Palladium- and nickel-catalyzed kumada cross-coupling reactions of gem -difluoroalkenes and monofluoroalkenes with Grignard reagents

Article abstract of DOI:10.1021/jo5022234

A novel Kumada-Tamao-Corriu cross-coupling reaction of gem-di- or monofluoroalkenes with Grignard reagents, with or without β-hydrogen atoms, in the presence of a catalytic amount of palladium- or nickel-based catalysts has been developed. The reaction is performed under mild conditions (room temperature or reflux in diethyl ether for 1-2 h) and leads to di-cross- or mono-cross-coupled products in good to high yields.

Full text of DOI:10.1021/jo5022234

Article
pubs.acs.org/joc
Palladium- and Nickel-Catalyzed Kumada Cross-Coupling Reactions
of gem-Difluoroalkenes and Monofluoroalkenes with Grignard
Reagents
Wenpeng Dai,† Juan Xiao,† Guanyi Jin,† Jingjing Wu,*,‡,§ and Song Cao*,†,‡
†Shanghai Key Laboratory of Chemical Biology, School of Pharmacy, East China University of Science and Technology (ECUST),
Shanghai 200237, China
‡Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai
200032, China
§School of Chemical and Environmental Engineering, Shanghai Institute of Technology, Shanghai 201418, China
S
* Supporting Information
ABSTRACT: A novel Kumada−Tamao−Corriu cross-coupling reaction of gem-di- or monofluoroalkenes with Grignard
reagents, with or without β-hydrogen atoms, in the presence of a catalytic amount of palladium- or nickel-based catalysts has been
developed. The reaction is performed under mild conditions (room temperature or reflux in diethyl ether for 1−2 h) and leads to
di-cross- or mono-cross-coupled products in good to high yields.
(Pd)-catalyzed coupling reactions of fluorine-containing olefins,
such as tetrafluoroethylene and hexafluoropropylene, with
Grignard reagents with the aid of a ligand (PPh3); however,
the yields of these reactions were not high, and a mixture of di-
cross- and mono-cross-coupled products was obtained.7
Furthermore, despite their synthetic utility, these methods
suffer from several drawbacks such as narrow substrate scope,
lack of stereocontrol over double-bond geometry, the presence
of inseparable E/Z isomers, and a mixture of mono- and
disubstitution products. Thus, the development of alternative
transition-metal-catalyzed coupling reactions of alkenyl fluo-
rides with Grignard reagents via CF bond activation that can
be performed under milder conditions is highly desirable. In
continuation of our interest in the functionalization of the C
F bond of fluoroalkene and aryl fluoride,8 we report here
palladium- and nickel-catalyzed coupling reactions of gem-di- or
monofluoroalkenes with different Grignard reagents, which
afford di-cross- or mono-cross-coupled products in good to
high yields (Scheme 1).
INTRODUCTION
■
Transition-metal-catalyzed cross coupling of aryl or alkenyl
halides with Grignard reagents (RMgX), known as the
Kumada−Tamao−Corriu cross-coupling reaction, is one of
the most valuable and versatile methods for the construction of
carboncarbon bonds since its discovery in the 1970s.1 With
more than 40 years of extensive investigation of Kumada
reactions, it currently matters not whether coupling partners are
very reactive organic bromides and iodides or unactivated alkyl
chlorides, the Kumada reaction can proceed smoothly through
modification of the reaction conditions.2
Recently, the use of aryl fluorides as the electrophile coupling
partner in Kumada reactions has attracted much attention due
to the importance of functionalization of the CF bond.3
However, cross-coupling reactions of alkenyl fluorides with
Grignard reagents have been little studied, and only a few
examples of CC bond formation using alkenyl fluorides have
been reported.4 Earlier studies have demonstrated that
fluoroolefins bearing a greater number of fluorine or chlorine
atoms, such as 1-arylpentafluoropropene and 1,l-dichloro-2,2-
difluoroethylene, could react with RMgX without a metal
catalyst.5 Ishihara and co-workers reported that the reaction of
various fluorine-containing alkenes containing an electron-
withdrawing group, such as pentafluorocrotonate, trifluoroa-
crylic ester, and trifluorovinyl sulfone, with Grignard reagents
proceeds smoothly in the presence of CuCN to give their
corresponding addition−elimination products in good to high
yields.6 In 2011, Nagai described nickel (Ni)- and palladium
RESULTS AND DISCUSSION
■
Generally, the Kumada cross-coupling reaction of Grignard
reagents with organohalides is achieved by using a catalytic
amount of a nickel or palladium catalyst.4b,9 Therefore, we first
tested nickel catalyst NiCl2(dppe) using the model reaction of
Received: September 28, 2014
© XXXX American Chemical Society
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Scheme 1. Pd- or Ni-Catalyzed Cross-Coupling Reaction of gem-Difluoroalkenes with R2MgX
1-(2,2-difluorovinyl)-4-methoxybenzene 1a with methylmagne-
sium chloride 2a in diethyl ether in different reaction
conditions (Table 1, entries 1−6). Although the use of
Having optimized the reaction conditions (Table 1, entry
11), we next examined the scope of this Pd(PPh3)4-catalyzed
cross-coupling reaction of gem-difluoroalkenes with Grignard
reagents (Table 2, utilized substrates listed in the Supporting
Information). Difluoroethenes with electron-donating substitu-
ents such as CH3O (1a), BnO (1b), and CH3S (1c) on the
aromatic ring underwent coupling reactions with high yields. 1-
Aryl-2,2-difluoroethenes that have a naphthyl group could also
be converted to a double cross-coupling product with a good
yield (1d). When an aliphatic difluoroalkene such as 1,1-
difluoro-2-benzyl ethylene was used as the substrate, the
reaction did not proceed well, and only a small amount of di-
cross-coupled product was observed. The aromatic ring in
difluoroalkenes seems necessary to ensure a high yield.
Unfortunately, the cross coupling of Grignard reagents
bearing β-hydrogen atoms, such as n-BuMgCl, EtMgCl, n-
PrMgBr, n-C5H11MgBr, and C6H5CH2CH2MgCl, with gem-
difluoroalkenes in the presence of Pd(PPh3)4 afforded only
disubstituted alkenes in moderate yields (60−80%, GC/MS).
This might be partly attributable to facile β-hydride elimination
of Grignard reagents catalyzed by Pd(PPh3)4, which leads to
undesired olefin products.10
In the following investigation, our attention was directed
toward the reaction of gem-difluoroalkenes with alkyl Grignard
reagents containing β-hydrogen atoms. Grignard reagent n-
BuMgCl 2f was used as a test substrate for screening reaction
conditions (Table 3). In the absence of catalyst, only a trace
amount of double cross-coupling product 3af was detected
(entry 1). The use of Co(acac)2 resulted in the formation of the
double cross-coupled product in a very low yield; however,
dehydrofluorinated cross-coupled product 3af′ was predom-
inantly observed (entry 2).11 It was suprising to find that when
the reaction was catalyzed with PdCl2(dppf), a highly effective
catalyst for cross coupling of primary and secondary alkyl
Grignard reagents containing β-hydrogen atoms with organic
halides,12 substrate 1a was almost completely recovered in the
reaction mixture (entry 3). Although Pd(PPh3)4 exhibited
excellent catalytic activity in the cross coupling of gem-
difluoroalkenes with Grignard reagents without β-hydrogen
atoms, the Pd(PPh3)4-catalyzed coupling reaction of 1a with 2f
was unsuccessful, giving the expected product 3af only in
moderate yield along with a considerable amount of 3af′
(entries 4 and 5). Hydrodefluorination of 1-(2,2-difluorovinyl)-
4-methoxybenzene 1a to afford 1-methoxy-4-vinylbenzene
under the above-mentioned reaction conditions is difficult.
