Synthesis of (Z)-α-Trifluoromethyl Alkenyl Triflate: A Scaffold for Diverse Trifluoromethylated Species

Article abstract of DOI:10.1021/acs.joc.6b00855

An efficient method for the synthesis of (Z)-selective α-trifluoromethyl alkenyl triflates is described. As an important fluorinated building block, it is utilized successfully for the synthesis of various trifluoromethyl derivatives such as diarylethylen

Full text of DOI:10.1021/acs.joc.6b00855

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Article
Synthesis of (Z)-alpha-Trifluoromethyl Alkenyl Triflate:
a Scaffold for Diverse Trifluoromethylated Species
Yilong Zhao, Yuhan Zhou, Juan Liu, Dongmei Yang, Liang
Tao, Yang Liu, Xiaoliang Dong, Jianhui Liu, and Jingping Qu
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.6b00855 • Publication Date (Web): 12 May 2016
Downloaded from http://pubs.acs.org on May 14, 2016
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Synthesis of (Z)-α-Trifluoromethyl Alkenyl Triflate: a Scaffold for Diverse
Trifluoromethylated Species
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Yilong Zhao,† Yuhan Zhou,*† Juan Liu,† Dongmei Yang,† Liang Tao,† Yang Liu,† Xiaoliang Dong,†
Jianhui Liu,‡ Jingping Qu†
†State Key Laboratory of Fine Chemicals, School of Pharmaceutical Science and Technology, Dalian University of
Technology, Dalian 116024, P.R. China
‡School of Petroleum and Chemical Engineering, Dalian University of Technology, Panjin 124221, P.R. China
Abstract: An efficient method for the synthesis of (Z)-selective α-trifluoromethyl alkenyl
triflates is described. As an important fluorinated building block, it is utilized successfully
for the synthesis of various trifluoromethyl derivatives such as diarylethylenes, enynes,
alkynes and benzofurans.
INTRODUCTION
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It is generally known that introducing fluorine atoms into bioactive molecules can
have some positive effects, such as rendering them more selective, potent, or increasing
efficacy.1 Among numerous fluorine-containing compounds, trifluoromethyl group
constitutes an important structural motif of many biologically active compounds. Thus,
an extensive variety of synthesis methodologies have been used to target
trifluoromethyl-containing compounds.2 In recent years, the trifluoromethylation
catalyzed by transition-metals, such as silver,3 copper including Cu(I)4 and Cu(II),5
nickel,6 palladium,7 platinum,8 rhodium9 etc. have been developed rapidly. Besides, a
particularly promising approach for the synthesis of trifluoromethyl-containing
compounds is through the use of appropriate trifluoromethylated building blocks.
Avoiding the harsh reaction conditions and the use of toxic or expensive fluorinated
reagents, trifluoromethylated building blocks have received much attention.10
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Including C-C double bond and sulfonate ester unit, enol sulfonate ester is well
known as an important organic synthesis intermediate because of easy derivatization.11
Thus, introducing trifluoromethyl group to this framework would offer an effective
fluorinated building block. However, only few countable reports on the synthesis and
reactions of trifluoromethylated enol sulfonate esters with limited structures were
available. The synthesis and applications of the enol sulfonate ester derived from ethyl
trifluoroacetoacetate were disclosed by de Lera12 and Lin.13 Then, Shimizu and
co-workers reported the synthesis and reactions of 1,1-dibromo-3,3,3-trifluoro-2-
tosyloxypropene
and
1,1-dichloro-3,3,3-trifluoro-2-tosyloxy-propene.14
Also,
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photoredox-catalyzed stereoselective trifluoromethyl-triflation of alkynes afforded
(E)-β-trifluoromethyl alkenyl triflates.15 Herein, a general method to prepare
trifluoromethylated enol sulfonate esters with various functional groups has yet to be
developed. In view of the high geometrical specificity of C-C double bond units present
in many biologically active compounds, geometrically selective synthesis of
trifluoromethylated enol sulfonate ester, especially with Z-selectivity, is still highly
desirable.
