Palladium-catalyzed hydroarylation of alkynes with arylboronic acids

Article abstract of DOI:10.1016/j.tet.2010.01.086

Reaction of symmetrical and unsymmetrical alkynes with arylboronic acids, using PdCl₂ as catalyst source and i-Pr₂NPPh₂ as ligand, afforded trisubstituted alkenes with regioselectivity in good to excellent yields without a common additional acetic acid. Its efficiency has been demonstrated by its good functional groups, high yield and crowded substrates.

Full text of DOI:10.1016/j.tet.2010.01.086

Tetrahedron 66 (2010) 2433–2438
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Palladium-catalyzed hydroarylation of alkynes with arylboronic acids
,
a
a
,
a,
Xiaoling Xu a, Jiuxi Chen a , Wenxia Gao , Huayue Wu , Jinchang Ding b, Weike Su a
*
*
a College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou 325035, China
b Wenzhou Vocational and Technical College, Wenzhou 325035, China
a r t i c l e i n f o
a b s t r a c t
Article history:
Reaction of symmetrical and unsymmetrical alkynes with arylboronic acids, using PdCl2 as catalyst
source and i-Pr2NPPh2 as ligand, afforded trisubstituted alkenes with regioselectivity in good to excellent
yields without a common additional acetic acid. Its efficiency has been demonstrated by its good
functional groups, high yield and crowded substrates.
Received 23 November 2009
Received in revised form 20 January 2010
Accepted 26 January 2010
Available online 1 February 2010
Ó 2010 Elsevier Ltd. All rights reserved.
Keywords:
Palladium-catalyzed
Hydroarylation
Arylboronic acids
Trisubstituted alkenes
1. Introduction
proceeded in the present of acetic acid as additive,10,11 thereby, to
some extent, the reaction is confined to acid-compatible substrates
In the past few decades, great attention has been delivered to
metal-catalyzed hydroarylation of alkynes due to its fast accessi-
bility to highly functionalized alkenes.1 The use of organometallic
compounds such as arylmagnesium bromide2 and tetraphenyltin3
as arylation reagents has been reported in hydroarylation with
high selectivity. Of particular note, the arylboron reagents have
drawn considerable attention in recent years due to their advan-
tages such as, good functional group tolerance, readily available, as
well as air and moiety stability.4 In 2001, Hayashi and co-workers
first reported rhodium-catalyzed addition reaction of arylboronic
acid to alkynes.5 Subsequently, a range of rhodium-catalyzed
approaches for unsymmetric addition-type reactions has been
developed.6,7 Then, the nickel-catalyzed8 selective synthesis of
multi-substituted aryl-alkenes and aryl-dienes, copper-catalyzed9a
conjugate additions of alkynoates with arylboronic acid, cobalt-
catalyzed9b similarly regio- and stereoselective transformation as
well as palladium-catalyzed hydroarylation reaction of alkyne have
been reported soon after that.10,11
and equipments.
In our previous report, we have successfully developed some
methodologies for palladium-catalyzed additions of organoboronic
acids to the carbon–carbon and carbon–heteroatom unsaturated
bond.12 Herein, we wish to report an efficient palladium-catalyzed
hydroarylation of alkynes with arylboronic acids, using inorganic
base and easily available ligand in common organic solvent, pro-
viding multifunctionalized alkenes in one pot with satisfactory
yields.
2. Results and discussion
Initially, we examined the ligand effects in the hydroarylation
reaction of diphenylacetylene 1a and 3-methoxyphenylboronic
acid 2b using PdCl2 as the catalyst, and the results were listed in
Table 1. As determined by GC–MS analysis (entry 1), treatment of
substrate 1a with arylboronic acid 2b using PdCl2 as the palladium
precursor and K2CO3 as the base afforded only a trace amount of the
desired product 3ab in the absence of ligands. When ligand L1 was
used, the reaction gave 3ab in 5% yield (entry 2). When the com-
mon ligand i-Pr2NPPh2 was employed, we were delight to find that
the yield was remarkably improved, and 3ab was obtained with up
to 95% yield (entry 3). Further studies showed that other mono-
phosphine and biphospine ligands such as L3–L8 were essentially
inefficient for this hydroarylation reaction (entries 4–9). Sub-
sequently, the effects of bases and solvents were evaluated (entries
10–16). We found that potassium carbonate and cesium carbonate
However, palladium-catalyzed approaches for hydroarylation of
sterically hindered or electron-deficient substrates often gave poor
yields and the regioselectivity of the addition of organometallics to
alkynes still need to be improved. Especially, all of reported
Pd-catalyzed hydroarylation of alkynes with arylboron must be
* Corresponding authors. Tel./fax: þ86 577 8836 8280.
E-mail addresses: jiuxichen@wzu.edu.cn (J. Chen), huayuewu@wzu.edu.cn
(H. Wu).
0040-4020/$ – see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2010.01.086

2434
X. Xu et al. / Tetrahedron 66 (2010) 2433–2438
are both suitable bases, but some other bases such as NaOH and
Et3N are ineffective (entries 10–12), THF is the best solvent among
the solvents examined, and no reaction occurred in alcohol (entries
14–16). It should be noted that both palladium and bases are nec-
essary, no 3ab was given in the absence of bases and palladium
catalysts (entries 13 and 17). The palladium species screening ex-
periments showed that the reaction could also proceed using other
Pd catalysts, such as Pd(OAc)2, Pd2(dba)3, and PdCl2(PhCN)2, but all
of them were less efficient than PdCl2 (entries 17–20). Moreover,
we also examined the amounts of ligand and 2b (entries 21 and 22).
And the results showed that the increased loading of L2 had little
effects on the yield of the reaction; however, the yield was reduced
to 75% when using 1.2 equiv of 2b (entry 22). Cu(OAc)2$H2O/L2 and
NiCl2$6H2O/L2 catalytic systems show less reactivities (entries 23
and 24).
reacted smoothly with 2b to afford 3db, 3eb, and 3fb in 95%, 90%,
and 90% yields, respectively (entries 4–6). It was reported that
heteroarylboronic acids were not suitable substrates since the
heteroatoms may coordinate to transition metal.13 However, good
yield of product 3hb was furnished in the reaction of di(thiophen-
3-yl)acetylene 1h with 2b (entry 8). Next, a series of arylboronic
acids containing different substituted were investigated. The re-
sults showed that the mono-substituted group on the arylboronic
acid had little influence on the reaction (entries 9–22). To our de-
light, a number of functional groups, including ether, halide, formyl,
nitro, and cyano groups were readily tolerated in this system.
Boronic acids 2c and 2d containing a p-chloro or p-fluoro group, for
example, were treated with substrate 1a using PdCl2/L2 system
smoothly affording the arylated products in 92% and 89% yields,
respectively (entries 17 and 18). Diarylacetylenes 1f bearing chloro
group underwent the hydroarylation reaction with arylboronic
acids 2a, 2c, and 2e, respectively, to produce corresponding alkenes
in excellent yields (entries 14, 19, and 20). In addition, we found
that reaction of 1f with electron-deficient arylboronic acids 2f and
2g gave the desired products in relatively lower yields (entries 21
and 22), due to formation of homocoupling and protodeboronation
byproducts as determined by GC–MS analysis.