The second CF bond in 1a reacts quickly with RMgX to
form 3af′, and no 1-methoxy-4-vinylbenzene was detected at
all.
Table 1. Optimization of the Reaction Conditions for the
Synthesis of 3aa
a
entry
catalyst (mol %)
MeMgCl (equiv)
T (°C)
yield (%)
1
NiCl2(dppe) (5)
NiCl2(dppe) (5)
NiCl2(dppe) (5)
NiCl2(dppe) (5)
NiCl2(dppe) (5)
NiCl2(dppe) (5)
PdCl2(dppb) (5)
PdCl2(dppf) (5)
PdCl2(dppe) (5)
Pd2(dba)3 (5)
Pd(PPh3)4 (5)
Pd(PPh3)4 (5)
Pd(PPh3)4 (5)
Pd(PPh3)4 (4)
none
2.4
2.4
2.4
3.6
3.6
1.0
2.4
2.4
2.4
2.4
2.4
2.4
2.4
2.4
2.4
2.0
1.2
0.8
0
15
25
60
51
78
0
2
rt
3
reflux
rt
4
5
reflux
reflux
reflux
reflux
reflux
reflux
reflux
25
6
7
3
8
0
9
0
10
11
12
13
14
15
16
17
18
28
95
75
0
15
reflux
reflux
reflux
reflux
reflux
77
0
Pd(PPh3)4 (5)
Pd(PPh3)4 (5)
Pd(PPh3)4 (5)
37
4
0
a
Yields refer to desired product 3aa and are determined by GC
analysis based on 1a (1 mmol).
NiCl2(dppe) resulted in the formation of the double cross-
coupling product in moderate yield (78%, GC/MS, entry 5), a
sizable amount of the starting material 1a was recovered. Next,
we focused on the Kumada coupling reaction of 1a with 2a in
the presence of various Pd catalysts (entries 7−18). Among the
Pd catalysts tested, Pd(PPh3)4 was found to be the most
effective (entry 11). Working at lower reaction temperatures
resulted in a decrease in the reaction rate (entries 12 and 13).
Decreasing the amount of Pd(PPh3)4 or 2a obviously
diminished the yield (entries 14 and 16−18). In addition, the
control experiment showed that no reaction occurred in the
absence of a nickel or palladium catalyst (entry 15).
Interestingly, only a trace amount of the monocoupled product
was detected in this case, regardless of whether the reaction was
performed in the presence of either a palladium or a nickel
catalyst. Furthermore, no relationship could be found for the
formation of the monocoupled product based on the amount of
2a added.
Based on the pioneering contributions of Kumada, the cross-
coupling reaction of organic halides with alkylmagnesium
halides bearing β-hydrogen atoms could proceed efficiently in
the presence of a nickel catalyst.13 Therefore, we next focused
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a
Table 2. Pd(PPh3)4-Catalyzed Cross Coupling of gem-Difluoroalkenes with Grignard Reagents
a
Reaction conditions: gem-difluoroalkenes 1a−d (1.0 mmol), R2MgX 2a−e (2.4 mmol), diethyl ether (8 mL), 2 h.
Table 3. Optimization of the Reaction Conditions for the Synthesis of 3af
a
entry
catalyst (mol %)
solvent
n-BuMgCl (equiv)
3af/3af′ yield (%)
1
none
Et2O
Et2O
Et2O
Et2O
2.4
2.4
2.4
2.4
2.4
2.4
2.4
2.4
2.4
2.4
2.4
2.4
2.4
2.4
2.4
2.4
2.0
1.2
4/0
5/60
NR
2
Co(acac)2 (5)
PdCl2(dppf) (5)
Pd(PPh3)4 (5)
Pd(PPh3)4 (5)
NiCl2 (5)
3
4
75/25
80/20
64/27
48/51
40/32
32/69
95/5
99
b
5
Et2O
6
Et2O
Et2O
Et2O
Et2O
Et2O
Et2O
Et2O
Et2O
THF
DMF
CH3CN
Et2O
Et2O
7
Ni(acac)2 (5)
8
NiCl2(PCy3)2 (5)
NiBr2(PPh3)2 (5)
NiCl2(dppp) (5)
NiCl2(dppe) (5)
NiCl2(dppe) (4)
NiCl2(dppe) (3)
NiCl2(dppe) (5)
NiCl2(dppe) (5)
NiCl2(dppe) (5)
NiCl2(dppe) (4)
NiCl2(dppe) (4)
9
10
11
12
13
14
15
16
17
18
99
90
95/2
NR
NR
75/5
34/33
a
b
Single yields refer to the desired product 3af and are determined by GC analysis based on 1a (1 mmol). Reflux.
on screening various nickel-based catalysts. Different nickel
complexes, such as NiCl2, Ni(acac)2, NiCl2(PCy3)2,
NiBr2(PPh3)2, NiCl2(dppp), and NiCl2(dppe), were separately
applied in the reaction (entries 6−11). The results indicated
C
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a
Table 4. NiCl2(dppe)-Catalyzed Cross Coupling of gem-Difluoroalkenes with Grignard Reagents
a
Reaction conditions: gem-difluoroalkenes 1a−f (1.0 mmol), R2MgX 2f−j (2.4 mmol), diethyl ether (8 mL), 2 h.
that NiCl2(dppe) was clearly the best choice, and NiCl2(dppp)
provided a slightly lower yield. Catalyst loading was found to
affect the yield, and 4 mol % NiCl2(dppe) seemed to be
optimal for this reaction (entries 11−13). The use of different
solvents revealed that diethyl ether is the best reaction medium
among those tested for this reaction (entries 12 and 14−16).
On the other hand, a significant decrease in yield was observed
when the amount of 2f was reduced to 1.2 equiv, giving
expected product 3af in 34% yield along with 33% of the
dehydrofluorinated product 3af′ (entries 17 and 18).
Table 5. Pd(PPh3)4-Catalyzed Coupling Reaction of
a
Symmetrical gem-Difluoroalkenes 1g with R2MgX
Using the optimized conditions described above (Table 3,
entry 12), we next tried to extend the Kumada coupling
reactions to other alkylmagnesium halides bearing β-hydrogen
atoms. As can be seen in Table 4, in most cases, gem-
difluoroalkenes 1a−f could react with alkylmagnesium halides
2f−j efficiently and transform into di-cross-coupled products
with good to high yields. To our delight, only trace amounts of
mono-cross-coupled and dehydrofluorinated products were
observed. Difluoroalkenes bearing a halide atom on the aryl
ring such as 1-bromo-3-(2,2-difluorovinyl)benzene 1f also
afforded the expected product in a good yield (3ff). However,
when this nickel catalytic system was applied to Kumada
coupling of Grignard reagents without β-hydrogen atoms, such
as 2a−e, the yield of the coupling product decreased sharply
(25−72%, GC).
