (400 MHz, CDCl3):
d 7.81 (d,
J¼16.0, ]CHCOOBu, 1H), 7.58 (t, J¼8.0, aromatic, 1H), 7.50 (d, J¼8.0,
aromatic, 2H), 7.41 (d, J¼8.0, aromatic, 2H), 7.35 (d, J¼8.0, aromatic,
1H), 7.29 (d, JHF¼12.0, C6H3F, 1H), 6.56 (d, J¼16.0, CH]CHCOOBu,
1H), 4.28 (m, CH2, 2H), 1.34 (t, J¼7.2, CH3, 3H). 13C NMR (100 MHz,
4.2.2. (E)-Ethyl 3-(40-chlorobiphenyl-4-yl)acrylate (Table 2, Entry 2,
2b). White solid. 1H NMR (400 MHz, CDCl3):
d
7.71 (d, J¼16.0,
]CHCOOEt, 1H), 7.58 (d, J¼8.4, C6H4, 4H), 7.52 (d, J¼8.0, C6H4, 2H),

X. Zhang et al. / Tetrahedron 66 (2010) 1188–1195
1193
CDCl3):
d
166.8, 162.9, 160.3, 143.5, 143.4, 137.4, 136.7, 136.6, 134.6,
125.8, 125.7, 125.3, 125.2, 118.0, 64.4, 30.7, 20.0, 19.2, 13.7. HRMS
129.6, 129.5, 129.2, 128.1, 122.8, 122.7, 121.7, 121.5, 120.9, 120.8,
114.5, 114.3, 60.6, 14.3. HRMS (ESI) m/e calcd (MþþNa) 327.0564,
found 327.0559.
(ESI) m/e calcd (MþþNa) 367.1674, found 367.1669.
4.2.13. (E)-Butyl 3-(2,40-dimethylbiphenyl-4-yl)acrylate (Table 2,
Entry 13, 2m). White solid. 1H NMR (400 MHz, CDCl3):
d 7.69 (d,
4.2.7. (E)-Butyl 3-(30-methoxy-3-methylbiphenyl-4-yl)acrylate (Ta-
J¼16.0, ]CHCOOBu, 1H), 7.39–7.42 (m, aromatic, 2H), 7.20–7.25 (m,
aromatic, 5H), 6.46 (d, J¼16.0, CH]CHCOOBu, 1H), 4.22 (t, J¼6.4,
CH2, 2H), 2.41 (s, C6H3(CH3), 3H), 2.29 (s, C6H3(CH3), 3H), 1.72–1.67
(m, CH2, 2H), 1.48–1.42 (m, CH2, 2H), 0.98 (t, J¼7.2, CH3, 3H). 13C
ble 2, Entry 7, 2g). White solid. 1H NMR (400 MHz, CDCl3):
d 8.00 (d,
J¼16.0, ]CHCOOBu, 1H), 7.63 (d, J¼8.0, aromatic, 1H), 7.43 (m, ar-
omatic, 2H), 7.36 (t, J¼8.0, aromatic, 1H), 7.18 (d, J¼8.0, aromatic,
1H), 7.12 (m, aromatic, 1H), 6.91 (d, J¼8.0, aromatic, 1H), 6.40 (d,
J¼16.0, CH]CHCOOBu, 1H), 4.22 (t, J¼6.4, 2H), 3.87 (s, OCH3, 3H),
2.50 (s, C6H3(CH3), 3H), 1.74–1.67 (m, CH2, 2H), 1.49–1.40 (m, CH2,
NMR (100 MHz, CDCl3):
d 167.2, 144.3, 143.9, 138.1, 136.8, 135.9,
133.1, 130.3, 130.1, 128.9, 128.8, 125.4, 117.8, 64.3, 30.7, 21.1, 20.5,
19.1, 13.7. HRMS (ESI) m/e calcd (MþþNa) 331.1674, found 331.1669.
2H), 0.97 (t, J¼7.2, CH3, 3H). 13C NMR (100 MHz, CDCl3):
d 167.2,
159.9, 142.4, 141.7, 141.6, 138.0, 132.4, 129.8, 129.4, 126.8, 125.0,
119.4, 119.0, 113.0, 112.6, 64.4, 55.2, 30.7, 19.9, 19.1, 13.7. HRMS (ESI)
m/e calcd (MþþNa) 347.1618, found 347.1616.