Table 1
PdCl2-catalyzed hydroarylation of diphenylethyne with phenylboronic acida
OMe
Ph
Ph
+
(HO)2B
OMe
Ph
Ph
3ab
Table 2
1a
2b
PdCl2-catalyzed hydroarylation of alkynes with arylboronic acidsa
R2
H
Entry Pd source
Ligand
Base
Solvent
Yieldb (%)
PdCl2/L2(5 mol %)
R1
R1
+
R2B(OH)2
1
2
3
4
5
6
7
8
PdCl2
PdCl2
PdCl2
PdCl2
PdCl2
PdCl2
PdCl2
PdCl2
PdCl2
PdCl2
PdCl2
PdCl2
PdCl2
PdCl2
PdCl2
PdCl2
d
d
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
THF
THF
THF
THF
THF
THF
THF
THF
THF
THF
Trace
5
95
K2CO3, THF, 65 °C
R1 R1
3
(S)-Binap L1
i-Pr2NPPh2 L2
dppf L3
PPh3 L4
P(4-MeO-C6H4)3 L5 K2CO3
dppp L6
dppe L7
PhNHPPh2 L8
L2
L2
L2
L2
L2
L2
L2
L2
L2
L2
1
2
Trace
Trace
Trace
Trace
Trace
Trace
Trace
79
Entry
R1 (1)
Ph 1a
R2 (2)
Product
Yieldb (%)
1
2
3
4
5
6
7
8
3-(OMe)C6H4 2b
3-(OMe)C6H4 2b
3-(OMe)C6H4 2b
3-(OMe)C6H4 2b
3-(OMe)C6H4 2b
3-(OMe)C6H4 2b
3-(OMe)C6H4 2b
3-(OMe)C6H4 2b
Ph 2a
Ph 2a
Ph 2a
Ph 2a
Ph 2a
3ab
3bb
3cb
3db
3eb
3fb
3gb
3hb
3aa
3ba
3ca
3da
3ea
3fa
3bc
3ec
3ac
3ad
3fc
95
82
89
95
90
90
62
80
96
99
94
95
79
83
86
84
92
89
86
84
68
51
4-Me–C6H4 1b
3,5-(Me)2–C6H3 1c
4-MeO–C6H4 1d
4-F–C6H4 1e
4-Cl–C6H4 1f
3-OHC–C6H4 1g
3-Thienyl 1h
Ph 1a
4-Me–C6H4 1b
3,5-(Me)2–C6H3 1c
4-MeO–C6H4 1d
4-F–C6H4 1e
4-Cl–C6H4 1f
4-Me–C6H4 1b
4-F–C6H4 1e
Ph 1a
K2CO3
K2CO3
K2CO3
NaOH
Cs2CO3 THF
NEt3
d
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
THF
THF
DMF
Trace
NR
9
9
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
10
11
12
13
14
15
16
17
18
19
20
21
22
Toluene 68
EtOH
THF
THF
THF
THF
THF
THF
THF
THF
Trace
NR
49
68
Pd(OAc)2
Pd2(dba)3
PdCl2(PhCN)2 L2
Ph 2a
4-Cl–C6H4 2c
4-Cl–C6H4 2c
4-Cl–C6H4 2c
4-F–C6H4 2d
4-Cl–C6H4 2c
4-F3C–C6H4 2e
4-NC–C6H4 2f
3-O2N–C6H4 2g
86
PdCl2
PdCl2
de
L2
L2
L2
L2
93c
75d
Trace
Trace
Ph 1a
4-Cl–C6H4 1f
4-Cl–C6H4 1f
4-Cl–C6H4 1f
4-Cl–C6H4 1f
df
3fe
3ff
3fg
NR¼No reaction.
a
Reactions were carried out using 1a (0.2 mmol), 2a (2 equiv), PdCl2 (5 mol %),
Ligand (5 mol %), and base (3 equiv) in solvent (3 mL) at 65 ꢀC for 24 h.
a
Reactions were carried out using 1 (0.2 mmol), 2 (2 equiv), PdCl2 (5 mol %), L2
b
Isolated yield.
L2 (10 mol %) was used.
PhB(OH)2$2a (1.2 equiv) was used.
Cu(OAc)2$H2O (5 mol %) instead of PdCl2.
(5 mol %), and K2CO3 (3 equiv) in THF (3 mL) at 65 ꢀC for 2–12 h.
c
b
Isolated yield.
d
e
f
The steric effect was further examined and results were sum-
marized in Table 3. As shown in Table 3, for most cases, the
hydroarylation with hindered substrates also proceeded smoothly
in excellent yields. For example, diarylacetylenes 1a–e underwent
the reaction successfully with 2i in quantitative yields (entries 1–4).
Naphthylboronic acid 2j also react with 2a giving 98% yield of target
product (entry 9). Besides, the hydroarylation of dialkylacetylene
1k with 2a and 2i also gave high yields (entries 11 and 12).
Finally, the hydroarylation of unsymmetric alkynes were ex-
amined in the hydroarylation reaction (Scheme 1). It has been
reported that the aryl alkyl alkyne 1m is prone to low regiose-
lectivity as a result of the nature of substitutents.11 However, under
the optimal reaction conditions, 1m could proceed smoothly with
arylboronic acid 2a, 2b, or 2i to furnish the corresponding olefins
NiCl2$6H2O (5 mol %) instead of PdCl2.
Under the optimized conditions, we next tried to extend the
hydroarylation reaction to other alkynes and arylboronic acids, and
results were summarized in Table 2. As we expected, the reaction
took place smoothly with good functional group tolerance.
Above all, a variety of diarylacetylenes were examined through
the reactions with 3-methoxyphenylboronic acid 2b (entries 1–7).
Both electron-rich and electron-deficient diarylacetylenes un-
derwent the hydroarylation reaction with 2b in good to excellent
yields. It was observed that the reaction of diarylacetylenes 1
bearing electron-rich functional groups with 2b gave much better
yields of hydroarylated product. Diarylacetylenes 1d, 1e, and 1f,

X. Xu et al. / Tetrahedron 66 (2010) 2433–2438
2435
3ma, 3mb, or 3mi in excellent yields and regioselectivities
(Eqs. 1–3). The addition of the aryl groups occurs exclusively at the
-position of the phenyl group. The ability of the catalytic system to
perform the hydroarylation in excellent yields and high regiose-
lectivities may be a consequence of the intrinsic properties (steric
and electronic) of the phosphine.14 Unfortunately, the reaction of
phenylacetylene (1n) with phenylboronic acid (2a) was un-
successful under the same reaction condition (Eq. 4). May because
of C–H of terminal alkynes, in the metal-catalyzed reaction, is so
active that could not contain in the present of base.
PdCl2
b
ArB(OH)2
2
R'
Ar
R
H
Pd(0)
A
3
R'
Ar
(HO)2B Pd
B
R
Ar
Pd
H
D
Table 3
B(OH)3
alkyne
1
PdCl2-catalyzed hydroarylation of alkynes with arylboronic acidsa
R'
R
R2
-E
H
PdCl2/L2(5 mol %)
PhB(OH)2
H2O
R1
R1
R2B(OH)2
+E
Ar
(HO)2B
C
Pd
K2CO3, THF, 65 °C
R1
3
R1
1
2
Ph
B
Entry
1
2
Product
3ai
Yieldb (%)
O
B
O
B
E:
Ph
Ligand was omitted for simplicity
1
2
3
4
5
6
7
8
Ph 1a
2-Me–C6H4 2i
99
99
99
99
96
89
86
98
98
75
82
86
O
Ph
4-Me–C6H4 1b
3,5-(Me)2–C6H3 1c
4-MeO–C6H4 1d
4-F–C6H4 1e
3-Thienyl 1h
2-Me–C6H4 1i
1-Nap 1j
Ph 1a
2-Me–C6H4 1i
n-Pr 1k
2-Me–C6H4 2i
2-Me–C6H4 2i
2-Me–C6H4 2i
2-Me–C6H4 2i
2-Me–C6H4 2i
Ph 2a
Ph 2a
1-Nap 2j
2-Me–C6H4 2i
Ph 2a
2-Me-C6H4 2i
3bi
3ci
3di
3ei
3hi
3ia
3ja
3aj
3ii
Scheme 2. Proposed mechanism for palladium-catalyzed hydrophenylation of alkynes
with arylboronic acids.