To further verify the generality of the cross-coupling reaction
involving the CF bond of fluoroalkene, symmetrical gem-
difluoroalkene 1g and six monofluoroalkenes, (E)-1h, (E)-1i,
and 1j−m, were subjected to cross coupling with Grignard
reagents in the presence of Pd(PPh3)4 as a catalyst under the
optimized reaction conditions (Table 1, entry 11). The results
are shown in Tables 5−7. The coupling reaction of
fluoroalkenes with Grignard reagents without β-hydrogen
atoms proceeded very well to afford the desired products in
good to excellent yields, regardless of whether the fluoroalkenes
were symmetrical gem-difluoroalkenes or monofluoroalkenes.
However, the reaction of (2,2-difluoroethene-1,1-diyl)-
a
Reaction conditions: gem-difluoroalkenes 1g (1.0 mmol), R2MgX
(2.4 mmol), diethyl ether (8 mL), 2 h.
dibenzene 1g with p-tolylMgBr 2d proceeded less efficiently,
affording the desired product in only 43% yield, presumably
due to steric repulsion between the neighboring benzene rings
(Table 5, 3gd). An alkynyl group next to the fluoroalkene did
not affect this transformation and gave the expected products in
high yields (Table 7). As shown in Tables 6 and 7, the reaction
of monofluoroalkenes with CH3 MgCl, PhMgBr,
C6H5CH2MgCl, p-tolylMgBr, and 4-FC6H4MgBr and catalyzed
by Pd(PPh3)4 gives only cross-coupling products in high yields.
A novel NiCl2(dppe) catalytic system was also expanded to
the coupling reaction of n-BuMgCl with some fluoroalkenes,
such as 1g, (E)-1i, and 1j (Table 8). Unfortunately, these
reactions were unsuccessful; only (E)-1i afforded desired
coupled product (E)-3if in moderate yield (62%).
D
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a
Table 6. Pd(PPh3)4-Catalyzed Coupling Reaction of Monofluoroalkenes (E)-1h and (E)-1i with R2MgX
a
Reaction conditions: (E)-1h and (E)-1i (1.0 mmol), R2MgX (2.0 mmol), diethyl ether (8 mL), 2 h.
a
Table 7. Pd(PPh3)4-Catalyzed Coupling Reaction of Monofluoroalkenes 1j−m with R2MgX
a
Reaction conditions: 1j−m (1.0 mmol), R2MgX (2.0 mmol), diethyl ether (8 mL), 2 h.
On the basis of the observations described above and related
literature, we hypothesize that the reaction mechanism is
essentially analogous to previous reports regarding Ni- or Pd-
catalyzed coupling reactions of alkenyl halides (X = Cl, Br, I)
and aryl fluorides with Grignard reagents.1d,3a,10a The proposed
mechanism of the Ni-catalyzed coupling reaction of fluo-
roalkene with Grignard reagents bearing β-hydrogen atoms
(2f−j) is depicted in Scheme 2. The Ni-catalyzed coupling
reaction involves three elementary steps: oxidative addition of
RF, transmetalation of RMgX, and reductive elimination of the
Ni complex. The mechanism of the Pd-catalyzed coupling
reaction of fluoroalkene with Grignard reagents without β-
hydrogen atoms (2a−e) is almost the same as that of the Ni-
catalyzed coupling reaction.
It has been reported that when primary and secondary alkyl
Grignard reagents that have β-hydrogen atoms were used as
coupling partners with organic halides, that aside from their
corresponding cross-coupling products, a small amount of
reduction product was observed.1d,10b,13,14 A putative mecha-
nism for the formation of a dicoupled product (VII) and a
monocouple-reduced byproduct (XI) via a Pd(PPh3)4-catalyzed
coupling reaction of difluoroalkene with n-BuMgCl is illustrated
in Scheme 3. We tried to isolate intermediates I and IV and
cultivate single crystals but failed to get them to cultivate.
In summary, we have developed two new and efficient
palladium- and nickel-based catalytic systems for the coupling
of gem-difluoroalkenes or monofluoroalkenes with Grignard
reagents under simple and mild reaction conditions without any
E
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a
Table 8. NiCl2(dppe)-Catalyzed Coupling Reaction of 1g, (E)-1i, and 1j with R2MgX
a
Reaction conditions: 1g, (E)-1i, and 1j (1.0 mmol), n-BuMgCl (2.4 or 2.0 mmol), diethyl ether (8 mL), 2 h. Yields determined by GC analysis and
based on 1g, (E)-1i, and 1j (1 mmol).
resolution mass spectra (HRMS) were acquired in electron-impact
(EI) mode using a TOF mass analyzer.
Scheme 2. Proposed Mechanism for the Ni-Catalyzed Cross-
Coupling Reaction of Fluoroalkene with Grignard Reagents
Synthesis of Compounds 1a−m. Substrates 1a−g were synthe-
sized according to literature procedures.8d Substrates (E)-1h and (E)-
1i were synthesized according to methods in the literature.15
Substrates 1j−m were prepared according to reported methods.16
General Procedure for the Cross-Coupling Reaction. To a solution
of gem-difluoroalkenes or monofluoroalkenes (1 mmol) and Pd-
(PPh3)4 (57.8 mg, 0.05 mmol) or NiCl2(dppe) (21.2 mg, 0.04 mmol)
in diethyl ether was added dropwise a solution of Grignard reagent in
THF or Et2O (2.4 or 2.0 mmol) at room temperature under an argon
atmosphere. The mixture was stirred for 2 h at reflux or at room
temperature (monitored by TLC and GC/MS). After completion of
the reaction, the reaction mixture was quenched with a saturated
aqueous solution of NH4Cl (5 mL) and extracted with ethyl acetate (3
× 10 mL). The combined organic layer was washed with water and
brine, then dried over anhydrous Na2SO4, filtered, and concentrated
under vacuum. The crude residue was then purified by column
chromatography on silica gel using n-hexane as the eluent to afford
pure target compound 3.
1-Methoxy-4-(2-methyl-1-propen-1-yl)benzene (3aa, CAS: 877-
99-6).2f Colorless oil: yield 82% (132.9 mg); H NMR (400 MHz,
1
CDCl3) δ 7.14 (d, J = 8.8 Hz, 2H), 6.84 (d, J = 8.4 Hz, 2H), 6.20 (s,
1H), 3.78 (s, 3H), 1.87 (s, 3H), 1.83 (s, 3H); 13C NMR (100 MHz,
CDCl3) δ 157.9, 134.2, 131.6, 130.1, 124.8, 113.7, 55.5, 27.1, 19.6.
1-(Benzyloxy)-4-(2-methylprop-1-en-1-yl)benzene (3ba). White
solid: yield 86% (204.8 mg); mp 66.6−67.8 °C; 1H NMR (400
MHz, CDCl3) δ 7.42−7.30 (m, 5H), 7.14 (d, J = 8.0 Hz, 2H), 6.91 (d,
J = 8.0 Hz, 2H), 6.20 (s, 1H), 5.03 (s, 2H), 1.87 (s, 3H), 1.83 (s, 3H);
13C NMR (100 MHz, CDCl3) δ 156.9, 137.2, 134.0, 131.6, 129.8,
128.6, 127.9, 127.5, 124.5, 114.4, 70.0, 26.8, 19.4; HRMS (EI) calcd
for C17H18O ([M]+) 238.1358, found 238.1359.
additional ligands. The catalytic system involving Pd(PPh3)4
was found to be exceptionally effective for the coupling reaction
of fluoroalkenes with Grignard reagents without β-hydrogen
atoms to exclusively afford the corresponding dicoupled
product in high yield, whereas NiCl2(dppe) exhibited superior
reactivity in the cross coupling of fluoroalkenes with Grignard
reagents bearing β-hydrogen atoms. Using a combination of the
two new catalytic systems will provide a powerful and practical
tool for the synthesis of multisubstituted alkenes from
fluoroalkenes.
