Preparation of trifluorostyrenes via palladium-catalyzed coupling of arylboronic acids with chloro- and bromotrifluoroethylene

Article abstract of DOI:10.1021/jo301998g

A highly efficient and cost-effective method for the preparation of α,β,β-trifluorostyrene (TFS) and its derivatives is described. The method required only 0.2 mol % of Pd(dba)₂ and 0.4 mol % of P^tBu₃ and occurred to full conversion within 2.0 h. With this method, a wide range of arylboronic acids were efficiently incorporated to generate α,β,β-trifluorostyrene derivatives.

Full text of DOI:10.1021/jo301998g

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Article
Preparation of Trifluorostyrenes via Palladium-Catalyzed Coupling
of Aryl Boronic Acids with Chloro- and Bromo-Trifluoroethylene
Chunfa Xu, Sheng Chen, Long Lu, and Qilong Shen
J. Org. Chem., Just Accepted Manuscript • Publication Date (Web): 18 Oct 2012
Downloaded from http://pubs.acs.org on October 24, 2012
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Preparation of Trifluorostyrenes via Palladium-Catalyzed Coupling of Aryl Boronic Acids with
Chloro- and Bromo-Trifluoroethylene
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Chunfa Xu, Sheng Chen, Long Lu* and Qilong Shen*
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Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese
Academy of Science
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345 Lingling Rd., Shanghai, 200032
E-mail: lulong@mail.sioc.ac.cn; shenql@mail.sioc.ac.cn
RECEIVED DATE (will be automatically inserted after manuscript is accepted).
0.2 mol % Pd(dba)
2
t
F
F
F
X
F
F
F
0.4 mol % Bu P•HBF
3
4
ArB(OH)
+
2
Ar
X = Cl, Br
32 examples
44--95% yield
Abstract. A high efficient and cost-effective method for the preparation of α,β,β-trifluorostyrene
(TFS) and its derivatives is described. The method required only 0.2 mol % of Pd(dba)2 and 0.4 mol
% of PtBu3 and occurred to full conversion within 2.0 h. With this method, a wide range of aryl
boronic acids were efficiently incorporated to generate α,β,β-trifluorostyrene derivatives.
Introduction
α,β,β-Trifluorostyrene (TFS) and its derivatives are a type of interesting monomers for fluorinated
polymers,1-2 mainly due to its unique structure that combines a trifluorovinyl group and a benzene
ring. The polymers contain a perfluorinated main chain often exhibit high thermal, chemical stability
and more importantly, high solubility that allows the polymers more processible. The presence of the
benzene ring ensures the possibility of introducing a variety of functional groups. For example,
copolymers of trifluorostyrene and substituted trifluorostyrene developed by Stone and coworkers at
Ballard have been used as membrane electrolytes in proton exchange membrane fuel cell (PEMFC), a
leading candidate to replace the aging alkaline fuel cell.3 Thus, development of efficient methods for
the preparation of α,β,β-trifluorostyrene in good yields and high purity have become the subject of
special interest.4
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Most of the early methods for the syntheses of TFS derivatives typically required multisteps and
suffered from low overall yields.5,6 A more direct method was reported in 1980s7 through the Pd-
catalyzed cross-coupling of trifluorovinyl zinc or tin reagent with aryl halides. More recently, a stable
trifluorovinyl borate was developed to replace the zinc or tin reagent, thus provide a more convenient
route for the preparation of TFS derivatives.8 These trifluorovinyl reagents were synthesized from
easily available chlorotrifluoroethylene or 1,1,1,2-tetrafluorethane (HFC-134a) with butyl lithium
through halogen exchanging or deprotonation. Direct coupling of tetrafluoroethylene with
diphenylzinc reagent was also reported by Ogoshi recently.9 While these methods are quite effective
for the preparation of TFS and its derivatives, we envisioned that if a direct cross-coupling of chloro-
or bromo-trifluoroethene with aryl boronic acids can be realized, a more efficient and straightforward
strategy could be developed for the preparation of TFS and its derivatives (Scheme 1). In this context,
in 2010, we reported in a patent for the first time that Pd(PPh3)4 were able to couple
chlorotrifluoroehtylene with a variety of aryl boronic acids in good yields, albeit with 5.0 mol%
catalyst loading.10 In 2012, Yamamoto and Yamakawa reported that when 1-3 mol% of Pd(dppf)Cl2
was used as the catalyst, various of functionalized aryl boronic acids were coupled with
chlorotrifluoroethylene to give the corresponding trifluorostyrene derivatives in good to excellent
yields.11 Herein, we report that the same transformation can be realized when a combination of
Pd(dba)2 with PtBu3 was used. Most importantly, the reactions require only 0.2 mol% of the palladium
catalyst and tolerates a variety of functional groups. In addition, under slightly modified conditions,
the coupling of bromotrifluoroethylene with aryl boronic acids also occurred to good to excellent
yields.12
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Scheme 1. Strategies for the preparation of α,β,β-trifluorostyrene
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Previous work
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Zn
(1)
(2)
CF COCl
3
PhCFClCF
PhCF=CF
2
ref. 5
ref. 6
3
EtOH
PhLi
+
CF =CF
2
PhCF=CF
PhCF=CFPh
2
2
o
Et O, -78 C
2
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CF =CFX
2
ArY
[Pd]
or
CF =CFM
2
ArCF=CF
(3)
ref. 7-8
ref. 9
2
CF CH F
3
2
X = H, Cl, Br, or I; M = ZnR, SnR' or B(OMe) K
3
3
[Pd]
LiI
CF =CF
2
+
Ph Zn
2
PhCF=CF
2
(4)
(5)
2
This work
[Pd]
+
CF =CFX
2
ArCF=CF
ArB(OH)
2
2
Results and Discussion
We began our investigation by isolation of the [LPd(CF=CF2)(Cl)] species and testing its
stoichiometric reaction with aryl boronic acid in the presence of base under various conditions.
Heating of a mixture of [Pd(PPh3)4] with excess chlorotrifluoroethylene in toluene in a screw-caped
o
Schlenk tube at 80 C for 10 h generated the [trans-(PPh3)2Pd(CF=CF2)(Cl)] 1 in 60% yield (Eq. 6),
while no formation of oxidative-addition product 1 was observed when the reaction was conducted at
room temperature.
F
F
F
F
F
F
Toluene
Pd(PPh ) +
3 4
(6)
(7)
Ph P Pd PPh
3
3
o
80 C, 10 h
Cl
Cl
1
F
F
F
K PO
3
4
+
1
PhB(OH)
2
Toluene/H O
2
Ph
(3/1)
RT, 8 h
Complex 1 was characterized by H, 13C, 19F, 31P NMR spectroscopies and element analysis.
Structure of complex [(trans)-Pd(PPh3)2(CF=CF2)(Cl)] 1 was further confirmed by single crystal X-
ray diffraction (see the supporting information of details).13 Interestingly, Stone reported that while
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[(PPh3)2PdCl2] was formed when [Pd(PPh3)4] was reacted with chlorotrifluoroethylene in acetone,
reaction of [Pd(PPh2Me)4] with chlorotrifluoroethylene did generate [(trans)-
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9
Pd(PPh2Me)2(CF=CF2)(Cl)] in high yield in benzene.14 Treatment of Complex 1 with one equivalent
of phenyl boronic acid in toluene /water (3/1) using K3PO4 as the base at room temperature for 8 h
afforded the corresponding α,β,β-trifluorostyrene in 74% yield (Eq 7). These results clearly indicated
that oxidative-addition of chlorotrifluoroethylene to Pd(0) species was much slower than those of
transmetalation and reductive-elimination steps. Thus, if a suitable ligand can be identified to facilitate
the oxidative-addition of chlorotrifluoroethylene to Pd(0) species, the efficient Pd-catalyzed cross-
coupling of chlorotrifluoroethylene and aryl boronic acids might be accomplished under mild
conditions.