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Recently, our group reported an efficient method for the preparation of
trifluoromethyl ketones via the reaction between alkyl aryl ketones and ethyl
trifluoroacetate.16 In that transformation, a C-C bond cleavage step was witnessed, and
trifluoromethylated enol anion was generated in the reaction mixture. The
trifluoromethylated enol anion was successfully captured as (Z)-α-trifluoromethyl alkenyl
triflates when Tf2O was added to the reaction mixture upon the consumption of the
substrate. This procedure represents an operationally simple, highly efficient method for
the synthesis of (Z)-α-trifluoromethyl alkenyl triflates. Herein, we present the synthesis of
(Z)-α-trifluoromethyl alkenyl triflates and their applications in the straightforward
synthesis of trifluoromethylated alkenes, alkynes, enynes and benzofurans.
RESULTS AND DISCUSSION
As an extension of our previous study, α-trifluoromethyl substituted alkenyl triflates
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(2) were synthesized in good yields from alkyl aryl ketones (1), ethyl trifluoroacetate and
triflic anhydride (Table 1). The alkyl aryl ketones and ethyl trifluoroacetate undergo the
“trifluoroacetic ester/ketone metathesis” to form the trifluoromethylated enol anions,
which were captured by triflic anhydride in the second step to generate α-trifluoromethyl
substituted alkenyl triflates. Different with our previous study,16 methyl tert-butyl ether
(MTBE) was used as reaction solvent instead of THF only because THF can be easily
transferred into the ring-opening polymerization byproduct when triflic anhydride was
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used in the second step. To our surprise, H NMR of the crude product showed that a
single isomer was formed. Further, a single-crystal of 2e was prepared, and its structure
was confirmed to be Z by X-ray single-crystal diffraction, as shown in Figure S1 (see SI).
Table 1. Z-Selective Synthesis of Trifluoromethylated Alkenyl Triflatesa
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aReaction conditions: 1 (5 mmol), CF3COOEt (10 mmol), NaH (10 mmol), MTBE (10
mL) at 55 °C for 6 - 12 h under Ar atmosphere and then drop Tf2O (10 mmol) at 0 °C for
b
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5 - 10 min. The yield was determined by F NMR with m-BrC6H4CF3 as an internal
standard. cThe reaction was conducted on a 30.5 mmol scale with CF3COOEt (10 mL)
d
and NaH (61 mmol) in MTBE (200 mL) and then Tf2O (6.5 mL). The reaction was
conducted on a 1 mmol scale with CF3COOEt (2 mmol) and NaH (2 mmol) in MTBE (5
e
mL) and then Tf2O (2 mmol) in CH2Cl2 (5 mL). The reaction was conducted on a 2.0
mmol scale 1-(3,4-dimethoxyphenyl)-3-phenylpropan-1-one with CF3COOEt (6.0 mmol)
and NaH (4.0 mmol) in MTBE (10 mL) and then Tf2O (6.0 mmol). fThe reaction was
conducted on a 2.0 mmol scale 1-phenyldodecan-1-one with CF3COOEt (8.0 mmol) and
NaH (4.0 mmol) in MTBE (10 mL) and then Tf2O (6.0 mmol).
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Encouraged by the results obtained, the scope in terms of ketones was explored
(Table 1). Various enolizable phenyl ketones bearing either electron-withdrawing or
–donating groups were converted smoothly to the corresponding alkenyl triflates. The
ketone substrates with functional groups such as phenyl, chloro, alkoxy, bromo, and
heterocycles etc. gave the desired products in moderate to excellent yields. Electronic
effect has little impact on the reaction. The ketone substrates with either
electron-withdrawing or –donating groups in the same position (2b, 2f; 2c, 2g) have the
similar results. Nonetheless, a slightly lower yield was observed with ortho-substituents
(2e) compared with para-substituents (2d). That is likely due to the steric hindrance.
Furthermore, the relatively low yield of 2i was attributed to the poor solubility of the
corresponding ketone (1i) in MTBE. The heteroaryl substrate 1p was converted
effectively into alkenyl triflate 2p in 67% yield as well as the ketones containing
β-oxygen or β-sulphur atom in 92% and 93% yield, respectively. Moreover, the substrate
with linear aliphatic chain (1q) gave the desired alkenyl triflate 2q in good yield. Similar
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with 2e, excellent Z-selectivity was confirmed by H NMR of the crude products for all
the substances.
Bearing easily derived C-C double bond and sulfonate ester unit, trifluoromethylated
alkenyl triflates can be used for the synthesis of various trifluoromethyl derivatives, such
as diarylethylenes,17 enynes,18 alkynes19 and benzofurans.20
Thus, the cross-coupling reactions of trifluoromethylated alkenyl triflates with aryl
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metal reagents to afford trifluoromethylated diarylethylenes were preferentially explored.