Ph
Ph
H
PdCl2/L2(5 mol %)
K2CO3, THF-d8, 65 °C, 24 h
95% yield
(5)
PhB(OH)2
Ph
+
Ph
Ph
1a
2a
3aa
9
10
11
12
PhB(OH)2
3ka
3ki
+ H2O - H2O
n-Pr 1k
a
Ph
B
Reactions were carried out using 1 (0.2 mmol), 2 (2 equiv), PdCl2 (5 mol %), L2
(5 mol %), and K2CO3 (3 equiv) in THF (3 mL) at 65 ꢀC for 2–12 h.
O
B
O
B
b
Isolated yield.
Ph
O
Ph
PdCl2/L2(5 mol %)
2 equiv 2a, 5 equiv D2O
K2CO3, THF, 65 oC, 24 h
+ D2O - D2O
PhB(OD)2
Ph
Ph
D
Ar
Ph
Ph
H
PdCl2/L2
+
(6)
(5 mol %)
Ph
+
ArB(OH)2
Ph
Ph
Ph
3ma 99 % (1)
3mb 99 % (2)
3mi 93 % (3)
K2CO3, THF
92% yield
3aa
3aa-d
65 oC, 24 h
2a
2b
2i
:
46%
54%
1m
Scheme 3.
Ar
The presence of acetic acid has been generally believed to be
fundamental for the success of the palladium-catalyzed hydro-
arylation of alkynes. The present study shows importantly that the
alkenylpalladium intermediates C could be smoothly hydrolyzed
even in basic media. It is noteworthy that no acid is involved in the
catalytic cycle.
PdCl2/L2
(5 mol %)
(4)
Ph
+
ArB(OH)2
Ph
3na
K2CO3, THF
65 oC, 24 h
trace
2a
1n
Scheme 1.
The mechanism of the reaction is suggested in Scheme 2. First,
the oxidative addition of Pd(0) species A with arylboronic acid 2
readily occurs to afford intermediate B.11,15 On the one hand, the
employment of electron-rich aminophosphine ligand facilitates
this oxidative addition step. However, no reaction could be carried
out in the absence of bases, so we think that C–B possible be acti-
vated by base. Subsequently, the selective insertion of alkyne 1 into
the Pd–C in a syn fashion take place to give intermediate C. Hy-
drolysis of C followed by reductive elimination of the D finally gives
the hydroarylating products 3 and regenerates the active Pd(0)
species.
To confirm the source of the hydrogen on the vinylic carbon,
isotope-labeling study was carried out (Scheme 3). In THF-d8, 3aa
was almost exclusively formed in excellent yield (Eq. 5). So the
hydrogen is not from solvent. There is an equilibrium between
PhB(OH)2 and triphenylboroxin,16 and the process can generate
water for hydrolysis. Next, the use of 5 equiv D2O in THF resulted in
the formation of the two products 3aa and 3aa-d (46:54) (Eq. 6) in
92% isolated yield. Those findings gave direct evidences to support
our proposed mechanism.
3. Conclusion
In summary, we have developed a palladium-catalyzed hydro-
arylation of symmetrical and unsymmetrical alkynes with aryl-
boronic acids by use of the easy-handling i-Pr2NPPh2 as the ligand
and in the presence of inorganic base. This reaction would be a good
approach for synthesis of functionalized alkenes. It should be
mentioned that the aryl alkyl acetylene (1-phenylpropyne) was
firstly transformed to alkenes with high regioselectivity by Pd-
catalyzed addition reaction. Further studies on this chemistry and
its application of palladium-catalyzed addition protocol are cur-
rently underway.
4. Experimental section
4.1. General
Chemical reagents were either purchased or purified by stan-
dard techniques. Diarylacetylenes17 and aminophosphine ligands14

2436
X. Xu et al. / Tetrahedron 66 (2010) 2433–2438
were prepared according to the reported procedures. 1H and 13C
NMR spectroscopy was performed on both a Bruck-300 spec-
trometer operating at 300 MHz (1H NMR) and 75 MHz (13C NMR),
and 19F NMR spectroscopy was performed on a Bruck-500 spec-
trometer operating at 470 MHz. TMS (tetramethylsilane) was used
as an internal standard and CDCl3 was used as the solvent. Mass
spectrometric analysis was performed on GC–MS analysis (SHI-
MADZU GC–MS-QP2010). Elemental analysis was determined on
a Carlo-Erba 1108 instrument. Column chromatography was per-
formed using EM Silica gel 60 (300–400 mesh).
132.1 (d, JC–F¼7.6 Hz), 133.2 (d, JC–F¼2.8 Hz), 135.8 (d, JC–F¼3.4 Hz),
141.2 (d, JC–F¼1.4 Hz), 144.5, 159.5, 161.5 (d, JC–F¼246.2 Hz), 162.2 (d,
JC–F¼245.6 Hz). 19F NMR (470 MHz)
d:
ꢁ114.3, ꢁ114.4. IR
(CH3CO2C2H5): 3403, 2924, 2361, 1205 cmꢁ1; LRMS (EI, 70 eV) m/z
(%): 322 (Mþ, 100), 289 (15), 288 (12), 183 (14). Anal. Calcd for
C21H16F2O: C, 78.25; H, 5.00. Found: C, 78.28; H, 4.94.
4.2.6. (E)-1-(2-m-Methoxyphenyl-2-p-chlorophenylvinyl)-4-chloro-
benzene (3fb). Colorless oil; 1H NMR (CDCl3, 300 MHz)
d
3.77 (s,
3H), 6.81–6.95 (m, 6H), 7.10–7.32 (m, 7H). 13C NMR (CDCl3, 75 MHz)
55.2, 113.1, 113.5, 120.2, 127.4, 128.3, 129.0, 129.2, 130.7, 131.7,
d
4.2. General procedure for synthesis of trisubstituted olefins
132.6, 133.5, 135.4, 138.2, 141.9, 144.1, 159.5. IR (CH3CO2C2H5): 2937,
2360, 1589, 1485, 1092 cmꢁ1; LRMS (EI, 70 eV) m/z (%): 352 (Mþ,
100), 254 (68), 253 (70), 252 (73). Anal. Calcd for C21H16Cl2O: C,
71.00; H, 4.54. Found: C, 69.94; H, 4.57.
Under
a
nitrogen atmosphere,
a mixture of alkynes 1
(0.2 mmol), arylboronic acid
2
(2 equiv), PdCl2 (5 mol %), L2
(5 mol %), and K2CO3 (3 equiv) in THF (3 mL) was stirred at room
temperature for 30 min and then heated to 65 ꢀC for a period of
time. After completion of the reaction as indicated by TLC, the re-
action mixture was cooled to room temperature. The residue was
diluted with EtOAc (5.0 mL) and washed with water (5 mL). Evap-
oration of the solvent followed by purification on silica gel afforded
the corresponding product 3. The organic layers were dried over
MgSO4, concentrated, and purified by flash column chromatogra-
phy on silica gel to give the desired product.