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Guided by these stoichiometric investigations, we first examined various supporting ligands,
especially those known to accelerate the oxidative-addition step for the model reaction between
chlorotrifluoroethylene and phenyl boronic acid. After careful investigation, we discovered that
reaction of chlorotrifluoroethylene and phenyl boronic acid in the presence of a combination of 0.2
mol% Pd2(dba)3 and 0.4 mol% PtBu315,16 occurred to 51% yield after 8 h at 80 oC using K3PO4 as the
base and a mixture of toluene and water (3:1, v/v) as the solvent. Reaction using Pd(OAc)2 or
Pd(PPh3)2Cl2 as the catalyst precursor occurred in much lower yields. When K2CO3, Na2CO3 or
Na3PO4 was used as the base, yields dropped slightly to 35-38%, while the yield of the reaction
decreased significantly to less than 5% when CsF was used as the base. Reactions in dioxane/H2O
(3/1) or benzene/H2O (3/1) occurred to 34% yield. Interestingly, when a mixture of DMF/H2O (3/1)
was used as the solvent, the yield increased dramatically to over 95%. However, this optimized
reaction conditions were not general. When other aryl boronic acid such as 4-biphenyl boronic acid
was used, only 38 % of the desired product was observed.
We then chose the reaction 4-biphenyl boronic acid with chlorotrifluoroethylene to further
optimize the reaction conditions, as summarized in Table 2. It was discovered that when a mixture of
DMF/toluene/water was used as the solvent, the desired product was generated in 95% yield. The
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reaction was much faster in these mixed solvent than those in DMF/H2O. Typically, the reaction
occurred to complete conversion after 2 h. Using of tBu3P as the reaction was critical for the reaction.
Bidentate ligands with a rigid backbone such as DPPF or BINAP were ineffective at all under these
conditions (Table 2, entries 8 and 9). Reactions using triphenylphosphine as the ligand occurred to
give the desired product in moderate 29% yield (Table 2, entry 10). Other monodentated electron-rich
alkyl phosphines such as PCy3 or BuP(Ad)2 were less efficient (Table 2, entries 11 and 12). N-
heterocyclic carbene (IPr), which have been used in a variety of cross-coupling reactions, was again
ineffective (Table 2, entry 13). The dialkylbiaryl phosphine ligands developed by Buchwald and
coworkers17 were known to accelerate the oxidative addition of aryl halides to Pd(0). Surprisingly,
(tBu)DavePhos, JohnPhos and SPhos were ineffective while reaction using (Cy)JohnPhos as the
ligand occurred to 65% yield (Table 2, entries 14-17).
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Table 1. Optimization for Pd-catalyzed coupling of chlorotrifluoro-ethylene with aryl boronic acid.a
F
F
F
F
F
F
Ph
Pd/L
+ PhB(OH)
ligand
2
Base, solvent
temperature
Cl
temp.
yield
time
(h)
Pd source
entry
solvent
base
o
b
( C)
(%)
c
1
2
3
4
Pd (dba)
tBu P
tol/H O
K PO
80
80
80
80
80
80
8
8
8
8
8
8
8
8
8
8
8
8
29
51
2
2
3
3
3
2
3
2
3
4
4
4
4
4
3
Pd (dba)
tBu P
tol/H O
K PO
3
2
3
2
d
Pd (dba)
tBu P
tol/H O
K PO
3
2
3
2
Pd(OAc)
tBu P
tol/H O
K PO
3
16
13
35
36
38
<5
34
34
>95
3
2
5 Pd(PPh ) Cl
tBu P
tol/H O
K PO
3
3 2
2
3
2
6
7
Pd(dba)
Pd(dba)
Pd(dba)
Pd(dba)
Pd(dba)
Pd(dba)
Pd(dba)
tBu P
tol/H O
K CO
2
2
2
2
2
2
2
2
3
2
tBu P
tol/H O
Na CO 80
2 3
3
2
8
tBu P
tol/H O
Na PO 80
3
2
3
4
9
tBu P
tol/H O
CsF
80
80
80
80
3
2
10
11
12
tBu P
dioxane/H O
K PO
3
3
2
4
tBu P
PhH/H O
K PO
3
3
2
4
4
tBu P
DMF/H O
K PO
3
3
2
aReaction conditions: aryl boronic (1.0 mmol), excess chlorotrifluoroethylene, palladium precursor (0.2 mol %), ligand
b
(0.4 mol %), base (3.0 mmol) in 5.4 mL of mixed solvent (solvent/H2O is 3:1). The yield was determined by 19F NMR
spectroscopy with fluorobezene as an internal standard. cThe ratio of solvent/H2O is 5:1; dThe ratio of solvent/H2O is 1:1.
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Table 2. Optimization for Pd-catalyzed coupling of chlorotrifluoro-ethylene with aryl boronic acid.a
4
5
6
7
8
B(OH)
F
F
F
2
F
F
Pd/L
+
Base, solvent
temperature
Cl
F
Ar
Ph
9
10
11
12
13
14
15
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17
18
19
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temp.
yield
time
(h)
Pd source
entry
ligand
tBu P
solvent
base
K PO
o
b
( C)
(%)
1
2
Pd(dba)
Pd(dba)
Pd(dba)
DMF/tol/H O
80
80
80
80
60
40
RT
80
80
80
80
80
80
80
80
80
80
8
6
4
2
2
2
2
2
2
2
2
2
2
2
2
2
2
>95
>95
90
>95
50
7
2
2
2
3
2
3
4
4
4
tBu P
DMF/tol/H O
K PO
3
3
2
3
tBu P
DMF/tol/H O
K PO
3
3
2
4
Pd(dba)
tBu P
DMF/tol/H O
K PO
3
2
2
2
2
2
2
2
2
2
2
2
2
3
2
4
4
4
4
4
4
4
4
4
4
4
4
4
4
5
Pd(dba)
Pd(dba)
Pd(dba)
Pd(dba)
Pd(dba)
Pd(dba)
Pd(dba)
Pd(dba)
Pd(dba)
Pd(dba)
Pd(dba)
tBu P
DMF/tol/H O
K PO
3
3
2
6
tBu P
DMF/tol/H O
K PO
3
3
2
7
tBu P
DMF/tol/H O
K PO
3
4
3
2
8
dppf
DMF/tol/H O
K PO
3
<5
<5
29
<5
70
5
2
9
BINAP
DMF/tol/H O
K PO
3
2
10
11
12
13
14
15
16
17
PPh
PCy
DMF/tol/H O
K PO
3
3
3
2
DMF/tol/H O
K PO
3
2
BuPAd
DMF/tol/H O
K PO
3
2
2
IPr(NHC) DMF/tol/H O
K PO
3
2
CyJohnPhos DMF/tol/H O
K PO
3
65
<5
<5
<5
2
JohnPhos DMF/tol/H O
K PO
3
2
Pd(dba) tBuDavePhos DMF/tol/H O
K PO
3
2
2
2
Pd(dba)
SPhos
DMF/tol/H O
K PO
3
2
aReaction conditions: aryl boronic (1.0 mmol), excess chlorotrifluoroethylene, palladium precursor (0.2 mol %), ligand
(0.4 mol %), base (3.0 mmol) in 5.4 mL of mixed solvent. The yield was determined by 19F NMR spectroscopy with
b
fluorobezene as an internal standard.
The superior reaction efficiencies of the palladium catalyst prompted us to further explore the scope
of the reaction, as summarized in Table 3. A wide range of arylboronic acids were readily converted
to the corresponding trifluorostyrene derivatives in moderate to excellent yields. Reactions of both
electron-rich and electron-poor aryl boronic acids gave the corresponding products in good to
excellent yields. It was found that the reaction conditions were compatible with various functional
groups. Reactions of arylboronic acids with functional groups such as enolizable ketones, aldehyde,
ester, amine, cyano group occurred in good to excellent yields (Table 3, entries 2n-q). Notably, 4-
chlorophenylboronic acid also coupled with chlorotrifluoroethylene to give the corresponding in 81%
yield (Table 3, entry 2j), which indicated that C-Cl bond in chlorotrifluoroethylene is more reactive
than those in aryl chlorides. The presence of chloride in the products is very useful for further
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synthetic manipulations. Reaction of heteroaryl boronic acid such as 3-pyridyl boronic acid, however,
didn’t generate the corresponding coupled product.