4.2.14. (E)-Butyl 3-(30-methoxy-2-methylbiphenyl-4-yl)acrylate (Table
2, Entry 14, 2n). White solid. 1H NMR (400 MHz, CDCl3):
d 7.70 (d,
J¼16.0, ]CHCOOBu, 1H), 7.41–7.44 (m, aromatic, 2H), 7.35 (t, J¼8.0,
aromatic, 1H), 7.28 (d, J¼2.0, aromatic, 1H), 6.93–6.91 (m, aromatic,
2H), 6.86 (s, C6H3(CH3),1H), 6.48 (d, J¼16.0, CH]CHCOOBu,1H), 4.24
(t, J¼6.4, CH2, 2H), 3.85 (s, OCH3, 3H), 2.31 (s, C6H3(CH3), 3H), 1.68–
4.2.8. (E)-Ethyl 3-(3-methyl-40-(trifluoromethyl)biphenyl-4-yl)acry-
late (Table 2, Entry 8, 2h). White solid. 1H NMR (400 MHz, CDCl3):
d
8.00 (d, J¼16.0, ]CHCOOBu, 1H), 7.69 (s, aromatic, 5H), 7.45 (s,
1.75 (m, CH2, 2H), 1.42–1.51 (m, CH2, 2H), 0.99 (t, J¼7.2, CH3, 3H). 13
C
aromatic, 2H), 6.42 (d, J¼16.0, CH]CHCOOBu, 1H), 4.28 (d, J¼6.0,
NMR (100 MHz, CDCl3): d 167.1, 159.3, 144.2, 143.7, 142.4, 135.9, 133.4,
CH2, 2H), 2.52 (s, C6H3(CH3), 3H), 1.36 (s, CH3, 3H). 13C NMR
130.1, 130.0, 129.1, 125.3, 121.4, 117.9, 114.6, 112.5, 64.3, 55.2, 30.7,
20.4, 19.1, 13.7. HRMS (ESI) m/e calcd (MþþNa) 347.1618, found
347.1619.
(100 MHz, CDCl3).
d 166.9, 143.7, 141.4, 140.9, 138.3, 133.2, 129.5,
127.2, 127.0, 125.7, 125.6, 125.5, 125.1, 119.6, 60.5, 19.9, 14.3. HRMS
(ESI) m/e calcd (MþþNa) 357.1078, found 357.1073.
4.2.15. (E)-Butyl 3-(40-chloro-2-methylbiphenyl-4-yl)acrylate (Table
4.2.9. (E)-4-(4-tert-Butylstyryl)-40-chloro-3-methylbiphenyl (Table 2,
2, Entry 15, 2o). White solid. 1H NMR (400 MHz, CDCl3):
d 7.69 (d,
Entry 9, 2i). White solid. 1H NMR (400 MHz, CDCl3):
d
7.66 (d, J¼8.0,
J¼16.0, ]CHCOOBu, 1H), 7.39–7.43 (m, aromatic, 4H), 7.31–7.26 (m,
aromatic, 3H), 6.47 (d, J¼16.4, CH]CHCOOBu, 1H), 4.21–4.24 (t,
J¼6.8, CH2, 2H), 2.28 (s, C6H3(CH3), 3H), 1.67–1.74 (m, CH2, 2H),
1.41–1.48 (m, CH2, 2H), 0.98 (t, J¼8.0, CH3, 3H). 13C NMR (100 MHz,
aromatic, 1H), 7.53 (d, J¼8.0, aromatic, 2H), 7.48 (d, aromatic, J¼8.0,
2H), 7.41–7.38 (m, 6H), 7.30, 7.04 (both d, J¼16.0, CH]CH, each 1H),
2.48 (s, C6H3(CH3), 3H), 1.34 (s, C(CH3)3, 9H). 13C NMR (100 MHz,
CDCl3):
d
150.9, 139.2, 138.7, 136.1, 135.9, 134.8, 133.2, 130.0, 128.8,
CDCl3): d 167.1, 144.1, 142.6, 139.5, 135.9, 133.8, 133.2, 130.3, 130.2,
128.1, 126.3, 125.8, 125.6, 125.1, 124.7, 34.6, 31.2, 20.1. HRMS (ESI)
130.1, 128.4, 125.5, 118.3, 64.4, 30.8, 20.4, 19.2, 13.7. HRMS (ESI) m/e
m/e calcd (MþþNa) 383.1537, found 383.1542.
calcd (MþþNa) 351.1128, found 351.1124.