Great challenge encountered by PhZnCl was the generation of the undesired
homocoupling byproduct, biphenyl, which is difficult to separate from the product,
trifluoromethylated diarylethylene (3). Fortunately, without any homocoupling byproduct,
introduction of an aryl or alkane group was accomplished with aryl-SnBu3 or alkyl-SnBu3.
Under the general condition of Stille coupling,21 trifluoromethylated alkenyl triflates were
converted into trifluoromethylated diarylethylenes with retention of the configuration of
C-C double bond (Table 2). Both trifluoromethylated alkenyl triflates and tributyl aryl
tins with electron-withdrawing or –donating groups worked well, giving the desired
trifluoromethylated diarylethylenes in good to excellent yields. Unfortunately, the
ortho-substituted ArSnBu3 was much less reactive under this condition as a result of
steric hindrance. The substrate with linear aliphatic chain reacted well to afford
corresponding product 3o. In all of the cases, 1H NMR of the crude products showed only
one isomer of the C-C double bond was formed. The absolute configuration of 3q was
determined to be E-configured double bond by X-ray single-crystal diffraction, as shown
in Figure S2 (see SI).
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Table 2. Stille Coupling Reactions of Alkenyl Triflatesa
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aReaction conditions: 2 (0.5 mmol), tributyl tin compounds (0.75 mmol), Pd(PPh3)2Cl2
(10% mmol), LiCl (20% mmol), toluene (3 mL) at 100 °C for 6-12 h under Ar
atmosphere. bThe reaction was conducted on a 3.0 mmol scale with (p-CH3O)C6H4SnBu3
c
(4.5 mmol), Pd(PPh3)2Cl2 (10% mmol), LiCl (20% mmol) in toluene (10 mL). The
reaction was conducted on a 2.8 mmol scale with (p-CH3)C6H4SnBu3 (4.2 mmol),
Pd(PPh3)2Cl2 (10% mmol), LiCl (20% mmol) in toluene (15 mL).
The trifluoromethylated enynes are important building blocks for functionalized
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trifluoromethylated compounds.22 Herein, successful Sonogashira coupling23 of
trifluoromethylated alkenyl triflates with alkynes was also established to afford
trifluoromethylated enynes (Table 3). (Z)-1-(4-bromophenyl)-3,3,3-trifluoroprop-1-en-
2-yl trifluoromethanesulfonate was investigated to react with diverse alkynes in most
cases. Remarkably, good regioselectivity between triflate and bromo was achieved. Thus,
trifluoromethylated enynes with methyl, chloro, methoxy and even amino were obtained
in good to excellent yields. In addition, alkyl-substituted alkyne was transformed into
corresponding enyne smoothly in 90% yield (4g).
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Table 3. Sonogashira Coupling Reaction of Alkenyl Triflatesa
R3
Pd(PPh3)2Cl2 (10% mmol)
CuI (20% mmol)
CF3
OTf
Et3N (3.0 eq)
THF, 25 oC
R1
R3
R1
+
F3C
4
2
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aReaction conditions: 2 (1.25 mmol or 2.5 mmol), alkyne (1.1 eq), Pd(PPh3)2Cl2 (10%
mmol), CuI (20% mmol), Et3N (3.0 eq), THF (5 mL) at 25 °C for 12 h under Ar
b
atmosphere. The reaction was conducted on a 0.51 mmol scale with alkyne (1.2 eq),
Pd(PPh3)2Cl2 (10% mmol), CuI (20% mmol), Et3N (2.0 eq) in THF (3 mL). cThe reaction
was conducted on a 0.5 mmol scale with alkyne (1.1 eq), Pd(PPh3)2Cl2 (10% mmol), CuI
(20% mmol) in Et3N (3 mL).
Also, as versatile building blocks have received much attention, trifluoromethylated
alkynes have found widespread use in medicinal, agrochemical, and material science.24
Therefore, synthesis of trifluoromethylated alkynes via elimination reaction of
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trifluoromethylated alkenyl triflates is put on our schedule. Trifluoromethylated alkenyl
triflate 2d was explored as the model substrate firstly. Preliminary results, using LC
analysis with biphenyl as an internal standard, indicated that polar aprotic solvents such
as DMF, DMSO, NMP gave the desire product in excellent yield with the promotion of
weak bases such as Et3N, NaHCO3 or KHCO3 under mild condition. The solvents, such
as THF, Et2O, toluene etc. were proved to be less effective even totally ineffective unless
the reactions were carried out at high temperature. In addition, the hydrolysis product,
trifluoromethyl ketone, was formed if the solvent was not sufficiently dried. With the
optimal conditions in hand, several substrates were investigated. As depicted in Table 4,
trifluoromethylated alkenyl triflates furnished trifluoromethylated alkynes in excellent
yields. Slightly lower yield of 5e is likely due to its chemical instability.