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Table 3. Scope of Pd-catalyzed coupling of chlorotrifluoroethylene with low loading.a
8
9
0.2 mol % Pd(dba)
2
10
11
12
13
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t
F
F
F
F
F
F
0.4 mol % Bu P´HBF
3
4
ArB(OH)
+
2
3.0 equiv K PO
4
Cl
3
Ar
DMF/Tol/H O (1:1:0.7)
2
2
80 °C, 2 h
F
F
F
F
F
F
F
F
F
R
Cl
b
81%, 2j
R = H, >95%, 2a
84%, 2i
t
Bu, 94%, 2b
F
c
Ph, 76%, 2c
MeO, 69%, 2d
PhO, 80%, 2e
vinyl, 51%, 2f
F
F
F
F
F
EtO C, 70%, 2g
2
70%, 2k
76%, 2l
Ac, 65%, 2h
F
F
F
F
F
R
F
OEt F
F
F
F
72%, 2r
F
R = OMe, 85%, 2m
NH , 53%, 2n
F
2
Cl
40%, 2t
Ac, 82%, 2o
CHO, 50%, 2p
CN, 57%, 2q
F
MeO
81%, 2s
F
F
F
O
F
F
F
O
F
F
F
O
N
90%, 2u
44%, 2v
NR
aReaction conditions: aryl boronic (1.0 mmol), excess chlorotrifluoro –ethylene, Pd(dba)2 (0.2 mol %), PtBu3•HBF4 (0.4
mol %), K3PO4 (3.0 mmol) in 5.4 mL of toluene/DMF/H2O (1/1/0.7). bThe yield was determined by 19F NMR
spectroscopy with fluorobezene as an internal standard. cThe yield was 88% when 4-bipheyl pinacol boronate was used.
Encouraged by the high efficiency and broad scope of the Pd-catalyzed coupling reaction of
chlorotrifluoroethylene, we tried to extend this method for the coupling of bromotrifluoroethylene.
While catalyst generated from Pd(dba)2/P(o-tol)3, Pd(dba)2/P(tBu3P)3 or Pd(dba)2/Xantphos gave the
desired product in good yield for the reaction of bromotrifluoroethylene with 4-biphenyl boronic acid
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in mixed DMF/H2O (3/1), less than 40% conversion was observed for the reaction of
bromotrifluoroethylene with 3-cyanophenyl boronic acid under these conditions even with prolong
reaction time. After a quick screening of the conditions, it was found that switching the solvent system
to 2/1 ratio of acetone/water results in significant improvement for the reactions of
bromotrifluoroethylene. The results were summarized in Table 4. A variety of aryl boronic acids were
subjected to the catalytic conditions to give the product in moderate to good yield. Generally, unlike
other cross-coupling reaction, couplings of bromotrifluoroethylene were much slower and less
effective than those of chlorotrifluoroethylene under the current reaction conditions.
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13
14
15
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19
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Table 4. Scope of Pd-catalyzed coupling of bromotrifluoroethylene with low loading.a
0.2 mol % Pd(dba)
2
F
F
F
t
F
F
F
0.4 mol % Bu P•HBF
3
4
+
F
ArB(OH)
2
3.0 equiv K PO
Br
3
4
Ar
acetone/H O (2:1)
2
3
80°C, 8 h
F
F
F
F
F
F
F
F
R
R = Ph, 79%, 2c
Cl, 69%, 2j
F
76%, 2k
65%, 2l
PhO, 74%, 2e
F
F
OMe F
MeO
F
F
F
F
F
60%, 3a
75%, 2i
77%, 2m
F
F
F
F
O
O
F
F
F
64%, 2u
79%, 2r
aReaction conditions: aryl boronic (1.0 mmol), excess bromo-trifluoroethylene, Pd(dba)2 (0.2 mol %), PtBu3•HBF4 (0.4
mol %), K3PO4 (3.0 mmol) in 3 mL of acetone/H2O (2/1).
To further demonstrate the synthetic application of our methodology for preparation of α,β,β-
Trifluorostyrene (TFS) and its derivatives, we attempted to scale up the reaction of 4-biphenyl boronic
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acid (2.0 g) with chlorotrifluoroethylene under the optimized conditions. The reaction occurred
smoothly to give the corresponding product in 80% yield (Eq. 8).
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8
9
0.2 mol % Pd(dba)2
0.4 mol % tBu3P•HBF4
F
B(OH)
F
F
F
2
F
+
(8)
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Cl
3.0 equiv K3PO4
DMF/Tol/H2O (1:1:0.7)
80 °C, 2 h
Ph
F
Ph
2.0 g
1.9 g, 80%
Conclusion
In summary, a high efficient and cost-effective method for the preparation of α,β,β-trifluorostyrene
(TFS) and its derivatives has been successfully developed.15-16 The method required only 0.2 mol % of
Pd(dba)2 and 0.4 mol % of PtBu3 and occurred to full conversion within 2.0 h. With this method, a
wide range of aryl boronic acids were efficiently incorporated to generate α,β,β-trifluorostyrene
derivatives. The method could also be extended to the coupling of bromotrifluoroethylene with simple
change of the solvent. In addition, the reaction can be easily scale up without loss in efficiency. Work
is ongoing to scale up the reaction to kilogram and to elucidate the mechanism of the reaction.
Experimental Section
Preparation of trans-Pd(CF=CF2)(PPh3)2Cl.
A 25 mL Schlenk tube was added tetrakis(triphenyl)phosphine (1.2 g, 1.0 mmol) and toluene (10.0
mL). The Schlenk tube was sealed and then subjected to three freeze-pump-thraw cycles before the
addition of chlorotrifluoroethylene (1.2 g, 10 mmol). The autoclave was heated at 80 oC for 10 h and
then was cooled to room temperature. The solvent was evaporated under reduced pressure and the
residue was recrystallized from chloroform to give trans-Pd(CF=CF2)(PPh3)2Cl as a orange solid (448
mg, 60% yield).
1H NMR (300 MHz, CDCl3, 293 K, TMS) δ 7.73-7.68 (m, 12 H), 7.46-7.38 (m, 18 H); 13C NMR (125
MHz，CDCl3，293K, TMS) δ 135.0, 134.5, 130.5, 130.4, 128.2, 128.0; 19F NMR (282.4 MHz,
CDCl3, 298 K, TMS) δ -95.87 (ddt, J = 102.2, 40.5.0, 7.1 Hz, 1 F), δ -128.21 (m, 1 F), -148.76 (ddt, J
= 105.6, 40.5, 6.2 Hz, 1 F) ppm; 31P{1H} NMR δ18.2 ppm. MS (EI): m/z (%) 746 (100).
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General Procedure A for preparation of trifluorostyrenes via palladium-catalyzed coupling of
CF2=CFCl.
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7
8
9
A 25 mL Schlenk-type sealed tube (with a Teflon high-pressure valve and side arm) equipped with a
magnetic stir bar was charged with the aryl boronic acid (1.0 mmol), potassium phosphate (3.0 mmol),
Pd(dba)2 (0.2 mmol %), tri-tert-butylphosphine tetrafluoroborate (0.4 mmol %). The reaction tube was
capped, then evacuated briefly under high vacuum and charged with argon, repeated three times. Then
freshly distilled toluene (2.0 mL) and DMF (2.0 mL), deionized water (1.4 mL) was added, and
chlorotrifluoroethene was bubbled about 5 min (saturated). Then the valve was screwed. The reaction
mixture was stirred at 80 °C for 2 h. Subsequently, the reaction vessel was cooled to room
temperature, 10 mL of deionized water and 10 mL of pentane (AR) was added. The organic phase was
separated and washed with deionized water three times. The aqueous phase was extracted with
pentane (3×10 mL). The organic phase was combined, dried with anhydrous Na2SO4 and added silica
gel, then evacuated under rotary evaporator, the resulting residue was purified by silica gel flash
column chromatography using pentane or pentane and ethyl ether mixed solvent as eluent.
General Procedure B for preparation of trifluorostyrenes via palladium-catalyzed coupling of
CF2=CFBr.
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A 25 mL Schlenk-type sealed tube (with a Teflon high-pressure valve and side arm) equipped with a
magnetic stir bar was charged with the aryllboronic acid (1.0 mmol), potassium phosphate (3.0
mmol), Pd(dba)2 (0.2 mmol %), tri-tert-butylphosphine tetrafluoroborate (0.4 mmol %). The reaction
tube was capped, then evacuated briefly under high vacuum and charged with argon, repeated three
times. Then freshly distilled acetone (2.0 mL) and deionized water (1.0 mL) was added, and
bromotrifluoroethene was bubbled about 1.0 min. Then the valve was screwed. The reaction mixture
was stirred at 80 °C for 8 h. Subsequently, the reaction vessel was cooled to room temperature, 10 mL
of CH2Cl2 was added and filtered through a celite. The CH2Cl2 phase was separated and washed with
deionized water three times. The aqueous phase was extracted with CH2Cl2 (3×5 mL). The CH2Cl2
phase was combined, dried with anhydrous Na2SO4 and added silica gel, then evacuated under rotary
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evaporator, the resulting residue was purified by silica gel flash column chromatography using
pentane or pentane and ethyl ether mixed solvent as eluent.