4.2.10. (E)-Butyl
3-(2-methyl-4-(naphthalen-1-yl)phenyl)acrylate
4.3. Typical procedure for Suzuki coupling of the substituted
biphenyl chloride
(Table 2, Entry 10, 2j). Colorless oil. 1H NMR (400 MHz, CDCl3):
d
8.06 (d, J¼16.0, ]CHCOOBu,1H), 7.90 (d, J¼8.4, aromatic, 2H), 7.86
(d, J¼7.6, aromatic, 1H), 7.68 (d, J¼8.4, aromatic, 1H), 7.54–7.41 (m,
aromatic, 4H), 7.35 (m, aromatic, 2H), 6.46 (d, J¼16.0,
CH]CHCOOBu, 1H), 4.24 (t, J¼6.8, CH2, 2H), 2.52 (s, C6H3(CH3), 3H),
1.76–1.70 (m, CH2, 2H), 1.49–1.43 (m, CH2, 2H), 0.99 (t, J¼7.2, CH3,
To 5 mL of degassed DMF in a Schlenk tube were subsequently
added (E)-butyl 3-(40-chlorobiphenyl-3-yl)acrylate (157 mg,
0.5 mmol), 3-methoxyphenylboronic acid (114 mg, 0.75 mmol),
Cs2CO3 (340 mg, 1.0 mmol), Pd(OAc)2 (2.2 mg, 2.0 mmol %), and
IPr$HCl (8.5 mg, 4.0 mmol %). The solution was heated to 80 ꢀC under
an atmosphere of N2 for 3 h. The reaction mixture was added to
20 mL of water and extracted with CH2Cl2 (3ꢁ20 mL). The combined
organic layer was washed with water (2ꢁ20 mL), dried over anhy-
drous MgSO4 and concentrated in vacuo. The residue was purified by
flash chromatography on silica gel to give the desired product.
3H). 13C NMR (100 MHz, CDCl3):
d 167.2, 142.5, 141.8, 139.3, 137.6,
133.7, 132.3, 132.2, 131.3, 128.3, 128.0, 127.8, 126.7, 126.2, 126.1,
125.8, 125.7, 125.3, 119.1, 64.4, 30.7, 19.9, 19.2, 13.7. HRMS (ESI) m/e
calcd (MþþNa) 367.1674, found 367.1669.
4.2.11. (E)-Butyl 3-(40-chloro-3-methylbiphenyl-4-yl)acrylate (Table
2, Entry 11, 2k). White solid. 1H NMR (400 MHz, CDCl3):
d 7.98 (d,
J¼16.0, ]CHCOOBu, 1H), 7.63 (d, J¼8.8, aromatic, 1H), 7.52 (d,
J¼8.8, aromatic, 2H), 7.39–7.41 (m, aromatic, 4H), 6.41 (d, J¼16.0,
CH]CHCOOBu, 1H), 4.27 (t, J¼6.8, CH2, 2H), 2.50 (s, C6H3(CH3),
3H), 1.74–1.67 (m, CH2, 2H), 1.49–1.42 (m, CH2, 2H), 0.98 (t, J¼7.2,
4.3.1. (E)-Butyl
(Table 3, Entry 1, 3a). White solid. 1H NMR (400 MHz, CDCl3):
3-(3-methoxy-[1,10;40,100]terphenyl-300-yl)acrylate
d
7.74–7.78 (m, aromatic, 2H), 7.64–7.69 (m, aromaticþ]CHCOOBu,
5H), 7.53–7.45 (m, aromatic, 2H), 7.38 (t, J¼8.0, aromatic, 1H), 7.23
(d, J¼8.0, aromatic, 1H), 7.18 (s, C6H3(OCH3) 1H), 6.92 (d, J¼8.0, 1H),
6.52 (d, J¼16.0, CH]CHCOOBu, 1H), 4.23 (t, J¼6.4, CH2, 2H), 3.88 (s,
OCH3, 3H), 1.67–1.72 (m, CH2, 2H), 1.49–1.42 (m, CH2, 2H), 0.97 (t,
CH3, 3H). 13C NMR (100 MHz, CDCl3):
d 167.1, 141.5, 141.3, 138.6,
138.2, 133.7, 132.6, 129.2, 128.9, 128.1, 126.9, 124.8, 119.2, 64.4, 30.7,
19.9, 19.1, 13.7. HRMS (ESI) m/e calcd (MþþNa) 351.1128, found
351.1122.