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Table 4. Elimination Reaction of Alkenyl Triflatesa
b
aReaction conditions: 2 (1.3 mmol), Et3N (1.5 eq), DMF (3 mL) at 30 °C for 12 h. The
reaction was conducted on a 0.51 mmol scale with Et3N (1.5 eq) in DMF (2 mL). cThe
d
reaction was conducted on a 1 mmol scale with Et3N (2.0 eq) in DMF (5 mL). Labile
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compound.
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Furthermore, using 2 and 2-iodophenol with the Pd(OAc)2/X-Phos/Cs2CO3 catalyst
system, we tried the synthesis of 3-trifluoromethylbenzofuran, an essential structural
motifs in biologically active compounds.25 After intensive investigation, as depicted in
Table 5, a series of 3-trifluoromethylbenzofuran compounds were obtained in moderate
yield in one-pot by two steps. According to the reported mechanism of similar
transformation,20e the elimination of 2 affords 1-aryltrifluoropropynes firstly, followed by
Michael-type addition with 2-iodophenol at 1-position of 1-aryltrifluoropropynes, then
the formed vinyl ether intermediates were transferred to the desired products,
3-trifluoromethylbenzofurans (6), via intramolecular Heck cross-coupling reaction.
Table 5. Synthesis of 3-Trifluoromethylbenzofuransa
aReaction conditions: 2 (0.5 mmol), KHCO3 (2.0 eq), DMF (5 mL), 30 °C for 12 h and
then 2-IC6H4OH (1.2 eq), Pd2(dba)3 (10% mmol), (t-Bu)3P (0.8 eq), K2CO3 (5.0 eq) were
added in situ under Ar, at 140 °C for 12 h. b24 h.
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Finally, as mentioned above, the trifluoromethylated alkenyl triflates are extremely
useful precursors and can be used to synthesize a series of bioactive molecules. As shown
in Scheme 1, an intermediate for a new type of pesticides26 was prepared according to our
method. 2r was obtained from ketone 1r with ethyl trifluoroacetate, and then transfer to
3t quantitatively via the Stille coupling. Under the catalysis of
Pd(OAc)2-Xantphos-DMSO in DMF, 3t isomerized to generate 7, from which a series of
compounds with high pesticidal activity can be easily prepared.
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Scheme 1. Synthesis of the intermediate for pesticides
In summary, using ethyl trifluoroacetate as a trifluoromethylation reagent, we
developed an efficient method to afford (Z)-α-trifluoromethyl alkenyl triflates with
excellent stereoselectivity via trifluoroacetic ester/ketone exchange process. Bearing the
biologically important CF3-moiety, easily derived C-C double bond and sulfonate ester
unit, trifluoromethylated alkenyl triflates are important scaffolds, from which diverse
trifluoromethyl derivatives, such as diarylethylenes, enynes, alkynes and benzofurans,
were easily prepared via Stille coupling, Sonogashira coupling, elimination and
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cyclization reactions, respectively. Further studies on the other application of
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(Z)-trifluoromethyl alkenyl triflates are currently underway in our laboratory.
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EXPERIMENTAL SECTION
General method. Unless otherwise noted, all reactions were performed under Ar
atmosphere in oven-dried glassware with magnetic stirring. Anhydrous solvents were
freshly distilled from sodium and benzophenone or calcium hydride. Column
chromatography was performed on silica gel (200−300 mesh) using petroleum ether/
ethyl acetate as an eluent. NMR spectra were recorded in CDCl3 at 400 MHz (1H), 100
MHz or 126 MHz (13C{H}), and 377 MHz or 470 MHz (19F) on a spectrometer.
Chemical shift (δ) were reported in parts per million (ppm) relative to the residual solvent
signal. HRMS (EI) spectra were measured with quadrupole and TOF mass spectrometers.