4.2.7. (E)-1-(2-m-Methoxyphenyl-2-m-formylphenylvinyl)-3-for-
mylbenzene (3gb). Yellow oil; 1H NMR (CDCl3, 300 MHz)
d
3.80 (s,
3H), 6.84–6.90 (m, 6H), 7.09–7.27 (m, 4H), 7.48–7.88 (m, 3H). 13C
NMR (CDCl3, 75 MHz) 55.2, 113.3, 113.6, 120.2, 127.7, 128.0, 128.8,
d
129.0, 129.4, 129.5, 131.0, 131.7, 135.1, 136.3, 136.5, 136.8, 137.7, 140.7,
142.8, 143.5, 159.6, 192.0. IR (CH3CO2C2H5): 3379, 2833, 2726, 1698,
1586 cmꢁ1; LRMS (EI, 70 eV) m/z (%): 342 (Mþ, 100), 253 (43), 252
(36), 149 (60). Anal. Calcd for C23H18O3: C, 80.68; H, 5.30. Found: C,
80.65; H, 5.37.
4.2.1. (E)-1-(2-Phenyl-2-m-methoxyphenylvinyl)benzene
(3ab)18. Colorless oil; 1H NMR (CDCl3, 300 MHz)
d
3.77 (s, 3H),
6.81–6.92 (m, 3H), 6.97 (s,1H), 7.01–7.22 (m, 8H), 7.30–7.36 (m, 3H).
13C NMR (CDCl3, 75 MHz)
55.2, 112.8, 113.4, 120.2, 126.8, 127.4,
4.2.8. (Z)-3-(2-m-Methoxyphenyl-2-(thiophen-3-yl)vinyl)thiophene
(3hb). Yellow oil; 1H NMR (CDCl3, 300 MHz)
d
3.78 (s, 3H), 6.57–
6.58 (m, 1H), 6.80–7.26 (m, 9H), 7.38–7.39 (m, 1H). 13C NMR (CDCl3,
75 MHz) 55.2, 112.6, 112.8, 119.5, 123.0, 124.4, 124.6, 124.7, 125.9,
d
127.9, 128.3, 128.6, 129.1, 129.5, 130.3, 137.2, 140.2, 142.4, 144.9,
159.4.
d
128.0, 129.1, 129.2, 135.5, 138.9, 140.3, 143.8, 159.4. IR
(CH3CO2C2H5): 3100, 2936, 2836,1592,1278 cmꢁ1; LRMS (EI, 70 eV)
m/z (%): 298 (Mþ, 100), 267 (26), 265 (25), 234 (21). Anal. Calcd for
C17H14OS2: C, 68.42; H, 4.73. Found: C, 68.48; H, 4.80.
4.2.2. (E)-1-Methyl-4-(2-m-methoxyphenyl-2-p-tolylvinyl) benzene
(3bb). Yellow oil; 1H NMR (CDCl3, 300 MHz)
d
2.26 (s, 3H), 2.37 (s,
3H), 3.76 (s, 3H), 6.79–6.94 (m, 8H), 7.07–7.23 (m, 5H). 13C NMR
(CDCl3, 75 MHz) 21.2, 21.3, 55.2, 112.6, 113.3, 120.2, 128.0, 128.7,
d
4.2.9. 1,1,2-Triphenylethene (3aa)12f. Colorless oil; 1H NMR (CDCl3,
129.0, 129.3, 129.4, 130.2, 134.5, 136.5, 136.9, 137.3, 141.5, 145.3,
159.4. IR (CH3CO2C2H5): 3018, 2923, 1594, 1047 cmꢁ1; LRMS (EI,
70 eV) m/z (%): 314 (Mþ, 100), 315 (25), 299 (24), 284 (17). Anal.
Calcd for C23H22O: C, 87.86; H, 7.05. Found: C, 87.79; H, 6.99.
300 MHz)
d
6.97 (s, 1H), 7.01–7.04 (m, 2H), 7.09–7.25 (m, 5H), 7.28–
126.7, 127.4, 127.5, 127.6,
7.35 (m, 8H). 13C NMR (CDCl3, 75 MHz)
d
127.9, 128.15, 128.18, 128.6, 129.5, 130.4, 137.4, 140.4, 142.6, 143.4.
4.2.10. (Z)-1-Methyl-4-(2-phenyl-2-p-tolylvinyl)benzene
4.2.3. (E)-1,3-Dimethyl-5-(2-(3,5-dimethylphenyl)-2-m-methoxy-
(3ba)12f. Colorless oil; 1H NMR (CDCl3, 300 MHz)
d
2.25 (s, 3H), 2.37
(s, 3H), 6.89 (s, 1H), 6.94–7.07 (m, 4H), 7.10–7.20 (m, 4H), 7.26–7.30
(m, 5H). 13C NMR (CDCl3, 75 MHz)
21.2, 21.3, 127.2, 127.5, 127.9,
phenylvinyl)benzene (3cb). Colorless oil; 1H NMR (CDCl3, 300 MHz)
d
2.13 (s, 6H), 2.26 (s, 6H), 3.78 (s, 3H), 6.64–6.75 (m, 3H), 6.82–6.95
d
(m, 7H), 7.18–7.24 (m, 1H). 13C NMR (CDCl3, 75 MHz)
d
21.22, 21.23,
128.1, 128.7, 129.3, 129.4, 130.2, 134.6, 136.4, 136.9, 137.5, 141.6,
143.8.
55.2, 112.4, 113.3, 120.2, 127.5, 127.7, 128.1, 128.5, 128.9, 129.0, 137.0,
137.1, 137.9, 140.1, 142.1, 145.3, 159.4. IR (CH3CO2C2H5): 3038, 3018,
1453, 783 cmꢁ1; LRMS (EI, 70 eV) m/z (%): 342 (Mþ, 100), 327 (13),
312 (17). Anal. Calcd for C25H26O: C, 87.68; H, 7.65. Found: C, 87.62;
H, 7.72.
4.2.11. (Z)-1,3-Dimethyl-5-(2-(3,5-dimethylphenyl)-2-phenyl-
vinyl)benzene (3ca). Colorless oil; 1H NMR (CDCl3, 300 MHz)
d
2.13
(s, 6H), 2.26 (s, 6H), 6.65–6.75 (m, 3H), 6.83–6.96 (m, 4H), 7.23–7.35
(m, 5H). 13C NMR (CDCl3, 75 MHz)
21.21, 21.22, 127.2, 127.4, 127.5,
d
4.2.4. (E)-1-(2-m-Methoxyphenyl-2-p-methoxyphenylvinyl)-4-me-
127.7, 127.9, 128.1, 128.4, 128.8, 127.12, 137.14, 138.0, 140.3, 142.3,
143.7. IR (CH3CO2C2H5): 2918, 1598, 1445, 697 cmꢁ1; LRMS (EI,
70 eV) m/z (%): 312 (Mþ, 100), 297 (14), 282 (25). Anal. Calcd for
C24H24: C, 92.26; H, 7.74. Found: C, 92.20; H, 7.69.
thoxybenzene (3db). Yellow oil; 1H NMR (CDCl3, 300 MHz)
d
3.74 (s,
3H), 3.76 (s, 3H), 3.82 (s, 3H), 6.67–6.69 (m, 2H), 6.79–7.00 (m, 8H),
7.11–7.23 (m, 3H). 13C NMR (CDCl3, 75 MHz)
55.09, 55.14, 55.2,
d
112.5, 113.2, 113.4, 114.0, 120.1, 127.5, 129.0, 130.2, 130.7, 131.5, 132.6,
140.1, 145.5, 158.2, 158.8, 159.4. IR (CH3CO2C2H5): 2952, 2835, 1601,
1508, 1248 cmꢁ1; LRMS (EI, 70 eV) m/z (%): 346 (Mþ, 100), 331 (6),
195 (25), 152 (6). Anal. Calcd for C23H22O3: C, 79.74; H, 6.40. Found:
C, 79.66; H, 6.36.