J¼7.2 CH3,, 3H). 13C NMR (100 MHz, CDCl3):
d 167.0, 159.9, 144.4,
142.0, 141.3, 140.3, 139.3, 134.9, 129.8, 129.3, 128.8, 127.6, 127.4,
126.8, 126.7, 119.5, 118.6, 112.7, 64.4, 55.3, 30.7, 19.1, 13.7. HRMS (ESI)
m/e calcd (MþþNa) 409.1774, found 409.1782.
4.2.12. (E)-Butyl
3-(3-methyl-4-(naphthalen-1-yl)phenyl)acrylate
(Table 2, Entry 12, 2l). Colorless oil. 1H NMR (400 MHz, CDCl3):
d
7.86–7.92 (m, aromatic, 2H), 7.76 (d, J¼16.0, ]CHCOOBu, 1H),
7.54–7.38 (m, aromatic, 6H), 7.26–7.32 (m, aromatic, 2H), 6.52 (d,
J¼16.0, CH]CHCOOBu, 1H), 4.24 (t, J¼6.8, CH2, 2H), 2.04 (s,
C6H3(CH3), 3H), 1.75–1.67 (m, CH2, 2H), 1.51–1.41 (m, CH2, 2H), 0.98
4.3.2. (E)-Ethyl 3-(4-cyano-[1,10;40,100]terphenyl-400-yl)acrylate (Table
3, Entry 2, 3b). White solid. 1H NMR (400 MHz, CDCl3):
d 7.74–7.64
(m, aromaticþ]CHCOOBu, 13H), 6.49 (d, J¼16.0, CH]CHCOOBu,
(t, J¼7.2, CH3, 3H). 13C NMR (100 MHz, CDCl3):
d 167.2, 144.4, 142.4,
1H), 4.28 (m, J¼5.6, CH2, 2H), 1.35 (t, CH3, 3H). 13C NMR (100 MHz,
138.9,137.5, 133.7,133.4,131.6,130.9, 129.6, 128.2, 127.7, 126.4, 126.1,
CDCl3): d 166.9, 144.9, 143.8, 141.8, 140.4, 138.4, 133.8, 132.6, 128.6,

1194
X. Zhang et al. / Tetrahedron 66 (2010) 1188–1195
127.7, 127.6, 127.5, 127.4, 118.8, 118.4, 111.0, 60.5, 14.3. HRMS (ESI)
1.75–1.68 (m, CH2, 2H), 1.50–1.41 (m, CH2, 2H), 0.98 (t, J¼7.2, CH3,
3H). 13C NMR (100 MHz, CDCl3):
167.2, 142.2, 141.7, 140.7, 140.5,
139.0, 138.4, 138.1, 132.4, 129.3, 128.7, 128.2, 127.8, 127.5, 127.3,
126.9, 124.9, 124.1, 119.0, 64.4, 30.7, 21.5, 20.0, 19.2, 13.8. HRMS (ESI)
m/e calcd (MþþNa) 407.1982, found 407.1985.
m/e calcd (MþþNa) 376.1308, found 376.1311.
d
4.3.3. (E)-Ethyl3-(3-methoxy-[1,10;40,100]terphenyl-400-yl)acrylate(Table
3, Entry3,3c). White solid.1H NMR (400 MHz, CDCl3):
d 7.75–7.60 (m,
aromatic, 9H), 7.40–7.36 (m, aromatic, 1H), 7.25–7.22 (m, aromatic,
1H), 7.17 (s, C6H3(OCH3) 1H), 6.91 (d, J¼6.0, aromatic, 1H), 6.48 (d,
J¼16.0, CH]CHCOOBu, 1H), 4.26–4.31 (m, CH2, 2H), 3.88 (s, OCH3,
4.4. Typical procedure for amination of the substituted
biphenyl chloride
3H),1.35 (t, J¼6.8, CH3, 3H).13C NMR (100 MHz, CDCl3):
d 169.9,160.0,
144.0, 142.4, 142.0, 140.6, 139.2, 133.6, 129.8, 128.6, 127.6, 127.4, 127.3,
119.5, 118.2, 112.8, 60.5, 55.3, 14.3. HRMS (ESI) m/e calcd (MþþNa)
381.1461, found 381.1476.