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(1,2,2-Trifluorovinyl)benzene 2a.7d When the reaction vessel was cooled to room temperature,
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fluorobenznene (1.0 mol) was added as internal standard. Yield was determined to be >95% by F
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NMR spectroscopy.
1-tert-Butyl-4-(1,2,2-trifluorovinyl)benzene 2b.18 The general procedure A with 4-tert-
butylphenylboronic acid (180 mg, 1.00 mmol), Pd(dba)2 (1.2 mg) and tBu3PHBF4 (1.2 mg) gave 202.0
1
mg (94%) of 1-tert-butyl-4-(1,2,2-trifluorovinyl)benzene as a colorless liquid. H NMR (300.0 MHz,
19
CDCl3, 298 K, TMS) δ 7.42 (dd, J = 7.45, 7.40 Hz, 4 H), 1.33 (s, 9 H) ppm; F NMR (282.4 MHz,
CDCl3, 298 K, TMS) δ -101.20 (dd, J = 73.5, 32.0 Hz, 1 F), δ -116.11 (dd, J = 109.2, 73.4 Hz, 1 F), -
177.21 (dd, J = 109.5, 32.2 Hz, 1 F) ppm; 13C NMR (100.5 MHz, CDCl3, 298 K, TMS) 153.8 (ddd, J
= 289.9, 282.0, 50.1 Hz), 152.6, 128.8 (ddd, J = 226.3, 45.6, 19.5 Hz), 125.6, 124.5 (d, J = 6.6 Hz),
124.3 (dd, J = 10.5, 6.1 Hz), 34.7, 31.1 ppm.
4-(1,2,2-Trifluorovinyl)biphenyl 2c.18 The general procedure A with biphenyl-4-ylboronic acid (200
t
mg, 1.00 mmol), Pd(dba)2 (1.2 mg) and Bu3PHBF4 (1.2 mg) gave 177.8 mg (76%) of 4-(1,2,2-
trifluorovinyl)biphenyl as a white solid. 1H NMR (300.1 MHz, CDCl3, 298 K, TMS) δ 7.60-7.30 (m, 9
19
H) ppm; F NMR (282.4 MHz, CDCl3, 298 K, TMS) δ -99.47 (dd, J = 70.6, 32.5 Hz, 1 F), -114.32
(dd, J = 109.0, 70.6 Hz, 1 F), -176.87 (dd, J = 109.0, 32.2 Hz, 1 F) ppm; 13C NMR (100.6 MHz,
CDCl3, 299 K, TMS) δ 154.1 (ddd, J = 290.8, 283.0, 49.8 Hz), 141.7, 140.2, 129.0, 128.8 (ddd, J =
225.4, 45.7, 19.7 Hz,), 126.3 (dd, J = 22.3, 6.8 Hz), 127.9, 127.4, 127.1, 124.9 ppm; IR: 3034, 1756,
1605, 1557, 1488, 1450, 1407, 1343, 1293, 1153, 1130, 1115, 1028, 1005, 984, 840, 764, 743, 721,
690 cm-1. MS (EI) m/z(%) 234.2 (100); HRMS (ESI): Calculated for C14H9F3: 234.0656, Found
234.0659; Mp: 57 – 59℃。
1-Methoxy-4-(1,2,2-trifluorovinyl)benzene (Table 2, 2d).7d The general procedure A with 4-
t
methoxyphenylboronic acid (155 mg, 1.00 mmol), Pd(dba)2 (1.2 mg) and Bu3PHBF4 (1.2 mg) gave
1
129.7 mg (69%) of 1-methoxy-4-(1,2,2-trifluorovinyl)benzene as a colorless liquid. H NMR (399.6
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MHz, CDCl3, 298 K, TMS) δ 7.41 (d, J = 8.7 Hz, 2 H), 6.96 (d, J = 8.7 Hz, 2 H), 3.84 (s, 3 H) ppm;
19F NMR (376.0 MHz, CDCl3, 298 K, TMS) δ -102.41 (dd, J = 77.7, 31.7 Hz, 1 F), -117.40 (dd, J =
6
7
13
110.0, 77.7 Hz, 1 F), -175.48 (dd, J = 110.3, 31.7 Hz, 1 F) ppm; C NMR (100.5 MHz, CDCl3, 298
8
9
K, TMS) δ 159.9, 153.4 (ddd, J = 288.9, 280.4, 50.6 Hz), 128.6 (ddd, J = 226.1, 46.2, 19.7 Hz), 126.1
(dd, J = 10.0, 6.0 Hz), 119.6 (dd, J = 23.0, 6.4 Hz) 114.1, 55.2 ppm.
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1-Phenoxy-4-(1,2,2-trifluorovinyl)benzene 2e. The general procedure
A
with 4-
t
phenoxyphenylboronic acid (214 mg, 1.00 mmol), Pd(dba)2 (1.2 mg) and Bu3PHBF4 (1.2 mg) gave
1
200.0 mg (80%) of 1-phenoxy-4-(1,2,2-trifluorovinyl)benzene as a colorless liquid. H NMR (399.6
19
MHz, CDCl3, 298 K, TMS) δ 7.47-7.38 (m, 4 H), 7.26-7.17 (m, 1 H), 7.09-7.06 (m, 4 H) ppm; F
NMR (376.0 MHz, CDCl3, 298 K, TMS) δ -101.12 (dd, J = 74.8, 32.1 Hz, 1 F), -116.15 (dd, J =
13
110.1, 74.7 Hz, 1 F), -175.76 (dd, J = 109.9, 32.1 Hz, 1 F) ppm; C NMR (100.6 MHz, CDCl3, 298
K, TMS) 158.0, 156.3, 153.6 (ddd, J = 289.9, 281.4, 50.1 Hz), 129.9, 128.5 (ddd, J = 226.3, 46.0, 20.0
Hz), 126.2 (dd, J = 10.2, 6.1 Hz), 124.1 (d, J = 25.0 Hz), 121.8 (dd, J = 22.7, 6.5 Hz), 119.5, 118.5
ppm. IR: ν
1762, 1612, 1591, 1509, 1490, 1289, 1244, 1202, 1172, 1148, 1109, 1071, 984, 908,
max
870, 838, 798, 757, 693 cm-1; MS (EI) m/z(%) 250.1(100); HRMS (ESI): Calculated for C14H9F3O:
250.0605; Found: 250.0604.
1-(1,2,2-Trifluorovinyl)-4-vinylbenzene 2f. The general procedure A with 4-vinylphenylboronic acid
t
(148 mg, 1.00 mmol), Pd(dba)2 (1.2 mg) and Bu3PHBF4 (1.2 mg) gave 93.8 mg (51%) of 1-(1,2,2-
1
trifluorovinyl)-4-vinylbenzene as a colorless liquid. H NMR (400.1 MHz, CDCl3, 300 K, TMS) δ
7.52-7.47 (m, 4 H), 6.77 (dd, J = 17.6, 10.9 Hz, 1 H), 5.85 (d, J = 17.6 Hz, 1 H), 5.37 (d, J = 10.9 Hz,
1 H) ppm; 19F NMR (282.4 MHz, CDCl3, 297 K, TMS) δ -99.61 (dd, J = 70.3, 32.3 Hz, 1 F), -114.25
(dd, J = 108.9, 70.4 Hz, 1 F), -176.95 (dd, J = 108.9, 32.3 Hz, 1 F) ppm; 13C NMR (100.5 MHz,
CDCl3, 298 K, TMS) δ 153.9 (ddd, J = 291.0, 283.3, 50.1 Hz), 138.1, 136.00, 128.7 (ddd, J = 226.4,
45.3, 19.8 Hz), 126.5 (dd, J = 22.2, 6.8 Hz), 126.5, 124.5 (dd, J = 10.6, 6.6 Hz), 115.1 ppm. IR: ν max
3092, 3046, 3012, 2928, 1758, 1631, 1558, 1515, 1406, 1288, 1261, 1211, 1151, 1118, 984, 909, 843,
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735, 605 cm-1; MS (EI): m/z (%) 166 (100); HRMS (ESI): Calculated for C10H7F3: 184.0500; Found:
184.0504.