4.2.12. (Z)-1-(2-Phenyl-2-p-methoxyphenylvinyl)-4-methoxy-
benzene (3da)19. Colorless oil; 1H NMR (CDCl3, 300 MHz)
d 3.74 (s,
3H), 3.83 (s, 3H), 6.67–6.70 (m, 2H), 6.86–6.89 (m, 3H), 6.98–7.01
(m, 2H), 7.11–7.14 (m, 2H), 7.23–7.31 (m, 5H). 13C NMR (CDCl3,
75 MHz)
d 55.09, 55.14, 113.3, 114.0, 127.1, 127.3, 127.4, 128.1, 130.2,
4.2.5. (E)-1-(2-m-Methoxyphenyl-2-p-fluorophenylvinyl)-4-fluo-
130.7, 131.6, 132.7, 140.2, 143.9, 158.2, 158.7.
robenzene (3eb). White solid, mp 89–91 ꢀC; 1H NMR (CDCl3,
300 MHz)
NMR (CDCl3, 75 MHz)
21.4 Hz), 115.6, 115.9, 120.1, 127.4, 129.2, 131.1 (d, JC–F¼7.6 Hz),
d
3.77 (s, 3H), 6.80–7.04 (m, 10H), 7.12–7.25 (m, 3H). 13
C
4.2.13. (Z)-1-(2-Phenyl-2-p-fluorophenylvinyl)-4-fluoro
benzene
6.80–
d
55.2, 113.2 (d, JC–F¼35.8 Hz), 115.0 (d, JC–F
¼
(3ea). White solid, mp 61–63 ꢀC; 1H NMR (CDCl3, 300 MHz)
d
6.86 (m, 2H), 6.91 (s, 1H), 6.96–7.17 (m, 6H), 7.27–7.31 (m, 5H). 13C

X. Xu et al. / Tetrahedron 66 (2010) 2433–2438
2437
NMR (CDCl3, 75 MHz)
d
115.0 (d, JC–F¼21.4 Hz), 115.7 (d, JC–
300 MHz)
7.59–7.62 (m, 2H). 13C NMR (CDCl3, 75 MHz)
128.5, 129.4, 130.0, 130.8, 131.6, 132.1, 133.4, 134.2, 134.6, 137.2,
d
6.95–6.98 (m, 3H), 7.08–7.16 (m, 4H), 7.33–7.39 (m, 4H),
¼21.3 Hz), 127.2, 127.5, 127.7, 128.3, 131.1 (d, JC–F¼7.6 Hz), 132.1 (d,
d
111.1, 118.8, 128.0,
F
JC–F¼7.6 Hz),133.3,135.9,141.4,143.0,161.5 (d, JC–F¼245.6 Hz),162.2
(d, JC–F¼245.5 Hz). 19F NMR (470 MHz)
d
: ꢁ114.3, ꢁ114.5. IR
140.3, 147.0. IR (CH3CO2C2H5): 3401, 3038, 2226, 1597, 1092 cmꢁ1
;
(CH3CO2C2H5): 3400, 2924, 2401,1505,1228 cmꢁ1; LRMS (EI, 70 eV)
m/z (%): 292 (Mþ, 100), 293 (20), 271 (22), 196 (21). Anal. Calcd for
C20H14F2: C, 82.17; H, 4.83. Found: C, 82.11; H, 4.78.
LRMS (EI, 70 eV) m/z (%): 349 (Mþ,100), 351 (63), 279 (86), 278 (60).
Anal. Calcd for C21H13Cl2N: C, 72.01; H, 3.74; N, 4.00. Found: C,
72.09; H, N, 3.67.
4.2.14. (Z)-1-(2-Phenyl-2-p-chlorophenylvinyl)-4-chloro
(3fa). Colorless oil; 1H NMR (CDCl3, 300 MHz)
6.89–6.96 (m, 3H),
7.10–7.13 (m, 4H), 7.26–7.31 (m, 7H). 13C NMR (CDCl3, 75 MHz)
127.3, 127.6, 127.9, 128.28, 128.33, 129.0, 130.7, 131.8, 132.6, 133.5,
benzene
4.2.22. (E)-1-(2-m-Nitrophenyl-2-p-chlorophenylvinyl)-4-chloro-
d
benzene (3fg). Yellow solid, mp 91–93 ꢀC; 1H NMR (CDCl3,
300 MHz)
75 MHz) d 122.1, 122.5, 123.5, 128.5, 129.3, 129.5, 129.7, 130.8, 131.6,
d
6.97–7.17 (m, 6H), 7.34–8.25 (m, 7H). 13C NMR (CDCl3,
d
135.5, 138.4, 142.0, 142.7. IR (CH3CO2C2H5): 3409, 3025, 2925, 1489,
1090 cmꢁ1; LRMS (EI, 70 eV) m/z (%): 324 (Mþ, 100), 254 (92), 253
(72), 126 (75). Anal. Calcd for C20H14Cl2: C, 73.86; H, 4.34. Found: C,
73.80; H, 4.41.
133.5, 134.3, 134.6, 137.0, 139.7, 144.4, 148.4. IR (CH3CO2C2H5): 2923,
2358, 1261, 1024, 805 cmꢁ1; LRMS (EI, 70 eV) m/z (%): 369 (Mþ,
100), 371 (69), 252 (97), 126 (52). Anal. Calcd for C20H13Cl2NO2: C,
64.88; H, 3.54. Found: C, 64.94; H, 3.59.
4.2.15. (E)-1-Methyl-4-(2-o-chlorophenyl-2-p-tolylvinyl)
(3bc)12f. Yellow oil; 1H NMR (CDCl3, 300 MHz)
2.26 (s, 3H), 2.37 (s,
3H), 6.86 (s, 1H), 6.90–6.93 (m, 4H), 7.04–7.15 (m, 4H), 7.20–7.26 (m,
4H). 13C NMR (CDCl3, 75 MHz)
21.2, 21.3, 128.2, 128.7, 128.8, 129.1,
benzene
4.2.23. (E)-1-(2-Phenyl-2-o-tolylvinyl)benzene
oil; 1H NMR (CDCl3, 300 MHz)
2.11 (s, 3H), 6.61 (s, 1H), 7.14–7.22
(m, 14H), 7.26–7.29 (m, 1H). 13C NMR (CDCl3, 75 MHz)
20.5, 125.6,
126.7, 127.1, 127.4, 128.0, 128.2, 129.4, 129.9, 130.1, 130.2, 130.4,
136.2, 137.4, 140.2, 142.9, 144.0.
(3ai)12f. Colorless
d
d
d
d
129.4, 130.1, 131.4, 133.0, 134.3, 136.7, 137.0, 137.2, 140.5, 142.3.
4.2.16. (E)-1-(2-p-Chlorophenyl-2-p-fluorophenylvinyl)-4-fluo-
4.2.24. 1,1,2-Tri-o-tolylethene (3bi). Colorless oil; 1H NMR (CDCl3,
robenzene (3ec). White solid, mp 71–73 ꢀC; 1H NMR (CDCl3,
300 MHz)
d
2.10 (s, 3H), 2.29 (s, 3H), 2.30 (s, 3H), 6.53 (s, 1H), 6.96–
20.5,
300 MHz)
d
6.81–6.88 (m, 3H), 6.95–7.06 (m, 4H), 7.10–7.22 (m, 4H),
115.1 (d,
7.06 (m, 8H), 7.15–7.27 (m, 4H). 13C NMR (CDCl3, 75 MHz)
d
7.27–7.29 (m, 2H). 13C NMR (CDCl3, 75 MHz)
d
21.19, 21.24, 125.5, 127.2, 128.7, 128.9, 129.2, 129.5, 129.7, 130.1,
130.3,134.6,136.3,136.4, 136.7,137.4,142.0,144.4. IR (CH3CO2C2H5):
3016, 2920, 1508, 1449, 1043 cmꢁ1; LRMS (EI, 70 eV) m/z (%): 298
(Mþ, 100), 283 (33), 193 (33), 105 (29). Anal. Calcd for C23H22: C,
92.57; H, 7.43. Found: C, 92.62; H, 7.38.