To 5 mL of degassed dioxane in a Schlenk tube were sub-
sequently added (E)-4-(4-tert-butylstyryl)-40-chloro-3-methyl-
biphenyl (130 mg, 0.5 mmol), morpholine (65 mg, 0.75 mmol),
KtOBu (112 mg, 1.0 mmol), Pd2(dba)3 (8.0 mg, 2.0 mmol %), and
IPr$HCl (8.5 mg, 4.0 mmol %). The solution was heated to 80 ꢀC
under an atmosphere of N2 for 6 h. The reaction mixture was added
to 20 mL of water and extracted with CH2Cl2 (3ꢁ20 mL). The
combined organic layer was washed with water (2ꢁ20 mL), dried
over anhydrous MgSO4 and concentrated in vacuo. The residue was
purified by flash chromatography on silica gel using ethyl acetate/
petroleum ether mixed solvent to give the desired product.
4.3.4. (E)-Ethyl 3-(4-trifluoromethyl-300-fluoro-[1,10;40,100]terphenyl-
400-yl)acrylate (Table 3, Entry 4, 3d). White solid. 1H NMR (400 MHz,
CDCl3):
d
7.85 (d, J¼16.0, ]CHCOOBu, 1H), 7.73–7.71 (m, aromatic,
8H), 7.63 (t, J¼8.0, aromatic, 1H), 7.47–7.45 (m, aromatic, 1H), 7.41–
7.38 (m, aromatic, 1H), 6.59 (d, J¼16, CH]CHCOOBu, 1H), 4.32–4.27
(m, CH2, 2H), 1.36 (t, J¼7.6, CH3, 3H). 13C NMR (100 MHz, CDCl3):
d
166.8, 162.9, 160.4, 144.0, 143.9, 143.8, 139.7, 138.7, 136.8, 129.6,
129.5, 127.8, 127.5, 127.3, 125.9 125.8, 125.7, 122.9,121.6, 121.5, 120.8,
120.7, 114.5, 114.3, 60.7, 14.3. HRMS (ESI) m/e calcd (MþþNa)
437.1135, found 437.1153.
4.4.1. (E)-4-(40-(4-tert-Butylstyryl)-30-methylbiphenyl-4-yl)morpho-
line (Table 4, Entry 1, 4a). Pale yellow solid. 1H NMR (400 MHz,
CDCl3):
d
7.65 (d, J¼8.0, aromatic, 1H), 7.55 (d, J¼8.0, aromatic, 2H),
4.3.5. (E)-Ethyl 3-(3-fluoro-40-(naphthalen-1-yl)biphenyl-4-yl)acry-
7.48 (d, J¼8.0, aromatic, 2H), 7.42–7.39 (m, aromatic, 4H), 7.32, 7.02
(both d, J¼16.0, CH]CH, each 1H), 6.98 (d, J¼8.0, 2H), 3.89 (t, J¼4.8,
OCH2CH2N, 2H), 3.21 (t, J¼4.8, OCH2CH2N, 2H), 2.48 (s, C6H3(CH3),
late (Table 3, Entry 5, 3e). White solid. 1H NMR (400 MHz, CDCl3):
d
7.97–7.86 (m, aromatic, 4H), 7.73 (d, J¼8.0, aromatic, 2H), 7.67–
3H), 1.34 (s, C(CH3)3, 9H). 13C NMR (100 MHz, CDCl3):
d 150.8, 136.1,
7.44 (m, aromatic, 9H), 6.61 (d, J¼16.0, CH]CHCOOBu, 1H), 4.34–
4.28 (m, CH2, 2H), 1.38 (t, J¼7.6, CH3, 3H). 13C NMR (100 MHz,
135.4, 134.9, 129.7, 129.4, 128.5, 128.2, 127.9, 126.2, 125.7, 125.6,
125.2, 125.0, 124.6, 124.4, 72.7, 65.7, 34.4, 30.7, 19.6. HRMS (ESI) m/e
calcd (MþþH) 412.2635, found 412.2643.
CDCl3):
d 166.8, 162.9, 160.4, 144.5, 144.4, 140.9, 139.3, 137.7, 136.8,
136.7, 133.8, 131.4, 130.7, 129.5, 129.4, 128.3, 127.9, 126.9, 126.7,
126.1, 125.8, 125.7, 125.3, 122.8, 122.7, 121.3, 121.2, 120.6, 120.5,
114.5, 114.3, 60.6, 14.2. HRMS (ESI) m/e calcd (MþþNa) 419.1418,
found 419.1431.