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7
Ethyl
4-(1,2,2-trifluorovinyl)benzoate
2g.
The
general
procedure
A
with
4-
8
9
(ethoxycarbonyl)phenylboronic acid (194 mg, 1.00 mmol), Pd(dba)2 (1.2 mg) and tBu3PHBF4 (1.2 mg)
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1
gave 161.0 mg (70%) of ethyl 4-(1,2,2-trifluorovinyl)benzoate as a colorless liquid. H NMR (400.1
MHz, CDCl3, 299 K, TMS) δ 8.06 (d, J = 8.5 Hz, 2 H), 7.49 (d, J = 8.4 Hz, 2 H), 4.38 (q, J = 7.1, Hz,
19
2 H), 1.39 (t, J = 7.1 Hz, 3 H) ppm; F NMR (282.4 MHz, CDCl3, 297 K, TMS) δ -97.50 (dd, J =
70.3, 32.1 Hz, 1 F), -112.05 (dd, J = 108.7, 63.6 Hz, 1 F), -178.16 (dd, J = 108.7, 33.3 Hz, 1 F) ppm;
13C NMR (100.5 MHz, CDCl3, 298 K, TMS) δ 165.6, 154.1 (ddd, J = 293.0, 285.4, 49.3 Hz), 131.3
(dd, J = 21.9, 7.1 Hz), 130.5, 129.7, 128.2 (ddd, J = 228.4, 44.5, 20.1 Hz), 123.9 (dd, J = 11.0, 6.9 Hz),
61.1, 14.1 ppm; IR: ν
2985, 2940, 2908, 1755, 1720, 1621, 1569, 1465, 1447, 1412, 1390, 1368,
max
1336, 1314, 1277, 1186, 1154, 1108, 1023, 985, 857, 771, 733, 697, 495 cm-1; MS (EI): m/z (%)
185.1 (100); HRMS (ESI): Calculated for C11H9F3O2: 230.0555; Found: 230.0559.
1-(4-(1,2,2-Trifluorovinyl)phenyl)ethanone 2h.11 The general procedure
A
with 4-
t
acetylphenylboronic acid (164 mg, 1.00 mmol), Pd(dba)2 (1.2 mg) and Bu3PHBF4 (1.2 mg) gave
1
130.0 mg (65%) of 1-(4-(1,2,2-trifluorovinyl)phenyl)ethanone as a colorless liquid. H NMR (300.0
MHz, CDCl3, 298 K, TMS) δ 7.95 (d, J = 8.4 Hz, 2 H), 7.50 (d, J = 8.4 Hz, 2 H), 2.56 (s, 3 H) ppm;
19F NMR (282.4 MHz, CDCl3, 298 K, TMS) δ -96.94 (dd, J = 62.3, 33.0 Hz, 1 F), -111.56 (dd, J =
13
108.4, 62.4 Hz, 1 F), -178.10 (dd, J = 108.5, 33.0 Hz, 1 F) ppm; C NMR (100.6 MHz, CDCl3, 298
K, TMS) 196.9, 154.2 (ddd, J = 293.4, 285.8, 49.2 Hz), 136.8, 131.5 (dd, J = 21.9, 7.2 Hz), 129.0,
128.2 (ddd, J = 226.8, 45.4, 20.0 Hz), 124.82-123.61 (m), 26.42 ppm.
2-(1,2,2-Trifluorovinyl)naphthalene 2i.11 The general procedure A with naphthalen-2-ylboronic acid
t
(172 mg, 1.00 mmol), Pd(dba)2 (1.2 mg) and Bu3PHBF4 (1.2 mg) gave 174.7 mg (84%) of 2-(1,2,2-
trifluorovinyl)naphthalene as a colorless liquid. 1H NMR (399.6 MHz, CDCl3, 298 K, TMS) δ 7.97 (s,
19
1 H), 7.90-7.84 (m, 3 H), 7.58-7.53 (m, 3 H) ppm; F NMR (376.0 MHz, CDCl3, 298 K, TMS) δ -
99.15 (dd, J = 70.5, 32.2 Hz, 1 F), -114.34 (dd, J = 108.8, 70.5 Hz, 1 F), -176.22 (dd, J = 108.8, 32.2
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Hz, 1 F) ppm; 13C NMR (100.6 MHz, CDCl3, 299 K, TMS) δ 154.0 (ddd, J = 290.7, 283.3, 50.0 Hz),
133.0, 132.9, 128.7 (ddd, J = 245.2, 42.9, 17.8 Hz), 128.5, 128.3, 127.7, 127.00, 126.8, 124.6 (dd, J =
22.0, 6.9 Hz), 124.0 (m), 121.5 (m) ppm; MS (EI) m/z (%) 234.2 (100) ppm.
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1-Chloro-4-(1,2,2-trifluorovinyl)benzene 2j.7d The general procedure A with 4-chlorophenylboronic
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t
acid (156 mg, 1.00 mmol), Pd(dba)2 (1.2 mg) and Bu3PHBF4 (1.2 mg) gave 155.5 mg (81%) of 1-
1
chloro-4-(1,2,2-trifluorovinyl)benzene as a colorless liquid. H NMR (399.6 MHz, CDCl3, 298 K,
19
TMS) δ 7.41 (s, 4 H) ppm; F NMR (376.0 MHz, CDCl3, 298 K, TMS) δ -98.96 (dd, J = 69.6, 33.1
Hz, 1 F), -113.78 (dd, J = 109.6, 69.6 Hz, 1 F), -176.97 (dd, J = 109.6, 33.0 Hz, 1 F) ppm; 13C NMR
(100.6 MHz, CDCl3, 298 K, TMS) 153.7 (ddd, J = 291.7, 283.4, 49.6 Hz), 134.7, 130.0, 128.2, 128.1
(ddd, J = 240.9, 44.9, 19.9 Hz), 125.8 (dd, J = 20.2, 6.9 Hz), 125.5 (m) ppm.
1-(1,2,2-Trifluorovinyl)naphthalene 2k.7g The general procedure A with naphthalen-1-ylboronic
t
acid (172 mg, 1.00 mmol), Pd(dba)2 (1.2 mg) and Bu3PHBF4 (1.2 mg) gave 145.6 mg (70%) of 1-
1
(1,2,2-trifluorovinyl)naphthalene as a colorless liquid. H NMR (399.6 MHz, CDCl3, 298 K, TMS) δ
19
8.03-7.91 (m, 3 H), 7.61-7.50 (m, 4 H) ppm; F NMR (376.0 MHz, CDCl3, 298 K, TMS) δ -101.49
(dd, J = 74.0, 29.1 Hz, 1 F), -117.14 (dd, J = 117.5, 74.2 Hz, 1 F), -159.91 (dd, J = 117.7, 29.1 Hz, 1
F) ppm; 13C NMR (100.6 MHz, CDCl3, 299 K, TMS) δ 154.1 (ddd, J = 290.8, 283.0, 49.8 Hz), 133.7,
131.4, 128.9, 128.7, 127.7 (ddd, J = 232.2, 45.7, 19.7 Hz), 127.3, 126.9, 125.0, 124.8, 123.8 (dd, J =
20.7, 4.1 Hz) ppm; MS (EI) m/z(%) 234.2 (100).
2-(1,2,2-Trifluorovinyl)biphenyl 2l.7c The general procedure A with biphenyl-2-ylboronic acid (198
t
mg, 1.00 mmol), Pd(dba)2 (1.2 mg) and Bu3PHBF4 (1.2 mg) gave 177.8 mg (76%) of 2-(1,2,2-
trifluorovinyl)biphenyl as a colorless liquid. 1H NMR (300.1 MHz, CDCl3, 298 K, TMS) δ 7.72-7.49
19
(m, 9 H) ppm; F NMR (282.4 MHz, CDCl3, 298 K, TMS) δ -102.73 (dd, J = 73.9, 29.7 Hz, 1 F), -
13
118.24 (dd, J = 116.7, 74.6 Hz, 1 F), -159.64 (dd, J = 116.8, 29.6 Hz, 1 F) ppm; C NMR (100.5
MHz, CDCl3, 298 K, TMS) δ 152.9 (ddd, J = 289.9, 276.9, 50.3 Hz), 142.7, 140.2, 130.7, 130.7,
130.6, 130.5 (m), 128.4, 127.6 (ddd, J = 231.5, 52.0, 20.0 Hz), 127.6, 127.4, 125.1 (dd, J = 20.2, 4.5
Hz) ppm; IR: ν max 3064, 3029, 1783, 1597, 1566, 1481, 1450, 1437, 1247, 1141, 1104, 1075, 1056,
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1009, 982, 953, 909, 766, 757, 742, 700, 617, 603, 570, 545, 476 cm-1; MS (EI) m/z (%) 234.1(100);
HRMS (ESI): Calculated for C14H9F3: 234.0656; Found: 234.0659.