JC–F¼21.3 Hz), 115.9 (d, JC–F¼20.6 Hz), 127.6, 128.4, 128.8, 131.1 (d,
JC–F¼7.6 Hz), 132.0 (d, JC–F¼8.3 Hz), 133.0 (d, JC–F¼3.4 Hz), 133.6,
135.5 (d, JC–F¼3.4 Hz), 140.2 (d, JC–F¼2.1 Hz), 141.5, 161.6 (d,
JC–F¼246.2 Hz), 162.3 (d, JC–F¼246.2 Hz). 19F NMR (470 MHz)
d
:
ꢁ113.8, ꢁ114.1; IR (CH3CO2C2H5): 2921, 1598, 1504,1228, 830 cmꢁ1
;
LRMS (EI, 70 eV) m/z (%): 326 (Mþ, 100), 290 (21), 271 (25), 270 (21).
4.2.25. (E)-1,3-Dimethyl-5-(2-(3,5-dimethylphenyl)-2-o-tolyl vinyl)-
Anal. Calcd for C20H13ClF2: C, 73.51; H, 4.01. Found: C, 73.58; H, 3.94.
benzene (3ci). Colorless oil; 1H NMR (CDCl3, 300 MHz)
d
2.16–2.18
(m, 15H), 6.47 (s, 1H), 6.75–6.84 (m, 6H), 7.16–7.23 (m, 4H). 13C NMR
(CDCl3, 75 MHz) 20.6, 21.18, 21.21, 125.5, 127.1, 127.2, 127.4, 128.4,
4.2.17. (E)-1-(2-Phenyl-2-p-chlorophenylvinyl)benzene
d
(3ac)12f. Colorless oil; 1H NMR (CDCl3, 300 MHz)
d
6.93 (s, 1H),
6.99–7.03 (m, 2H), 7.11–7.19 (m, 5H), 7.25–7.34 (m, 7H). 13C NMR
(CDCl3, 75 MHz) 126.9, 127.6, 128.0, 128.3, 128.5, 128.7, 128.8,
128.7, 130.1, 130.3, 136.2, 137.2, 137.3, 140.1, 142.5, 144.4. IR
(CH3CO2C2H5): 3011, 2919, 2861, 1597, 1041 cmꢁ1; LRMS (EI, 70 eV)
m/z (%): 326 (Mþ, 100), 220 (39), 207 (52), 205 (51). Anal. Calcd for
C25H26: C, 91.97; H, 8.03. Found: C, 92.02; H, 8.09.
d
129.5, 130.3, 133.3, 137.1, 139.9, 141.4, 141.9.
4.2.18. (E)-1-(2-Phenyl-2-p-fluorophenylvinyl)benzene
4.2.26. (E)-1-(2-p-Methoxyphenyl-2-o-tolylvinyl)-4-methoxy ben-
(3ad)20. White solid, mp 61–62 ꢀC; 1H NMR (CDCl3, 300 MHz)
zene (3di). Yellow oil; 1H NMR (CDCl3, 300 MHz)
d
1.99 (s, 3H),
3.66–3.67 (m, 6H), 6.39 (s, 1H), 6.61–6.66 (m, 4H), 6.97–7.13 (m,
8H). 13C NMR (CDCl3, 75 MHz)
20.5, 55.0, 55.1, 113.4, 113.5, 125.5,
d
6.89 (s, 1H), 6.95–7.03 (m, 4H), 7.10–7.19 (m, 5H), 7.25–7.32 (m,
5H). 13C NMR (CDCl3, 75 MHz)
d
115.0 (d, JC–F¼21.2 Hz), 126.8, 127.5,
d
128.0, 128.7, 129.2, 129.3, 129.5, 130.3, 137.2, 139.6 (d, JC–F¼2.8 Hz),
127.2, 128.6, 130.3, 130.5, 131.0, 132.8, 136.2, 140.7, 144.4, 158.2. IR
(CH3CO2C2H5): 2956, 2836, 1604, 1508, 1247 cmꢁ1; LRMS (EI, 70 eV)
m/z (%): 330 (Mþ, 100), 222 (18), 209 (26), 121 (18). Anal. Calcd for
C23H22O2: C, 83.60; H, 6.71. Found: C, 83.67; H, 6.67.
140.2, 141.6, 162.4 (d, JC–F¼245.5 Hz). 19F NMR (470 MHz)
: ꢁ114.9.
d
4.2.19. 1,1,2-Tri-p-chlorophenylethene (3fc)21. Colorless oil; 1H NMR
(CDCl3, 300 MHz) 6.87 (s,1H), 6.92–6.95 (m, 2H), 7.07–7.21 (m, 6H),
7.26–7.32 (m, 4H). 13C NMR (CDCl3, 75 MHz)
127.7, 128.3, 128.5,
d
d
4.2.27. (E)-1-(2-o-Tolyl-2-p-fluorophenylvinyl)-4-fluoro
(3ei). Colorless oil; 1H NMR (CDCl3, 300 MHz)
2.08 (s, 3H), 6.56 (s,
1H), 6.85–6.93 (m, 4H), 7.06–7.25 (m, 8H). 13C NMR (CDCl3, 75 MHz)
benzene
128.8, 129.1, 130.2, 130.7, 131.7, 132.8, 133.8, 135.2, 137.9, 140.9, 141.1.
d
4.2.20. (Z)-1-(2-p-(Trifluoromethyl)phenyl-2-p-chlorophenylvinyl)-
d
20.5, 115.0 (d, JC–F¼16.6 Hz), 115.3 (d, JC–F¼16.5 Hz), 125.7, 127.6,
4-chlorobenzene (3fe). White solid, mp 105–108 ꢀC; 1H NMR
129.0,130.1,130.5,130.9 (d, JC–F¼7.6 Hz),131.5 (d, JC–F¼8.3 Hz),133.2
(d, JC–F¼3.4 Hz), 135.9 (d, JC–F¼3.4 Hz), 136.2, 141.8 (d, JC–F¼1.3 Hz),
143.5, 161.6 (d, JC–F¼245.6 Hz), 161.9 (d, JC–F¼246.2 Hz). 19F NMR
(CDCl3, 300 MHz)
d
6.95–6.98 (m, 3H), 7.01–7.16 (m, 4H), 7.31–7.39
125.293 (q,
(m, 4H), 7.55–7.58 (m, 2H). 13C NMR (CDCl3, 75 MHz)
d
JC–F¼3.8 Hz), 127.725 (q, JC–F¼270.8 Hz), 127.833, 128.429, 129.162,
(470 MHz)
d: ꢁ114.5, ꢁ114.7. IR (CH3CO2C2H5): 2925, 2359, 1599,
129.254, 129.942, 130.804, 131.675, 133.986, 134.940, 137.636,
1506, 128 cmꢁ1; LRMS (EI, 70 eV) m/z (%): 306 (Mþ, 100), 291 (31),
197 (84), 196 (39). Anal. Calcd for C21H16F2: C, 82.33; H, 5.26. Found:
C, 82.37; H, 5.32.
140.754, 146.192. 19F NMR (470 MHz)
d
: ꢁ62.4; IR (CH3CO2C2H5):
3041, 2929, 1912, 1325, 1124 cmꢁ1; LRMS (EI, 70 eV) m/z (%): 392
(Mþ, 100), 322 (60), 252 (37), 126 (31). Anal. Calcd for C21H13Cl2F3:
C, 64.14; H, 3.33. Found: C, 64.19; H, 3.40.