Methyl(4-(2-methylprop-1-en-1-yl)phenyl)sulfane (3ca). Yellow
1
oil: yield 90% (160.3 mg); H NMR (400 MHz, CDCl3) δ 7.20 (d,
J = 8.4 Hz, 2H), 7.14 (d, J = 8.4 Hz, 2H), 6.20 (s, 1H), 2.46 (s, 3H),
1.88 (s, 3H), 1.84 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 135.8,
135.5, 129.2, 126.6, 124.6, 27.0, 19.5, 16.1; HRMS (EI) calcd for
C11H14S ([M]+) 178.0816, found 178.0815.
EXPERIMENTAL SECTION
General Comments. All reagents were analytical grade, obtained
from commercial suppliers, and used without further purification. H
■
1-(2,2-Diphenylethenyl)-4-methoxybenzene (3ab, CAS: 18648-
74-3).17 White solid: yield 87% (248.9 mg); mp 81.0−82.6 °C; H
1
1
NMR (400 MHz, CDCl3) δ 7.33−7.19 (m, 10H), 6.95 (d, J = 8.4 Hz,
2H), 6.91 (s, 1H), 6.65 (d, J = 8.4 Hz, 2H), 3.71 (s, 3H); 13C NMR
(100 MHz, CDCl3) δ 158.4, 143.6, 140.6, 130.8, 130.4, 130.0, 128.7,
128.1, 127.6, 127.4, 127.2, 113.4, 55.1.
NMR and 13C NMR spectra were recorded on a 400 MHz
spectrometer at 400 and 100 MHz, respectively, using TMS as an
internal standard. 19F NMR spectra were obtained using a 400 MHz
spectrometer at 376 MHz. CDCl3 was used as the NMR solvent in all
cases. GC and GC/MS were calibrated by authentic standards. High-
1-(2,2-Diphenylethenyl)-4-(phenylmethoxy)benzene (3bb, CAS:
18648-75-4).18 White solid: yield 87% (315.1 mg); mp 100.3−101.5
F
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Scheme 3. Proposed Mechanism for the Pd(PPh3)4-Catalyzed Cross-Coupling Reaction of Difluoroalkene with n-BuMgCl
°C; 1H NMR (400 MHz, CDCl3) δ 7.34−7.19 (m, 15H), 6.93 (d, J =
8.0 Hz, 2H), 6.89 (s, 1H), 6.70 (d, J = 8.0 Hz, 2H), 4.91 (s, 2H); 13C
NMR (100 MHz, CDCl3) δ 157.8, 143.7, 140.9, 140.8, 137.1, 131.0,
130.6, 130.5, 128.9, 128.7, 128.4, 128.1, 127.8, 127.7, 127.6, 127.5,
127.4, 114.5, 70.0; HRMS (EI) calcd for C27H22O ([M]+) 362.1671,
found 362.1672.
Hz, 2H), 3.74 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 162.5 (d, 1JCF
1
4
= 245.6 Hz), 162.3 (d, JCF = 245.2 Hz), 158.7, 139.8 (d, JCF = 3.1
4
3
Hz), 138.7, 136.5 (d, JCF = 3.4 Hz), 132.3 (d, JCF = 7.9 Hz), 130.9,
129.9, 129.2 (d, 3JCF = 7.9 Hz), 128.1, 116.0 (d, 2JCF = 21.2 Hz), 115.2
(d, JCF = 19.2 Hz), 113.7, 55.3; 19F NMR (376 MHz, CDCl3) δ
2
−114.3 to −114.4 (m, 1F), −115.0 to −115.1 (m, 1F).
1-(2,2-Diphenylethenyl)-4-(methylthio)benzene (3cb, CAS:
133776-80-4).19 Light yellow solid: yield 83% (250.8 mg); mp
106.9−108.6 °C; 1H NMR (400 MHz, CDCl3) δ 7.32−7.19 (m, 10H),
6.98 (d, J = 8.4 Hz, 2H), 6.92 (d, J = 8.8 Hz, 2H), 6.90 (s, 1H), 2.39
(s, 3H); 13C NMR (100 MHz, CDCl3) δ 143.4, 142.2, 140.5, 137.0,
134.3, 130.4, 130.0, 128.8, 128.3, 127.6, 127.5, 125.9, 15.6.
1-Methoxy-4-[3-phenyl-2-(phenylmethyl)-1-propenyl]benzene
(3ac, CAS: 61022-48-8).20 Light yellow oil: yield 72% (226.2 mg); 1H
NMR (400 MHz, CDCl3) δ 7.31−7.26 (m, 4H), 7.22−7.16 (m, 8H),
6.82 (d, J = 8.4 Hz, 2H), 6.51 (s, 1H), 3.76 (s, 3H), 3.53 (s, 2H), 3.36
(s, 2H); 13C NMR (100 MHz, CDCl3) δ 158.3, 139.8, 139.6, 138.9,
130.4, 129.7, 129.2, 128.7, 128.5, 128.4, 128.2, 126.1, 113.7, 55.3, 43.4,
36.0.
(4-(2-Benzyl-3-phenylprop-1-en-1-yl)phenyl)(methyl)sulfane
(3cc). White solid: yield 79% (260.8 mg); mp 95.4−96.5 °C; 1H NMR
(400 MHz, CDCl3) δ 7.26−7.25 (m, 4H), 7.19−7.12 (m, 10H), 6.48
(s, 1H), 3.52 (s, 2H), 3.34 (s, 2H), 2.36 (s, 3H); 13C NMR (100 MHz,
CDCl3) δ 140.4, 139.7, 139.6, 136.8, 134.9, 129.4, 129.2, 128.9, 128.8,
128.6, 128.5, 126.7, 126.5, 126.4, 43.7, 36.3, 16.0; HRMS (EI) calcd
for C23H22S ([M]+) 330.1442, found 330.1443.
1-(2,2-Bis(4-fluorophenyl)vinyl)naphthalene (3de). White solid:
yield 88% (301.1 mg); mp 76.5−77.9 °C; 1H NMR (400 MHz,
CDCl3) δ 8.12−8.10 (m, 1H), 7.85−7.83 (m, 1H), 7.67 (d, J = 8.4 Hz,
1H), 7.50−7.48 (m, 2H), 7.39−7.37 (m, 3H), 7.21−7.17 (m, 1H),
7.08−7.01 (m, 5H), 6.85−6.81 (m, 2H); 13C NMR (100 MHz,
1
1
CDCl3) δ 162.6 (d, JCF = 246.0 Hz), 162.0 (d, JCF = 245.4 Hz),
142.7, 139.3 (d, 4JCF = 3.2 Hz), 135.9 (d, 4JCF = 3.4 Hz), 134.9, 133.5,
132.4, 132.3 (d, 3JCF = 7.9 Hz), 129.8 (d, 3JCF = 8.0 Hz), 128.6, 127.7,
2
127.4, 126.5, 126.2, 125.9, 125.3, 124.6, 115.3 (d, JCF = 21.3 Hz),
115.2 (d, 2JCF = 21.3 Hz); 19F NMR (376 MHz, CDCl3) δ −114.3 to
−114.4 (m, 1F), −114.4 to −114.5 (m, 1F); HRMS (EI) calcd for
C24H16F2 ([M]+) 342.1220, found 342.1219.