6
7
1-Methoxy-3-(1,2,2-trifluorovinyl)benzene 2m.7g The general procedure
A
with 3-
8
9
t
methoxyphenylboronic acid (152 mg, 1.00 mmol), Pd(dba)2 (1.2 mg) and Bu3PHBF4 (1.2 mg) gave
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159.8 mg (85%) of 1-methoxy-3-(1,2,2-trifluorovinyl)benzene as a colorless liquid. H NMR (300.1
MHz, CDCl3, 297 K, TMS) δ 7.61 (t, J = 8.0 Hz, 1 H), 7.34 (d, J = 7.8 Hz, 1 H), 7.28 (s, 1 H), 7.18 (d,
19
J = 8.2 Hz, 1 H), 4.10 (s, 3 H) ppm; F NMR (282.4 MHz, CDCl3, 297 K, TMS) δ -99.31 (dd, J =
70.2, 32.7 Hz, 1 F), -113.70 (dd, J = 109.1, 70.2 Hz, 1 F), -176.07 (dd, J = 109.1, 32.7 Hz, 1 F) ppm;
13C NMR (100.5 MHz, CDCl3, 298 K, TMS) δ 159.8, 154.0 (ddd, J = 290.5, 283.0, 49.7 Hz), 129.8,
128.6 (ddd, J = 225.4, 44.4, 19.3 Hz), 128.6 (dd, J = 22.1, 6.7 Hz), 116.9, 114.5, 110.0, 55.5 ppm.
3-(1,2,2-Trifluorovinyl)aniline 2n. The general procedure A with 3-aminophenylboronic acid (137
t
mg, 1.00 mmol), Pd(dba)2 (1.2 mg) and Bu3PHBF4 (1.2 mg) gave 91.7 mg (53%) of 3-(1,2,2-
1
trifluorovinyl)aniline as a colorless liquid. H NMR (400.1 MHz, CDCl3, 299 K, TMS) δ 7.21 (t, J =
7.9 Hz, 1 H), 6.88 (d, J = 7.8 Hz, 1 H), 6.79 (s, 1 H), 6.67 (dd, J = 8.0, 2.1 Hz, 1 H). 3.73 (br, 2 H); 19F
NMR (282.4 MHz, CDCl3, 297 K, TMS) δ -99.69 (dd, J = 71.4, 32.3 Hz, 1 F), -113.91 (dd, J = 108.9,
71.4 Hz, 1 F), -176.00 (dd, J = 108.9, 32.3 Hz, 1 F) ppm; 13C NMR (100.5 MHz, CDCl3, 298 K,
TMS) δ 153.9 (ddd, J = 290.1, 282.8, 50.2 Hz), 146.7, 129.6 (d, J = 6.3 Hz), 128.8 (ddd, J = 226.0,
44.6, 19.5 Hz), 128.3 (dd, J = 21.9, 6.5 Hz), 115.5, 114.8 (m), 110.7 (dd, J = 10.6, 6.3 Hz) ppm; IR: ν
3465, 3381, 3222, 2928, 1757, 1622, 1589, 1496, 1455, 1345, 1308, 1292, 1244, 1173, 1144,
max
1080, 1027, 1012, 909, 866, 783, 734, 688, 620, 526, 453 cm-1; MS (EI): m/z (%) 173 (100); HRMS
(ESI): Calculated for C8H6F3N: 173.0452; Found: 173.0450.
1-(3-(1,2,2-Trifluorovinyl)phenyl)ethanone 2o. The general procedure
A
with 3-
t
acetylphenylboronic acid (164 mg, 1.00 mmol), Pd(dba)2 (1.2 mg) and Bu3PHBF4 (1.2 mg) gave
1
164.0 mg (82%) of 1-(3-(1,2,2-trifluorovinyl)phenyl)ethanone as a colorless liquid. H NMR (400.1
MHz, CDCl3, 299 K, TMS) δ 7.96 (s, 1 H), 7.86 (d, J = 7.6 Hz, 1 H), 7.56 (d, J = 7.8 Hz, 1 H), 7.46 (t,
19
J = 7.8 Hz, 1 H), 2.55 (s, 3 H) ppm; F NMR (282.4 MHz, CDCl3, 297 K, TMS) δ -99.12 (dd, J =
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68.7, 33.0 Hz, 1 F), -114.03 (dd, J = 109.8, 68.6 Hz, 1 F), -177.67 (dd, J = 109.6, 33.1 Hz, 1 F) ppm;
13C NMR (100.5 MHz, CDCl3, 298 K, TMS) δ 196.9, 153.9 (ddd, J = 291.7, 283.7, 49.4 Hz), 137.4,
129.0, 128.5-128.2 (m), 128.1 (ddd, J = 226.6, 45.0, 20.0 Hz), 127.7 (dd, J = 22.5, 6.8 Hz), 123.9 (dd,
8
9
J = 10.8, 6.3 Hz), 26.2 ppm; IR: ν
3364, 3076, 3007, 2926, 1758, 1691, 1604, 1583, 1488, 1434,
max
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1360, 1328, 1297, 1243, 1151, 1109, 1085, 1021, 1008, 957, 914, 795, 735, 687, 619, 590 cm-1; MS
(EI): m/z (%) 185 (100); HRMS (ESI): Calculated for C10H7F3O: 200.0449; Found: 200.0448.
3-(1,2,2-Trifluorovinyl)benzaldehyde 2p. The general procedure A with 3-formylphenylboronic acid
t
(150 mg, 1.00 mmol), Pd(dba)2 (1.2 mg) and Bu3PHBF4 (1.2 mg) gave 93.0 mg (50%) of 3-(1,2,2-
trifluorovinyl)benzaldehyde as a colorless liquid. 1H NMR (400.1 MHz, CDCl3, 299 K, TMS) δ 10.04
(d, J = 0.7 Hz, 1 H), 7.97 (s, 1 H), 7.88 (d, J = 7.7 Hz, 1 H), 7.72 (d, J = 7.9 Hz, 1 H), 7.62 (t, J = 7.7
19
Hz, 1 H) ppm; F NMR (282.4 MHz, CDCl3, 297 K, TMS) δ -98.23 (dd, J = 66.9, 33.1 Hz, 1 F), -
13
113.27 (dd, J = 109.5, 67.1 Hz, 1 F), -177.94 (dd, J = 109.5, 33.3 Hz, 1 F) ppm; C NMR (100.5
MHz, CDCl3, 298 K, TMS) δ 191.3, 153.0 (ddd, J = 292.5, 284.2, 49.1 Hz), 136.8, 129.6 (dd, J =
15.7, 7.5 Hz), 129.0, 128.4 (m), 127.9 (ddd, J = 226.7, 45.1, 20.2 Hz), 125.4 (dd, J = 10.8, 6.6 Hz)
ppm; IR: ν max 3389, 3072, 2836, 2739, 1757, 1704, 1604, 1584, 1484, 1442, 1384, 1333, 1296, 1287,
1190, 1172, 1145, 1088, 1027, 1013, 909, 853, 798, 733, 706, 686, 651, 619, 432 cm-1; MS (EI): m/z
(%) 186.1 (100); HRMS (ESI): Calculated for C9H5F3O: 186.0292; Found: 186.0290.