4.2.28. (E)-3-(2-o-Tolyl-2-(thiophen-3-yl)vinyl)thiophene
(3hi). Colorless oil; 1H NMR (CDCl3, 300 MHz)
d
2.09 (s, 3H), 6.52 (s,
1H), 6.83–6.84 (m,1H), 6.91–7.28 (m, 9H). 13C NMR (CDCl3, 75 MHz)
20.2, 124.0, 124.2, 124.4, 124.7, 124.8, 125.6, 127.4, 128.1, 128.8,
4.2.21. (Z)-1-(2-p-Cyanophenyl-2-p-chlorophenylvinyl)-4-chloro-
benzene (3ff). Yellow solid, mp 85–87 ꢀC; 1H NMR (CDCl3,
d

2438
X. Xu et al. / Tetrahedron 66 (2010) 2433–2438
129.6, 130.3, 136.2, 136.8, 138.7, 141.1, 143.7. IR (CH3CO2C2H5): 3099,
3015, 1452, 863, 769 cmꢁ1; LRMS (EI, 70 eV) m/z (%): 282 (Mþ, 100),
267 (26), 234 (47), 135 (21). Anal. Calcd for C17H14S2: C, 72.30; H,
5.00. Found: C, 72.37; H, 4.94.
125.6, 126.4, 126.8, 128.0, 128.2, 128.9, 129.1, 130.2, 134.7, 138.0,
139.0, 145.8. IR (CH3CO2C2H5): 3019, 2360, 1598, 1444, 759 cmꢁ1
;
LRMS (EI, 70 eV) m/z (%): 208 (Mþ, 94), 193 (100), 178 (72), 115 (77).
Anal. Calcd for C16H16: C, 92.26; H, 7.74. Found: C, 92.32; H, 7.81.
4.2.29. (Z)-1-Methyl-2-(2-phenyl-2-o-tolylvinyl)benzene
Yellow oil; 1H NMR (CDCl3, 300 MHz)
1.99 (s, 3H), 2.38 (s, 3H),
6.67–6.82 (m, 2H), 6.97–7.21 (m, 7H), 7.26–7.32 (m, 5H). 13C NMR
(CDCl3, 75 MHz) 19.8, 20.2, 125.2, 125.8, 126.8, 126.9, 127.1, 127.3,
(3ia).
4.2.38. Compounds3aa and 3aa-d (46:54). 1H NMR (CDCl3,
d
300 MHz)
75 MHz)
d
6.96 (m, 0.46H), 7.01–7.33 (m, 15H). 13C NMR (CDCl3,
d
126.7, 127.4, 127.5, 127.6, 127.9, 128.1, 128.2, 128.6, 129.50,
d
129.52, 130.4, 137.27, 137.34, 140.3, 142.5, 142.6, 143.38, 143.40.
128.3, 128.4, 128.6, 129.7, 130.2, 130.8, 136.5, 136.7, 136.8, 139.5,
142.0, 142.7; LRMS (EI, 70 eV) m/z (%): 284 (Mþ, 100), 269 (56), 192
(50), 179 (44). Anal. Calcd for C22H20: C, 92.91; H, 7.09. Found: C,
92.86; H, 7.15.
Acknowledgements
We thank the National Key Technology R&D Program (No.
2007BAI34B00) and Natural Science Foundation of Zhejiang Prov-
ince (No. Y4080107) for financial support.
4.2.30. (Z)-1-(2-(Naphthalen-1-yl)-2-phenylvinyl)
(3ja). White solid, mp 145–147 ꢀC; 1H NMR (CDCl3, 300 MHz)
6.82–6.90 (m, 2H), 7.18–7.51 (m,12H), 7.69–7.87 (m, 5H), 7.21–7.24
(m, 1H). 13C NMR (CDCl3, 75 MHz)
124.4, 125.1, 125.5, 125.59,
naphthalene
d
Supplementary data
d
125.60, 125.9, 126.0, 126.3, 126.4, 126.8, 126.9, 127.2, 127.6, 127.7,
127.9, 128.30, 128.32, 128.5, 132.3, 132.5, 133.3, 133.7, 134.6, 137.6,
142.8, 142.9. IR (CH3CO2C2H5): 3019, 2920, 1487, 1451 cmꢁ1; LRMS
Supplementary data associated with this article can be found in
the online version, at doi:10.1016/j.tet.2010.01.086.
(EI, 70 eV) m/z (%): 356 (Mþ, 100), 279 (68). Anal. Calcd for C28H20
:
References and notes
C, 94.34; H, 5.66. Found: C, 94.39; H, 5.72.
1. (a) Fagnou, K.; Lautens, M. Chem. Rev. 2003, 103, 169; (b) Li, C.-J. Chem. Rev.
2005, 105, 3095.
2. Shirakawa, E.; Yamagami, T.; Kimura, T.; Yamaguchi, S.; Hayashi, T. J. Am. Chem.
Soc. 2005, 127, 17164.
3. Ohe, T.; Uemura, S. Tetrahedron Lett. 2002, 43, 1269.
4. (a) Miyaura, N.; Suzuki, A. Chem. Rev. 1995, 95, 2457; (b) Darses, S.; Genet, J. P.
Chem. Rev. 2008, 108, 288.
4.2.31. (E)-1-(2-(Naphthalen-1-yl)-2-phenylvinyl)benzene
(3aj)22. colorless oil; 1H NMR (CDCl3, 300 MHz)
6.97 (s, 1H), 7.01–
7.04 (m, 2H), 7.09–7.25 (m, 5H), 7.28–7.35 (m, 8H). 13C NMR (CDCl3,
75 MHz) 126.7, 127.4, 127.5, 127.6, 127.9, 128.15, 128.18, 128.6,
d
d
129.5, 130.4, 137.4, 140.4, 142.6, 143.4.
5. Hayashi,T.;Inoue, K.; Taniguchi, N.; Ogasawara, M. J. Am.Chem. Soc. 2001,123, 9918.
ˆ
6. Rhodium-catalyzed unsymmetric addition: (a) Genin, E.; Michelet, V.; Genet,
4.2.32. 1,1,2-Tri-o-tolylethene (3ii). Colorless oil; 1H NMR (CDCl3,
J. P. Tetrahedron Lett. 2004, 45, 4157; (b) Genin, E.; Michelet, V.; Geneˆt, J.-P.
J. Organomet. Chem. 2004, 689, 3820.
300 MHz)
d
1.92 (s, 3H), 2.23 (s, 3H), 2.31 (s, 3H), 6.72–6.84 (m, 3H),
19.9, 20.2, 20.7,
7. Rhodium-catalyzed unsymmetric addition by using a variety of special alkynes
bearing heteroatoms in given locations as substrates: (a) Kim, N.; Kim, K. S.;
Guptab, A. K.; Oh, C. H. Chem. Commun. 2004, 618; (b) Lautens, M.; Yoshida, M.
J. Org. Chem. 2003, 68, 762; (c) Alfonsi, M.; Arcadi, A.; Chiarini, M.; Marinelli, F.
J. Org. Chem. 2007, 72, 9510; (d) Lautens, M.; Yoshida, M. Org. Lett. 2002, 4, 123;
(e) Oh, C. H.; Park, S. J.; Ryu, J. H.; Gupta, A. K. Tetrahedron Lett. 2004, 45, 7039.
8. Shirakawa, E.; Takahashi, G.; Tsuchimoto, T.; Kawakami, Y. Chem. Commun.
2001, 2688.