1-(2-Butyl-1-hexenyl)-4-methoxybenzene (3af, CAS: 836601-77-
5).23 Colorless oil: yield 85% (209.3 mg); 1H NMR (400 MHz,
CDCl3) δ 7.13 (d, J = 8.4 Hz, 2H), 6.84 (d, J = 8.4 Hz, 2H), 6.19 (s,
1H), 3.80 (s, 3H), 2.20 (t, J = 8.0 Hz, 2H), 2.14 (t, J = 7.6 Hz, 2H),
1.45−1.29 (m, 8H), 0.94 (t, J = 7.4 Hz, 3H), 0.89 (t, J = 7.4 Hz, 3H);
13C NMR (100 MHz, CDCl3) δ 157.9, 142.9, 131.6, 130.0, 124.4,
113.7, 55.5, 37.3, 30.9, 30.8, 30.7, 23.2, 22.9, 14.3, 14.2.
1-(Benzyloxy)-4-(2-butylhex-1-en-1-yl)benzene (3bf). Yellow oil:
yield 90% (290.0 mg); 1H NMR (400 MHz, CDCl3) δ 7.42−7.29 (m,
5H), 7.14−7.11 (m, 2H), 6.92−6.89 (m, 2H), 6.19 (s, 1H), 5.02 (s,
2H), 2.21−2.14 (m, 4H), 1.47−1.33 (m, 8H), 0.96−0.87 (m, 6H); 13C
NMR (100 MHz, CDCl3) δ 156.9, 142.6, 137.1, 131.6, 129.7, 128.5,
127.8, 127.4, 124.1, 114.4, 69.9, 37.0, 30.5, 30.4, 30.3, 22.9, 22.5, 14.0,
13.9; HRMS (EI) calcd for C23H30O ([M]+) 322.2297, found
322.2295.
4,4′-(2-(4-Methoxyphenyl)ethene-1,1-diyl)bis(methylbenzene)
(3ad, CAS: 1187460-27-0).21 White solid: yield 86% (270.2 mg); mp
1
75.7−77.0 °C; H NMR (400 MHz, CDCl3) δ 7.21 (d, J = 8.0 Hz,
2H), 7.12 (s, 4H), 7.08 (d, J = 8.0 Hz, 2H), 6.98 (d, J = 8.8 Hz, 2H),
6.87 (s, 1H), 6.65 (d, J = 8.8 Hz, 2H), 3.67 (s, 3H), 2.36 (s, 3H), 2.32
(s, 3H); 13C NMR (100 MHz, CDCl3) δ 158.4, 141.3, 140.7, 138.0,
137.1, 137.0, 131.0, 130.6, 130.5, 129.6, 129.1, 127.6, 126.9, 113.6,
55.2, 21.6, 21.3.
1-(2-Butylhex-1-en-1-yl)naphthalene (3df). Colorless oil: yield
81% (215.6 mg); 1H NMR (400 MHz, CDCl3) δ 7.98−7.94 (m, 1H),
7.84−7.83 (m, 1H), 7.73−7.71 (m, 1H), 7.47−7.28 (m, 4H), 6.61 (s,
1H), 2.31−2.29 (m, 2H), 2.08−2.06 (m, 2H) 1.61−1.15 (m, 8H),
1.02−0.98 (m, 3H), 0.76−0.73 (m, 3H); 13C NMR (100 MHz,
CDCl3) δ 145.1, 136.3, 133.5, 132.4, 128.2, 126.6, 126.4, 125.6, 125.5,
125.4, 125.3, 122.7, 36.2, 30.6, 30.5, 22.7, 14.1, 13.9; HRMS (EI) calcd
for C20H26 ([M]+) 266.2035, found 266.2036.
5-(2-Butylhex-1-en-1-yl)benzo[d][1,3]dioxole (3ef). Light yellow
oil: yield 84% (218.6 mg); 1H NMR (400 MHz, CDCl3) δ 6.76−6.64
(m, 3H), 6.15 (s, 1H), 5.93 (s, 2H), 2.19 (t, J = 7.8 Hz, 2H), 2.12 (t, J
= 7.6 Hz, 2H), 1.48−1.25 (m, 8H), 0.93 (t, J = 7.2 Hz, 3H), 0.89 (t, J
= 7.4 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 147.3, 145.5, 143.1,
1-[2,2-Bis(4-methylphenyl)ethenyl]naphthalene (3dd, CAS:
75078-97-6).4b White solid: yield 84% (280.7 mg); mp 145.0−146.3
1
°C; H NMR (400 MHz, CDCl3) δ 8.15−8.12 (m, 1H), 7.81−7.79
(m, 1H), 7.62 (d, J = 8.0 Hz, 1H), 7.46−7.44 (m, 2H), 7.37 (s, 1H),
7.31 (d, J = 8.0 Hz, 2H), 7.17−7.13 (m, 3H), 7.05 (d, J = 7.2 Hz, 1H),
6.98−6.91 (m, 4H), 2.37 (s, 3H), 2.25 (s, 3H); 13C NMR (100 MHz,
CDCl3) δ 144.8, 141.2, 137.8, 137.6, 137.0, 135.8, 133.8, 132.9, 130.9,
129.3, 129.0, 128.8, 128.4, 127.9, 127.2, 126.2, 126.0, 125.7, 125.5,
125.0, 21.6, 21.5.
4,4′-(2-(4-Methoxyphenyl)ethene-1,1-diyl)bis(fluorobenzene)
(3ae, CAS: 2069-81-0).22 White solid: yield 84% (270.6 mg); mp
1
67.4−68.9 °C; H NMR (400 MHz, CDCl3) δ 7.25−7.22 (m, 2H),
7.17−7.14 (m, 2H), 7.04−6.93 (m, 6H), 6.83 (s, 1H), 6.68 (d, J = 8.8
G
dx.doi.org/10.1021/jo5022234 | J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Article
132.9, 124.2, 122.0, 109.0, 108.0, 100.8, 36.9, 30.6, 30.5, 30.4, 22.9,
22.6, 14.1, 14.0; HRMS (EI) calcd for C17H24O2 ([M]+) 260.1776,
found 260.1775.
1,1′-(2-Methyl-1-propen-1-ylidene)bisbenzene (3ga, CAS: 781-
33-9).25 Colorless oil: yield 87% (181.1 mg); H NMR (400 MHz,
1
CDCl3) δ 7.30−7.26 (m, 4H), 7.20−7.17 (m, 6H), 1.84 (s, 6H); 13C
NMR (100 MHz, CDCl3) δ 143.5, 137.3, 131.1, 129.9, 128.0, 126.2,
22.6.
1-Butyl-3-(2-butylhex-1-en-1-yl)benzene (3ff). Yellow oil: yield
79% (215.1 mg); 1H NMR (400 MHz, CDCl3) δ 7.22−7.18 (m, 1H),
7.02−6.98 (m, 3H), 6.24 (s, 1H), 2.59 (t, J = 7.8 Hz, 2H), 2.22 (t, J =
8.0 Hz, 2H), 2.15 (t, J = 7.6 Hz, 2H), 1.60−1.29 (m, 12H), 0.96−0.87
(m, 9H); 13C NMR (100 MHz, CDCl3) δ 143.6, 142.4, 138.6, 128.7,
127.8, 125.8, 125.7, 124.8, 37.0, 35.6, 33.6, 30.6, 30.5, 30.4, 22.9, 22.5,
22.3, 14.0, 13.9; HRMS (EI) calcd for C20H32 ([M]+) 272.2504, found
272.2505.