3-(1,2,2-Trifluorovinyl)benzonitrile 2q.18b The general procedure A with 3-cyanophenylboronic acid
t
(147 mg, 1.00 mmol), Pd(dba)2 (1.2 mg) and Bu3PHBF4 (1.2 mg) gave 104.3 mg (57%) of 3-(1,2,2-
trifluorovinyl)benzonitrile as a colorless liquid. 1H NMR (400.1 MHz, CDCl3, 299 K, TMS) δ 7.77 (s,
19
1 H), 7.73 (d, J = 8.0 Hz, 1 H), 7.67 (d, J = 7.8 Hz, 1 H), 7.59 (t, J = 7.9 Hz, 1 H); F NMR (282.4
MHz, CDCl3, 297 K, TMS) δ -98.23 (dd, J = 64.7, 33.7 Hz, 1 F), -111.58 (dd, J = 109.8, 64.3 Hz, 1
13
F), -178.06 (dd, J = 109.8, 33.7 Hz, 1 F) ppm; C NMR (100.5 MHz, CDCl3, 298 K, TMS) δ 154.0
(ddd, J = 293.6, 284.9, 48.6 Hz), 132.1 (dd, J = 4.3, 2.4 Hz), 129.7, 128.8 (dd, J = 22.8, 7.0 Hz), 128.2
(ddd, J = 7.7, 5.9, 4.0 Hz), 127.9 – 127.5 (m), 127.3 (ddd, J = 227.0, 45.0, 20.6 Hz), 117.9, 113.4
ppm; IR: ν
2235, 1757, 1488, 1432, 1422, 1334, 1298, 1187, 1152, 1141, 1089, 1030, 1013, 912,
max
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824, 800, 735, 684, 475 cm-1; MS (EI): m/z (%) 183 (100); HRMS (ESI): Calculated for C9H4F3N:
183.0296; Found: 183.0295.
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2-Fluoro-4-(1,2,2-trifluorovinyl)biphenyl 2r. The general procedure A with 2-fluorobiphenyl-4-
ylboronic acid (216 mg, 1.00 mmol), Pd(dba)2 (1.2 mg) and tBu3PHBF4 (1.2 mg) gave 181.4 mg (72%)
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of 2-fluoro-4-(1,2,2-trifluorovinyl)biphenyl as a white solid. H NMR (400.1 MHz, CDCl3, 299 K,
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TMS) δ 8.06 – 6.45 (m, 8 H) ppm; F NMR (282.4 MHz, CDCl3, 297 K, TMS) δ -98.24 (dd, J =
66.7, 32.7 Hz, 1 F), -112.84 (dd, J = 109.0, 66.9 Hz, 1 F), -117.02 (t, J = 9.3 Hz, 1 F), -172.24 - -
13
181.09 (m, 1 F) ppm; C NMR (100.5 MHz, CDCl3, 298 K, TMS) δ 159.8 (d, J = 250.7 Hz), 154.1
(ddd, J = 292.1, 284.2, 49.2 Hz), 134.9 (d, J = 0.9 Hz), 131.1 (d, J = 3.0 Hz), 129.5 (d, J = 14.2 Hz),
129.0 (d, J = 3.1 Hz), 128.6, 128.2 (ddd, J = 14.1, 8.8, 1.6 Hz), 128.2 (d, J = 4.9 Hz), 127.9 (dddd, J =
206.0, 45.2, 20.0, 2.9 Hz), 120.2 (m), 112.9 (m) ppm; IR: ν
3078, 3031, 2926, 1756, 1618, 1580,
max
1557, 1522, 1486, 1448, 1410, 1347, 1305, 1245, 1197, 1156, 1134, 1125, 1075, 1038, 1026, 1018,
869, 829, 768, 721, 697, 641, 589, 552, 514, 490, 458 cm-1; MS (EI): m/z (%) 252 (100); HRMS (ESI):
Calculated for C14H8F4: 252.0562; Found: 252.0566. mp: 44-45℃.
2-Methoxy-6-(1,2,2-trifluorovinyl)naphthalene 2s. The general procedure
A
with 6-
methoxynaphthalen-2-ylboronic acid (202 mg, 1.00 mmol), Pd(dba)2 (1.2 mg) and tBu3PHBF4 (1.2 mg)
gave 192.8 mg (81%) of 2-methoxy-6-(1,2,2-trifluorovinyl)naphthalene as a colorless liquid. 1H NMR
(399.6 MHz, CDCl3, 298 K, TMS) δ 7.88 (s, 1 H), 7.77 (d, J = 8.7 Hz, 1 H), 7.76 (d, J = 8.9 Hz, 1 H),
7.52 (d, J = 8.7 Hz, 1 H), 7.20 (dd, J = 9.0, 2.2 Hz, 1 H),7.14 (d, J = 2.3 Hz, 1 H), 3.94 (s, 3 H) ppm;
19F NMR (376.0 MHz, CDCl3, 298K, TMS) δ -100.28 (dd, J = 73.3, 31.8 Hz, 1 F), -115.44 (dd, J =
13
109.1, 73.3 Hz, 1 F), -175.97 (dd, J = 108.9, 31.8 Hz, 1 F) ppm; C NMR (100.5 MHz, CDCl3, 298
K, TMS) 158.5, 153.9 (ddd, J = 290.4, 282.2, 50.3 Hz), 134.4, 129.8, 129.0 (ddd, J = 214.7, 45.3, 19.8
Hz), 128.3, 127.3 (d, J = 1.4 Hz), 123.9 (m), 122.3 (dd, J = 22.1, 6.6 Hz), 122.1 (m), 119.7, 105.6,
55.3 ppm. IR: ν max 3060, 3007, 2962, 2937, 2839, 1754, 1631, 1603, 1507, 1488, 1462, 1440, 1413,
1393, 1288, 1260, 1207, 1164, 1135, 1031, 1021, 905, 894, 855, 815, 749, 698 cm-1; MS (EI) m/z(%)
238.1(100); HRMS (ESI): Calculated for C13H9F3O: 238.0605; Found: 238.0603.
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4-Chloro-1-ethoxy-2-(1,2,2-trifluorovinyl)benzene 2t. The general procedure A with 5-chloro-2-
4
5
ethoxyphenylboronic acid (200 mg, 1.00 mmol), Pd(dba)2 (1.2 mg) and tBu3PHBF4 (1.2 mg) gave 94.4
6
7
1
mg (40%) of 4-chloro-1-ethoxy-2-(1,2,2-trifluorovinyl)benzene as a colorless liquid. H NMR (400.1
8
9
MHz, CDCl3, 299 K, TMS) δ 7.38 (m, 1 H), 7.36 (d, J = 0.9 Hz, 1 H), 6.90 (d, J = 9.5 Hz, 1 H), 4.10
(q, J = 7.0 Hz, 2 H), 1.45 (t, J = 7.0 Hz, 3H); 19F NMR (282.4 MHz, CDCl3, 297 K, TMS) δ -101.40
(ddd, J = 69.0, 30.8 Hz, 1 F), -114.50 (dd, J = 113.7, 69.2 Hz, 1 F), -166.83 (dd, J = 114.2, 30.3 Hz, 1
F) ppm; 13C NMR (100.5 MHz, CDCl3, 298 K, TMS) δ 155.2, 153.4 (ddd, J = 289.1, 279.2, 50.4 Hz),
131.9, 130.1, 124.8, 1284.7 (ddd, J = 230.8, 52.2, 22.1 Hz), 117.5 (dd, J = 21.5, 4.6 Hz), 113.6, 64.6,
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14.9 ppm; IR: ν
2968, 2933, 1778, 1599, 1496, 1474, 1396, 1326, 1293, 1277, 1245, 1149, 1125,
max
1042, 1007, 998, 924, 888, 824, 807, 793, 662 cm-1; MS (EI): m/z (%) 207 (100); HRMS (ESI):
Calculated for C10H8F3OCl: 236.0216; Found: 236.0215.