9. (a) Yamamoto, Y.; Kirai, N.; Harada, Y. Chem. Commun. 2008, 2010; (b) Lin, P.-S.;
Jeganmohan, M.; Cheng, C.-H. Chem.dEur. J. 2008, 14, 11296.
10. Palladium-catalyzed hydroarylations of alkynes with organoboronic acids: (a)
Oh, C. H.; Jung, H. H.; Kim, K. S.; Kim, N. Angew. Chem., Int. Ed. 2003, 42, 805; (b)
Gupta, A. K.; Kim, K. S.; Oh, C. H. Synlett 2005, 457.
7.00–7.21 (m, 10H). 13C NMR (CDCl3, 75 MHz)
d
125.2, 125.5, 125.6, 126.9, 127.0, 127.1, 128.9, 129.8, 130.1, 130.3,
130.7, 130.76, 130.79, 135.9, 136.2, 136.4, 136.9, 140.0, 142.0, 143.6. IR
(CH3CO2C2H5): 3059, 3016, 2923, 1453, 767 cmꢁ1; LRMS (EI, 70 eV)
m/z (%): 298 (Mþ, 100), 283 (63), 268 (31), 105 (43). Anal. Calcd for
C23H22: C, 92.57; H, 7.43. Found: C, 92.62; H, 7.50.
4.2.33. (E)-4-Phenyl-4-octene (3ka)2. Colorless oil; 1H NMR (CDCl3,
300 MHz)
d
0.88 (t, J¼7.5 Hz, 3H), 0.96 (t, J¼7.5 Hz, 3H), 1.32–1.50
(m, 4H), 2.13–2.21 (m, 2H), 2.45–2.50 (m, 2H), 5.66 (t, J¼7.2 Hz, 1H),
11. (a) Palladium-catalyzed hydroarylations of alkynes with sodium tetraphe-
nylborate: Zeng, H.; Hua, R. J. Org. Chem. 2008, 73, 558; (b) Palladium-catalyzed
addition of arylboronic acids to internal alkynes: Zhou, C.; Larock, R. C. J. Org.
Chem. 2006, 71, 3184.
7.18–7.36 (m, 5H). 13C NMR (CDCl3, 75 MHz)
31.7, 43.5, 126.3, 128.1, 129.2, 140.0.
d 14.0, 21.8, 23.1, 30.6,
12. Our previous work on transmetal-catalyzed additions of organoboronic acids to
the carbon–carbon or carbon–hetero unsaturated bonds: (a) Qin, C.; Wu, H.;
Cheng, J.; Chen, X.; Liu, M.; Zhang, W.; Su, W.; Ding, J. J. Org. Chem. 2007, 72,
4102; (b) Qin, C.; Chen, J.; Wu, H.; Cheng, J.; Zhang, Q.; Zou, B.; Su, W.; Ding, J.
Tetrahedron Lett. 2008, 49, 1884; (c) Qin, C.; Wu, H.; Chen, J.; Liu, M.; Cheng, J.;
Su, W.; Ding, J. Org. Lett. 2008, 10, 1537; (d) Zhang, Q.; Chen, J.; Liu, M.; Wu, H.;
Cheng, J.; Qin, C.; Su, W.; Ding, J. Synlett 2008, 935; (e) Zheng, H.; Zhang, Q.;
Che, J.; Liu, M.; Cheng, S.; Ding, J.; Wu, H.; Su, W. J. Org. Chem. 2009, 74, 943; (f)
Zhang, W.; Liu, M.; Wu, H.; Ding, J. Tetrahedron Lett. 2008, 49, 5214.
13. (a) Yang, Y. Synth. Commun. 1989, 19, 1001; (b) Menard, F.; Chapman, T. M.;
Dockendorff, C.; Lautens, M. Org. Lett. 2006, 8, 4569.
4.2.34. (E)-4-o-Tolyl-4-octene (3ki)2. Colorless oil; 1H NMR (CDCl3,
300 MHz)
d
0.87 (t, J¼7.2 Hz, 3H), 0.96 (t, J¼7.5 Hz, 3H), 1.25–1.32
(m, 2H), 1.41–1.49 (m, 2H), 2.12–2.19 (m, 2H), 2.26–2.34 (m, 5H),
5.24 (t, J¼7.2 Hz, 1H), 7.02–7.16 (m, 4H). 13C NMR (CDCl3, 75 MHz)
d
13.9, 14.2, 19.9, 21.4, 23.0, 30.1, 33.8, 125.1, 126.2, 129.0, 129.7,
129.9, 135.2, 140.5, 144.6.
4.2.35. (E)-1,2-Diphenylpropene (3ma)23. White solid, mp 80–
82 ꢀC; 1H NMR (CDCl3, 300 MHz)
d
2.27 (s, 3H), 6.83 (s, 1H), 7.19–
7.39 (m, 8H), 7.50–7.53 (m, 2H). 13C NMR (CDCl3, 75 MHz)
17.4,
126.0, 126.4, 127.2, 127.7, 128.1, 128.3, 129.1, 127.4, 138.3, 143.9.
14. Cheng, J.; Sun, Y.; Wang, F.; Guo, M.; Xu, J.-H.; Pan, Y.; Zhang, Z. J. Org. Chem.
2004, 69, 5428.
d
15. Oxidative addition of a carbon–boron bond to Pd(0) has so far been proposed in
several cases: (a) Ohe, T.; Ohe, K.; Uemura, S.; Sugita, N. J. Organomet. Chem.
1988, 344, C5; (b) Cho, C. S.; Uemura, S. J. Organomet. Chem. 1994, 465, 85; (c)
Cho, C. S.; Motofusa, S.-i.; Ohe, K.; Uemura, S. J. Org. Chem. 1995, 60, 883.
16. For review, see: Lappert, M. F. Chem. Rev. 1956, 56, 959.
17. Zhang, W.; Wu, H.; Liu, Z.; Zhong, P.; Zhang, L.; Huang, X.; Cheng, J. Chem.
Commun. 2006, 4826.
18. Sandro, C.; Giancarlo, F.; Antonella, G.; Daniela, P. Org. Lett. 2008, 10, 1597.
19. Lee, C. C.; Weber, U. J. Org. Chem. 1978, 43, 2721.
4.2.36. (E)-1-Phenyl-2-m-methoxyphenylpropene (3mb)6b. Color-
less oil; 1H NMR (CDCl3, 300 MHz)
2.27 (s, 3H), 3.84 (s, 3H), 6.84–
6.85 (m, 2H), 7.06–7.37 (m, 8H). 13C NMR (CDCl3, 75 MHz)
17.5,
d
d
55.2, 59.5, 111.9, 112.4, 118.5, 126.5, 127.8, 128.1, 129.1, 129.2, 137.2,
138.2, 145.5.
20. Sandro, C.; Giancarlo, F.; Antonella, G.; Marcial, M.-M.; Adelina, V. Tetrahedron
Lett. 2002, 43, 5537.
4.2.37. (E)-1-Phenyl-2-o-tolylpropene (3mi). Colorless oil; 1H NMR
21. Tadros, W.; Farahat, K.; Robson, J. M. J. Chem. Soc. 1949, 439.
22. Terao, Y.; Nomoto, M.; Satoh, T.; Miura, M.; Nomura, M. J. Org. Chem. 2004, 69,
6942.
(CDCl3, 300 MHz)
d
2.18 (s, 3H), 2.35 (s, 3H), 6.37 (s, 1H), 7.19–7.25
19.8, 19.9,
(m, 5H), 7.37–7.38 (m, 4H). 13C NMR (CDCl3, 75 MHz)
d
23. Cotter, J.; Hogan, A.-M. L.; O’Shea, D. F. Org. Lett. 2007, 9, 1493.