1-(2-Ethylbut-1-en-1-yl)-4-methoxybenzene (3ag). Colorless oil:
yield 88% (167.3 mg); 1H NMR (400 MHz, CDCl3) δ 7.14 (d, J = 8.8
Hz, 2H), 6.85 (d, J = 8.4 Hz, 2H), 6.17 (s, 1H), 3.79 (s, 3H), 2.25 (q, J
= 7.5 Hz, 2H), 2.18 (q, J = 7.5 Hz, 2H), 1.10 (t, J = 5.8 Hz, 3H), 1.06
(t, J = 6.0 Hz, 3H); 13C NMR (100 M Hz, CDCl3) δ 157.8, 145.3,
131.4, 129.7, 122.7, 113.6, 55.3, 29.5, 23.8, 13.1, 12.9; HRMS (EI)
calcd for C13H18O ([M]+) 190.1358, found 190.1357.
1-(Benzyloxy)-4-(2-ethylbut-1-en-1-yl)benzene (3bg). Yellow oil:
yield 83% (220.9 mg); 1H NMR (400 MHz, CDCl3) δ 7.43−7.29 (m,
5H), 7.15−7.13 (m, 2H), 6.93−6.90 (m, 2H), 6.17 (s, 1H), 5.03 (s,
2H), 2.27−2.16 (m, 4H), 1.12−1.04 (m, 6H); 13C NMR (100 MHz,
CDCl3) δ 156.9, 145.2, 137.1, 131.5, 129.6, 128.5, 127.8, 127.4, 122.6,
114.4, 69.9, 29.5, 23.7, 13.0, 12.8; HRMS (EI) calcd for C19H22O
([M]+) 266.1671, found 266.1672.
(4-(2-Ethylbut-1-en-1-yl)phenyl)(methyl)sulfane (3cg). Yellow oil:
yield 83% (171.1 mg); 1H NMR (400 MHz, CDCl3) δ 7.20 (d, J = 8.4
Hz, 2H), 7.13 (d, J = 8.0 Hz, 2H), 6.16 (s, 1H), 2.46 (s, 3H), 2.24 (q, J
= 7.5 Hz, 2H), 2.17 (q, J = 7.9 Hz, 2H), 1.09 (t, J = 6.4 Hz, 3H), 1.06
(t, J = 6.6 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 146.6, 135.7,
135.4, 129.0, 126.6, 122.6, 29.5, 23.8, 16.1, 13.0, 12.8; HRMS (EI)
calcd for C13H18S ([M]+) 206.1129, found 206.1128.
5-(2-Ethylbut-1-en-1-yl)benzo[d][1,3]dioxole (3eg). Light yellow
oil: yield 84% (171.5 mg); 1H NMR (400 MHz, CDCl3) δ 6.76−6.65
(m, 3H), 6.13 (s, 1H), 5.91 (s, 2H), 2.24 (q, J = 7.5 Hz, 2H), 2.16 (q, J
= 7.7 Hz, 2H), 1.09 (t, J = 6.0 Hz, 3H), 1.05 (t, J = 6.2 Hz, 3H); 13C
NMR (100 MHz, CDCl3) δ 147.5, 145.9, 145.8, 133.0, 123.0, 122.1,
109.1, 108.2, 101.0, 29.6, 23.9, 13.2, 13.0; HRMS (EI) calcd for
C13H16O2 ([M]+) 204.1150, found 204.1149.
1-Methoxy-4-(2-propyl-1-penten-1-yl)benzene (3ah, CAS:
860734-09-4).24 Colorless oil: yield 82% (178.9 mg); 1H NMR
(400 MHz, CDCl3) δ 7.13 (d, J = 8.4 Hz, 2H), 6.84 (d, J = 8.8 Hz,
2H), 6.20 (s, 1H), 3.79 (s, 3H), 2.18 (t, J = 8.0 Hz, 2H), 2.11 (t, J =
8.0 Hz, 2H), 1.54−1.45 (m, 4H), 0.94 (t, J = 6.8 Hz, 3H), 0.90 (t, J =
7.4 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 157.7, 142.2, 131.4,
129.7, 124.5, 113.5, 55.2, 39.5, 32.8, 21.6, 21.4, 14.3, 14.0.
1-(Benzyloxy)-4-(2-propylpent-1-en-1-yl)benzene (3bh). Colorless
oil: yield 80% (235.4 mg); 1H NMR (400 MHz, CDCl3) δ 7.44−7.31
(m, 5H), 7.13 (d, J = 8.4 Hz, 2H), 6.92 (d, J = 8.0 Hz, 2H), 6.20 (s,
1H), 5.04 (s, 2H), 2.18 (t, J = 7.8 Hz, 2H), 2.11 (t, J = 7.6 Hz, 2H),
1.52−1.47 (m, 4H), 0.96−0.89 (m, 6H); 13C NMR (100 MHz,
CDCl3) δ 157.2, 142.6, 137.5, 131.9, 130.0, 128.8, 128.2, 127.8, 124.7,
114.7, 70.3, 39.7, 33.0, 21.8, 21.6, 14.6, 14.2; HRMS (EI) calcd for
C21H26O ([M]+) 294.1984, found 294.1985.
1-Methoxy-4-(2-pentylhept-1-en-1-yl)benzene (3ai). Colorless oil:
yield 80% (219.4 mg); 1H NMR (400 MHz, CDCl3) δ 7.12 (d, J = 8.8
Hz, 2H), 6.84 (d, J = 8.8 Hz, 2H), 6.19 (s, 1H), 3.78 (s, 3H), 2.20 (t, J
= 8.0 Hz, 2H), 2.13 (t, J = 7.6 Hz, 2H), 1.51−1.42 (m, 4H), 1.36−1.27
(m, 8H), 0.91 (t, J = 6.8 Hz, 3H), 0.88 (t, J = 6.4 Hz, 3H); 13C NMR
(100 MHz, CDCl3) δ 157.7, 142.7, 131.4, 129.7, 124.2, 113.5, 55.2,
37.3, 32.1, 31.8, 30.7, 28.1, 28.0, 22.7, 22.6, 14.1, 14.0; HRMS (EI)
calcd for C19H30O ([M]+) 274.2297, found 274.2295.
1,1-Dibenzyl-2,2-diphenylethylene (3gc, CAS: 69275-86-1).26
Light yellow solid: yield 81% (291.8 mg); mp 78.0−78.9 °C; 1H
NMR (400 MHz, CDCl3) δ 7.30−7.25 (m, 12H), 7.22−7.17 (m, 4H),
7.10 (d, J = 7.6 Hz, 4H), 3.39 (s, 4H); 13C NMR (100 MHz, CDCl3) δ
142.8, 141.3, 140.4, 136.1, 129.5, 128.9, 128.4, 128.3, 126.6, 126.0,
37.3.