6-(1,2,2-Trifluorovinyl)-2,3-dihydrobenzo[b][1,4]dioxine 2u. The general procedure A with 2,3-
dihydrobenzo[b][1,4]dioxin-6-ylboronic acid (180 mg, 1.00 mmol), Pd(dba)2 (1.2 mg) and tBu3PHBF4
(1.2 mg) gave 194.4 mg (90%) of 6-(1,2,2-trifluorovinyl)-2,3-dihydrobenzo[b][1,4]dioxine as a
colorless liquid. 1H NMR (400.1 MHz, CDCl3, 299 K, TMS) δ 7.03 (d, J = 1.9 Hz, 1 H), 6.99(dd, J =
19
8.4, 1.6 Hz, 1 H)6.94 (d, J = 8.5 Hz, 1H), 4.31 (s, 4 H) ppm; F NMR (282.4 MHz, CDCl3, 297 K,
TMS) δ -101.65 (dd, J = 73.5, 32.0 Hz, 1 F), -116.34 (dd, J = 109.8, 75.5 Hz, 1 F), -175.39 (dd, J =
109.8, 31.9 Hz, 1 F) ppm; 13C NMR (100.5 MHz, CDCl3, 298 K, TMS) δ 153.9 (ddd, J = 289.0,
281.2, 50.3 Hz), 144.1, 143.7 (d, J = 1.9 Hz), 128.4 (ddd, J = 226.1, 45.7, 19.9 Hz), 120.5 (dd, J =
23.1, 6.5 Hz), 118.0 (m), 117.6, 113.8 (m), 64.4, 64.3 ppm; IR: ν
2985, 2938, 2881, 1762, 1618,
max
1585, 1514, 1461, 1433, 1426, 1339, 1327, 1296, 1264, 1250, 1253, 1193, 1123, 1070, 1025, 1019,
1007, 932, 893, 865, 814, 750, 699, 634, 585 cm-1; MS (EI): m/z (%) 216.0 (100); HRMS (ESI):
Calculated for C10H7F3O2: 216.0398; Found: 216.0400.
2-(1,2,2-Trifluorovinyl)benzofuran 2v. The general procedure A with benzofuran-2-ylboronic acid
t
(162 mg, 1.00 mmol), Pd(dba)2 (1.2 mg) and Bu3PHBF4 (1.2 mg) gave 87.1 mg (44%) of 2-(1,2,2-
trifluorovinyl)benzofuran as a colorless liquid. 1H NMR (400.1 MHz, CDCl3, 299 K, TMS) δ 7.50 (d,
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J = 7.4 Hz, 1 H), 7.42 (d, J = 8.1 Hz, 1 H), 7.25 (t, J = 7.6 Hz, 1 H), 7.18 (t, J = 7.3 Hz, 1 H), 6.81 (s,
1 H) ppm; 19F NMR (282.4 MHz, CDCl3, 297 K, TMS) δ -97.72 (dd, J = 60.0, 30.0 Hz, 1 F), -111.22
(dd, J = 110.5, 60.0 Hz, 1 F), -184.23 (dd, J = 110.5, 30.0 Hz, 1 F) ppm; 13C NMR (100.5 MHz,
CDCl3, 298 K, TMS) δ 155.2, 153.4 (ddd, J = 292.8, 288.4, 45.0 Hz), 143.2 (dd, J = 32.9, 8.3 Hz),
127.5, 125.5, 123.5, 123.4 (ddd, J = 223.6, 48.9, 24.0 Hz), 121.4, 111.5, 105.8 (dd, J = 7.5, 5.3 Hz)
ppm; IR: ν max 3068, 2928, 1764, 1653, 1616, 1575, 1558, 1541, 1507, 1476, 1452, 1378, 1351, 1302,
1256, 1180, 1152, 1143, 1108, 1032, 940, 910, 880, 855, 808, 749, 737, 658 cm-1; MS (EI): m/z (%)
198.0 (100); HRMS (ESI): Calculated for C10H5F3O: 198.0292; Found: 198.0293.
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1-Methoxy-2-(1,2,2-trifluorovinyl)benzene 3a.8a The general procedure
B
with 2-
t
methoxyphenylboronic acid (152 mg, 1.00 mmol), Pd(dba)2 (1.2 mg) and Bu3PHBF4 (1.2 mg) gave
112.8 mg (60%) of 1-methoxy-2-(1,2,2-trifluorovinyl) -benzene as a colorless liquid. 1H NMR (399.6
MHz, CDCl3, 298 K, TMS) δ 7.45 (t, J = 7.9 Hz, 1 H), 7.37 (d, J = 7.6 Hz, 1 H), 7.03 (t, J = 7.5 Hz, 1
19
H), 6.98 (d, J = 8.4 Hz, 1 H), 3.88 (s, 3 H); F NMR (282.4 MHz, CDCl3, 298 K, TMS) δ -101.93
(dd, J = 73.2, 29.3 Hz, 1 F), -116.00 (dd, J = 115.2, 73.4 Hz, 1 F), -164.45 (dd, J = 115.1, 29.4 Hz, 1
F); 13C NMR (100.5 MHz, CDCl3, 298 K, TMS) δ 157.6, 153.4 (ddd, J = 288.4, 277.2, 51.1 Hz),
132.0 (d, J = 1.6 Hz), 130.6 (d, J = 2.2 Hz), 125.6 (ddd, J = 231.0, 52.2, 21.1 Hz), 120.4, 115.7 (dd, J
= 21.1, 4.5 Hz), 111.2, 55.6 ppm.
Procedure of the scaled-up reaction.
A 250 mL Schlenk-type sealed tube (with a Teflon high-pressure valve and side arm) equipped with a
magnetic stir bar was charged with the biphenyl-4-ylboronic acid (2.0 g, 10.0 mmol), potassium
phosphate (6.36 g, 30.0 mmol), Pd(dba)2 (12 mg, 2.0 mmol %), tri-tert-butylphosphine
tetrafluoroborate (12 mg, 4.0 mmol %). The reaction tube was capped, then evacuated briefly under
high vacuum and charged with argon, repeated three times. Then freshly distilled toluene (20.0 mL)
and DMF (20.0 mL), deionized water (14.0 mL) was added, and chlorotrifluoroethene was bubbled
about 15 min (excess). Then the valve was screwed. The reaction mixture was stirred at 80 oC for 2 h.
The reaction vessel was then cooled to room temperature, filtered through a short plug of Celite. 20
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mL of Deionized water and 20 mL of pentane (AR) was added. The organic phase was separated and
washed with deionized water three times. The aqueous phase was extracted with pentane (3×10 mL).
The organic phase was combined, dried with anhydrous Na2SO4 and added silica gel, then evacuated
under vacuum. The residue was purified by silica gel flash column chromatography using pentane as
eluent to give 4-(1,2,2-trifluorovinyl)biphenyl a white solid (1.9 g, 80% yield).
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Acknowledgements. The authors gratefully acknowledge the financial support from National Basic
Research Program of China (2012CB821600, 2010CB126103), the Key Program of Natural Science
Foundation of China (21032006), National Natural Science Foundation of China
(21172245/21172244/B020304), Agro-scientific Research in the Public Interest (201103007), the
National Key Technologies R&D Program (2011BAE06B05), Shanghai Scientific Research Program
(10XD1405200), startup fund for financial support.
Supporting Information Available: Experimental details, spectra for compounds 2b-v, 3a-g. This
material is available free of charge via the Internet at http://pubs.acs.org.
References
(1) Hougham, G.; Cassidy, P. E.; Johns, K.; Davidson T. in Fluoropolymers 1: Synthesis, Kluwer
academic/Plenum Publisher, New York, 1999.
(2) Anilkumar, R.; Burton, D. J. in e-EROS Encyclopedia of Reagents for Organic Synthesis, 2001, pp
1-5.
(3) (a) Souzy, R.; Ameduri, B. Prog. Polym. Sci., 2005, 30, 644. (b) Wei, J.; Stone, C.; Steck, A. E.
US Patent 5422411; (c) Wei, J.; Stone, C.; Steck, A. E. US Patent 5498639, 1996; (d) Stone, C.;
Steck, A. E.; Lousenberg, R. D. US Patent 5602185; (e) Stone, C.; Steck, A. S.; Wei, J. US
Patent, 573480.
(4) Nikitina, T. S. Russia Chem. Rev. 1990, 59, 575.
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(5) (a) Cohen, S. G.; Wolosinski, H. T.; Scheuer, P. J. J. Am. Chem. Soc. 1949, 71, 3439. (b) Prober,
M. J. Am. Chem. Soc. 1953, 75, 968.
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(6) Dixon, S. J. Org. Chem. 1956, 21, 400.
9
(7) (a) Sorokina, R. S.; Rybakova, L. F.; Kalinovskii, I. O.; Chernoplekova, V. A.; Beletskaya, I. P.
Zh. Org. Chim. 1982, 18, 2458. (b) Sorokina, R. S.; Rybakova, L. F.; Kalinovskii, I. O.;
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(12) A provisional patent (application No PCT/CN2012/074374) on this work has been filed on April
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(13) CCDC 887510 contains the supplementary crystallographic data for the comlex [trans-
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