4.4.2. (E)-40-(4-tert-Butylstyryl)-30-methyl-N-phenylbiphenyl-4-
amine (Table 4, Entry 2, 4b). Pale yellow solid. 1H NMR (400 MHz,
CDCl3):
d
7.66 (d, J¼8.0, aromatic, 1H), 7.54 (d, J¼8.0, aromatic, 2H),
4.3.6. (E)-Butyl 3-(4-methyl-200-methyl-[1,10;40,100]terphenyl-400-yl)-
7.49 (d, J¼8.0, aromatic, 2H), 7.44–7.40 (m, aromaticþCH]CH, 4H),
7.35–7.27 (m, aromatic, 3H), 7.13 (t, J¼7.2, aromatic, 4H), 7.04 (d,
J¼16.0, CH]CH, 1H), 6.97 (d, J¼8.0, aromatic, 1H), 5.79 (s, NH, 1H),
2.50 (s, C6H3(CH3), 3H),1.36 (s, CH3, 9H). 13C NMR (100 MHz, CDCl3):
acrylate (Table 3, Entry 6, 3f). White solid. 1H NMR (400 MHz,
CDCl3):
d
7.70 (d, J¼16.0, ]CHCOOBu, 1H), 7.63 (d, J¼8.0, aromatic,
2H), 7.54 (d, J¼8.0, aromatic, 2H), 7.45–7.42 (m, aromatic, 2H), 7.38
(d, J¼8.0, aromatic, 2H), 7.31–7.25 (m, aromatic, 3H), 6.47 (d, J¼16.0,
CH]CHCOOBu, 1H), 4.22 (t, J¼8.0, CH2, 2H), 2.41 (s, C6H3(CH3), 3H),
2.35 (s, C6H3(CH3), 3H), 1.74–1.67 (m, CH2, 2H), 1.50–1.41 (m, CH2,
d
150.7, 142.9, 142.5, 139.7, 136.0, 135.0, 134.9, 133.3, 129.4, 129.3,
128.4, 127.7, 126.2, 125.7, 125.6, 125.4, 124.2, 121.2, 118.0, 117.8, 34.6,
31.2, 20.0. HRMS (ESI) m/e calcd (MþþNa) 418.2529, found
418.2542.
2H), 0.98 (t, J¼8.0, CH3, 3H). 13C NMR (100 MHz, CDCl3):
d 167.2,
144.3, 143.6, 140.0, 139.8, 137.8, 137.2, 136.0, 133.4, 130.4, 130.2,
129.5,129.4,126.9,126.7,125.5,118.0, 64.4, 30.8, 21.1, 20.6,19.2,13.7.
HRMS (ESI) m/e calcd (MþþNa) 407.1982, found 407.1990.
Acknowledgements
We are grateful to the support of the NSF of China (gs1)
(20872129 and J0830413), and Zhejiang University K.P. Chao’s
High Technology Development Foundation for financial support.
4.3.7. (E)-Butyl 3-(4-trifluoromethyl-200-methyl-[1,10;40,100]terphenyl-
400-yl)acrylate (Table 3, Entry 7, 3g). White solid. 1H NMR (400 MHz,
CDCl3):
d
7.65–7.76 (m, aromaticþ]CHCOOBu, 7H), 7.44 (t, J¼8.0,
aromatic, 4H), 7.29 (d, J¼8.0, aromatic, 1H), 6.48 (d, J¼16.0,
CH]CHCOOBu, 1H), 4.23 (t, J¼8.0, CH2, 2H), 2.35 (s, C6H3(CH3), 3H),
1.67–1.74 (m, CH2, 2H), 1.43–1.50 (m, CH2, 2H), 0.98 (t, J¼8.0, CH3,
Supplementary data
Supplementary data associated with this article can be found in
the online version at doi:10.1016/j.tet.2009.12.043.
3H). 13C NMR (100 MHz, CDCl3):
d 167.2, 167.1, 144.3, 144.2, 143.6,
143.1, 141.0, 139.9, 139.7, 138.5, 137.7, 137.2, 136.0, 135.9, 133.6, 133.4,
130.4, 130.3, 130.2, 130.1, 129.6, 129.5, 129.3, 127.3, 127.0, 126.8,
126.6, 125.8, 125.7, 125.5, 125.4, 118.2, 118.0, 64.4, 64.3, 30.7, 21.1,
20.5, 20.4, 19.2, 13.7. HRMS (ESI) m/e calcd (MþþNa) 461.1699,
found 461.1706.
References and notes
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