1,1-Diphenyl-2,2-di-p-tolylethylene (3gd, CAS: 32298-40-1).27
1
White solid: yield 43% (154.9 mg); mp 160.1−161.0 °C; H NMR
(400 MHz, CDCl3) δ 7.09−7.00 (m, 10H), 6.92−6.87 (m, 8H), 2.23
(s, 6H); 13C NMR (100 MHz, CDCl3) δ 144.2, 141.0, 140.9, 140.1,
136.0, 131.4, 131.3, 128.4, 127.7, 126.2, 21.3.
1-Methoxy-4-(2-phenyl-1-propenyl)benzene ((E)-3ha, CAS:
22692-69-9).28 White solid: yield 89% (199.5 mg); mp 83.6−84.9
1
°C; H NMR (400 MHz, CDCl3) δ 7.50 (d, J = 8.4 Hz, 2H), 7.37−
7.23 (m, 5H), 6.91 (d, J = 8.4 Hz, 2H), 6.78 (s, 1H), 3.82 (s, 3H) ;
2.27 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 158.2, 144.2, 135.9,
131.0, 130.4, 128.3, 127.3, 127.0, 126.0, 113.7, 55.3, 17.5.
1-Methoxy-4-[(1Z)-2-(4-methylphenyl)-2-phenylethenyl]benzene
((Z)-3hd, CAS: 780756-50-5).29 Colorless sticky liquid: yield 90%
(270.1 mg); 1H NMR (400 MHz, CDCl3) δ 7.31−7.22 (m, 5H), 7.14
(d, J = 8.0 Hz, 2H), 7.09 (d, J = 8.0 Hz, 2H), 6.98 (d, J = 8.8 Hz, 2H),
6.87 (s, 1H), 6.67 (d, J = 8.8 Hz, 2H), 3.74 (s, 3H), 2.38 (s, 3H); 13C
NMR (100 MHz, CDCl3) δ 158.4, 143.9, 140.7, 137.6, 136.9, 130.8,
130.4, 130.3, 129.5, 128.2, 127.5, 127.2, 113.4, 55.2, 21.4; HRMS (EI)
calcd for C22H20O ([M]+) 300.1514, found 300.1515.
(Z)-1-Fluoro-4-(2-(4-methoxyphenyl)-1-phenylvinyl)benzene ((Z)-
3he, CAS: 1619921−71−9).30 White solid: yield 93% (282.8 mg); mp
1
77.3−78.1 °C; H NMR (400 MHz, CDCl3) δ 7.28−7.24 (m, 5H),
7.18−7.15 (m, 2H), 7.03−6.98 (m, 2H), 6.94 (d, J = 8.8 Hz, 2H), 6.90
(s, 1H), 6.68 (d, J = 8.8 Hz, 2H), 3.73 (s, 3H); 13C NMR (100 MHz,
1
CDCl3) δ 162.2 (d, JCF = 244.9 Hz), 158.6, 143.5, 139.6, 136.6 (d,
3
4JCF = 3.4 Hz), 132.2 (d, JCF = 7.9 Hz), 130.9, 130.0, 128.3, 128.1,
2
127.5, 127.4, 115.8 (d, JCF = 21.1 Hz), 113.6, 55.2; 19F NMR (376
MHz, CDCl3) δ −114.6 to −114.7 (m, 1F); HRMS (EI) calcd for
C21H17FO ([M]+) 304.1263, found 304.1262.
1-(2-Phenyl-1-propenyl)-(E)-naphthalene ((E)-3ia, CAS: 131061−
06−8).31 Colorless oil: yield 91% (222.2 mg); H NMR (400 MHz,
1
CDCl3) δ 8.02−8.00 (m, 1H), 7.85−7.83 (m, 1H), 7.76 (d, J = 8.4 Hz,
1H), 7.63−7.61 (m, 2H), 7.48−7.43 (m, 3H), 7.41−7.37 (m, 3H),
7.32−7.27 (m, 2H), 2.11 (s, 3H); 13C NMR (100 MHz, CDCl3) δ
143.3, 139.0, 135.8, 133.8, 132.3, 128.6, 127.5, 127.4, 126.8, 126.1,
126.0, 125.9, 125.6, 125.5, 125.3, 17.6.
1-(2,2-Diphenylethenyl)naphthalene (3ib, CAS: 22837−11−2).17
White solid: yield 84% (257.2 mg); mp 80.9−81.6 °C; 1H NMR (400
MHz, CDCl3) δ 8.15−8.13 (m, 1H), 7.82−7.79 (m, 1H), 7.63 (d, J =
8.0 Hz, 1H), 7.48−7.41 (m, 5H), 7.37−7.32 (m, 3H), 7.17−7.03 (m,
7H); 13C NMR (100 MHz, CDCl3) δ 144.8, 143.5, 140.3, 135.3,
133.5, 132.6, 130.7, 128.5, 128.3, 128.2, 128.0, 127.7, 127.2, 126.4,
126.0, 125.8, 125.3, 124.7.
(Z)-1-(2-Phenyl-2-(p-tolyl)vinyl)naphthalene ((Z)-3id). White
1
solid: yield 96% (307.4 mg); mp 135.9−136.1 °C; H NMR (400
MHz, CDCl3) δ 8.15−8.13 (m, 1H), 7.82−7.79 (m, 1H), 7.63 (d, J =
8.0 Hz, 1H), 7.47−7.40 (m, 5H), 7.36−7.30 (m, 3H), 7.20−7.14 (m,
1H), 7.07 (d, J = 6.8 Hz, 1H), 6.97−6.92 (m, 4H), 2.25 (s, 3H); 13C
NMR (100 MHz, CDCl3) δ 144.8, 143.8, 137.2, 136.8, 135.5, 133.6,
132.6, 130.6, 128.8, 128.5, 128.3, 127.7, 127.6, 127.1, 126.0, 125.9,
125.8, 125.4, 124.8, 21.3; HRMS (EI) calcd for C25H20 ([M]+)
320.1565, found 320.1566.
(3-(4-Methoxybenzylidene)pentane-1,5-diyl)dibenzene (3aj).
Light yellow oil: yield 83% (284.0 mg); 1H NMR (400 MHz,
CDCl3) δ 7.29−7.12 (m, 10H), 7.09−7.05 (m, 2H), 6.83−6.80 (m,
2H), 6.25 (s, 1H), 3.74 (s, 3H), 2.84−2.75 (m, 4H), 2.57−2.46 (m,
4H); 13C NMR (100 MHz, CDCl3) δ 158.1, 142.3, 142.1, 140.5,
130.9, 129.8, 128.7, 128.6, 128.5, 128.4, 126.1, 126.0, 113.7, 55.3, 39.4,
35.1, 34.7, 33.0; HRMS (EI) calcd for C25H26O ([M]+) 342.1984,
found 342.1983.
(Z)-1-(2-(4-Fluorophenyl)-2-phenylvinyl)naphthalene ((Z)-3ie).
White solid: yield 90% (291.7 mg); mp 83.4−84.2 °C; 1H NMR
(400 MHz, CDCl3) δ 8.08−8.05 (m, 1H), 7.79−7.76 (m, 1H), 7.61
(d, J = 8.4 Hz, 1H), 7.44−7.36 (m, 5H), 7.33−7.28 (m, 3H), 7.15−
7.11 (m, 1H), 7.02−6.99 (m, 3H), 6.79−6.74 (m, 2H); 13C NMR
1
(100 MHz, CDCl3) δ 162.1 (d, JCF = 245.1 Hz), 143.9, 143.4, 136.3
(d, 4JCF = 3.4 Hz), 135.2, 133.7, 132.6, 132.5 (d, 3JCF = 7.8 Hz), 128.7,
H
dx.doi.org/10.1021/jo5022234 | J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Article
128.5, 128.3, 128.0, 127.8, 127.5, 126.8, 126.2, 126.0, 125.5, 124.8,
and 21302128) and the National Basic Research Program of
China (973 Program, 2010CB126101).
2
115.2 (d, JCF = 21.2 Hz); 19F NMR (376 MHz, CDCl3) δ −114.8 to
−114.9 (m, 1F); HRMS (EI) calcd for C24H17F ([M]+) 324.1314,
found 324.1315.
REFERENCES
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(4-(4-Methoxyphenyl)-2-methylbut-1-en-3-yne-1,1-diyl)-
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dibenzene (3ja). Yellow solid: yield 90% (291.7 mg); mp 86.3−87.8
1
°C; H NMR (400 MHz, CDCl3) δ 7.48−7.46 (m, 2H), 7.35−7.17
(m, 10H), 6.80−6.77 (m, 2H), 3.77 (s, 3H), 2.05 (s, 3H); 13C NMR
(100 MHz, CDCl3) δ 159.4, 146.8, 142.4, 141.5, 132.8, 130.1, 130.0,
128.1, 127.5, 127.2, 127.1, 116.4, 116.0, 114.0, 92.3, 91.3, 55.3, 22.0;
HRMS (EI) calcd for C24H20O ([M]+) 324.1514, found 324.1516.
1,1′,1″,1‴-(1-Buten-3-yne-2,4-diyl-1-ylidene)tetrakisbenzene
(3kb, CAS: 21979−82−8).32 White solid: yield 94% (334.8 mg); mp
131.8−132.5 °C; 1H NMR (400 MHz, CDCl3) δ 7.58−7.55 (m, 2H),
7.38−7.30 (m, 5H), 7.22−7.10 (m, 11H), 7.02−7.00 (m, 2H); 13C
NMR (100 MHz, CDCl3) δ 149.0, 142.8, 141.4, 139.7, 131.4, 131.2,
130.6, 130.0, 128.2, 128.0, 127.9, 127.8, 127.7, 127.3, 127.1, 123.7,
121.6, 93.0, 92.5.
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16, 3300. (h) Turkmen, H.; Kani, I. Appl. Organometal. Chem. 2013,
(4-Cyclopropyl-2-(p-tolyl)but-1-en-3-yne-1,1-diyl)dibenzene
(3ld). White solid: yield 82% (274.0 mg); mp 92.5−93.2 °C; 1H NMR
(400 MHz, CDCl3) δ 7.45−7.43 (m, 2H), 7.28−7.20 (m, 3H), 7.13
(d, J = 8.0 Hz, 2H), 7.06−7.04 (m, 3H), 6.95−6.93 (m, 2H), 6.91 (d, J
= 8.0 Hz, 2H), 2.22 (s, 3H), 1.26−1.20 (m, 1H), 0.68−0.63 (m, 2H),
0.54−0.50 (m, 2H); 13C NMR (100 MHz, CDCl3) δ 146.1, 142.5,
141.2, 136.5, 135.8, 130.4, 129.6, 129.1, 127.8, 127.1, 126.8, 126.7,
126.2, 121.2, 96.8, 77.6, 20.5, 7.8, 0; HRMS (EI) calcd for C26H22
([M]+) 334.1722, found 334.1721.
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Non-1-en-3-yne-1,1,2-triyltribenzene (3mb). White solid: yield
1
87% (304.7 mg); mp 54.6−55.5 °C; H NMR (400 MHz, CDCl3) δ
7.50−7.47 (m, 2H), 7.29−7.24 (m, 5H), 7.13−7.04 (m, 6H), 6.97−
6.93 (m, 2H), 2.23 (t, J = 7.0 Hz, 2H), 1.44−1.36 (m, 2H), 1.26−1.19
(m, 4H), 0.85 (t, J = 6.8 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ
147.4, 143.1, 141.8, 140.5, 131.2, 130.4, 130.0, 127.8, 127.7, 127.6,
127.0, 126.9, 122.1, 94.8, 83.1, 31.1, 28.2, 22.3, 19.8, 14.1; HRMS (EI)
calcd for C27H26 ([M]+) 350.2035, found 350.2032.
1-[(1E)-2-Phenyl-1-hexen-1-yl]naphthalene ((E)-3if, CAS:
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1469445−07−5).33 Colorless oil: yield 62% (177.4 mg); H NMR
1
(400 MHz, CDCl3) δ 8.02−8.01 (m, 1H), 7.84−7.82 (m, 1H), 7.76
(d, J = 8.0 Hz, 1H), 7.57−7.55 (m, 2H), 7.47−7.36 (m, 6H), 7.32−
7.28 (m, 1H), 7.09 (s, 1H), 2.56 (t, J = 7.6 Hz, 2H), 1.38−1.27 (m,
2H), 1.19−1.12 (m, 2H), 0.71−0.68 (m, 3H); 13C NMR (100 MHz,
CDCl3) δ 144.8, 142.7, 136.0, 133.7, 132.5, 128.6, 128.5, 127.4, 127.3,
126.9, 126.2, 126.0, 125.5, 125.4, 31.0, 30.3, 22.7, 13.9.
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ASSOCIATED CONTENT
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Commun. 2007, 3679. (b) Yamada, S.; Shimoji, K.; Takahashi, T.;
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Lett. 2006, 8, 843. (e) Yamada, S.; Noma, M.; Hondo, K.; Konno, T.;
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■
S
* Supporting Information
1H and 13C NMR spectra of compounds 3aa−aj, 3ba, 3bb,
3bf−bh, 3ca−cc, 3cg, 3dd−df, 3ef, 3eg, 3ff, 3ga, 3gc, 3gd, (E)-
3ha, (Z)-3hd, (Z)-3he, (E)-3ia, 3ib, (Z)-3id, (Z)-3ie, 3ja, 3kb,
3ld, 3mb, and (E)-3if, 19F NMR spectra of compounds 3ae,
3de, (Z)-3he, and (Z)-3ie, and HRMS (EI) spectra of
compounds 3ba, 3ca, 3bb, 3cc, 3de, 3bf, 3df−ff, 3ag−cg,
3eg, 3bh, 3ai, 3aj, (Z)-3hd, (Z)-3he, (Z)-3id, (Z)-3ie, 3ja, 3ld,
and 3mb. This material is available free of charge via the
Internet at http://pubs.acs.org.
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2,011,108,668, 2011.
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2013, 78, 4599. (b) Jin, G.-Y.; Zhang, X.-X.; Cao, S. Org. Lett. 2013,
15, 3114. (c) Xiao, S.-H.; Xiong, Y.; Zhang, X.-X.; Cao, S. Tetrahedron
2014, 70, 4405. (d) Xiong, Y.; Zhang, X.-X.; Huang, T.; Cao, S. J. Org.
Chem. 2014, 79, 6395.
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AUTHOR INFORMATION
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Corresponding Authors
*E-mail: scao@ecust.edu.cn.
*E-mail: wujj@sit.edu.cn.
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Notes
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The authors declare no competing financial interest.
̀
R.; Figadere, B.; Peyrat, J.; Provot, O.; Brion, J.; Alami, M. Synlett
ACKNOWLEDGMENTS
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2004, 2697.
We are grateful for financial support from the National Natural
Science Foundation of China (Grants 21472043, 21272070,
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