NaH (60% in mineral oil) was washed with dry n-hexane to remove mineral oil prior to
use. The enolizable ketones were purchased from commercial sources or prepared from
corresponding acetophenone and aldehydes, reduced by Pd/C-catalyzed hydrogenation
according to the literature27 or prepared from corresponding phenylacetic acid and
anisole.28
General procedure for the preparation of trifluoromethylated alkenyl triflates (2).
To a suspension of NaH (240 mg, 10.0 mmol, powder) in MTBE (5 mL) was added
ethyl trifluoroacetate (1.2 mL, 10.0 mmol) at room temperature under Ar atmosphere.
After 1 min of stirring, a solution of enolizable ketone (5.0 mmol) in MTBE (5 mL) was
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added, and the mixture was refluxed for 6-12 h. After reaction completed (monitored by
TLC and GC analysis), the reaction solution was cooled to 0 °C. Tf2O (2.82 g, 10 mmol)
was added dropwise to the reaction mixture. After reaction completion (monitored by
TLC and GC analysis), the reaction was quenched with ice-water. The aqueous layer was
separated and extracted with EtOAc. The combined organic extracts were washed with
brine, dried over MgSO4, and solvent was removed under reduced pressure. The crude
product was purified by column chromatography on silica gel (petroleum ether as eluent)
to afford the trifluoromethanesulfonate products.
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(Z)-1-Phenyl-3,3,3-trifluoroprop-1-en-2-yl trifluoromethanesulfonate (2a). Colorless
oil; yield 75% (1.2 g); 1H NMR (400 MHz, CDCl3) δ 7.60 - 7.58 (m, 2H), 7.47 - 7.45 (m,
13
3H), 7.13 (s, 1H). C{1H}NMR (100 MHz, CDCl3) δ 132.4 (q, J = 38.3 Hz), 131.1,
129.9, 129.1, 128.6, 128.1 (q, J = 3.5 Hz), 119.2 (q, J = 271.0 Hz), 118.3 (q, J = 319.1
Hz). 19F NMR (470 MHz, CDCl3) δ -69.18 (q, J = 5.7 Hz, 3F); -72.99 (q, J = 5.7 Hz, 3F).
HRMS (EI) m/z: calcd for C10H6F6O3S [M+·] 319.9942, found: 319.9944.
(Z)-1-(4-Chlorophenyl)-3,3,3-trifluoroprop-1-en-2-yl trifluoromethanesulfonate (2b).
Colorless oil; yield 65% (7.03 g); 1H NMR (400 MHz, CDCl3) δ 7.54 (d, J = 8.8 Hz, 2H),
7.44 (d, J = 8.8 Hz, 2H), 7.08 (s, 1H). 13C{1H}NMR (100 MHz, CDCl3) δ 137.4, 132.8 (q,
J = 38.5 Hz), 131.1, 129.5, 127.0, 126.9 (q, J = 4.0 Hz), 119.1 (q, J = 271.2 Hz), 118.3 (q,
J = 319.4 Hz). 19F NMR (470 MHz, CDCl3) δ -69.17 (q, J = 5.8 Hz, 3F); -72.69 (q, J =
5.8 Hz, 3F). HRMS (EI) m/z: calcd for C10H5ClF6O3S [M+·] 353.9552, found: 353.9561.
(Z)-1-(3-Chlorophenyl)-3,3,3-trifluoroprop-1-en-2-yl trifluoromethanesulfonate (2c).
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Corlorless oil; yield 74% (1.3 g); H NMR (400 MHz, CDCl3) δ 7.56 (s, 1H), 7.36-7.47
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(m, 3H), 7.08 (s, 1H). 13C{1H}NMR (100 MHz, CDCl3) δ 135.2, 133.4 (q, J = 38.8 Hz),
131.1, 130.4, 130.2, 129.7, 127.8, 126.7 (q, J = 3.6 Hz), 119.0 (q, J = 280.8 Hz), 118.3 (q,
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J = 318.6 Hz). F NMR (470 MHz, CDCl3) δ -69.43 (q, J = 6.0 Hz, 3F); -72.88 (q, J =
6.0 Hz, 3F). HRMS (EI) m/z: calcd for C10H5ClF6O3S [M+·] 353.9552, found: 353.9553.
(Z)-1-(4-Bromophenyl)-3,3,3-trifluoroprop-1-en-2-yl trifluoromethanesulfonate (2d).
Colorless oil; yield 85% (1.7 g); 1H NMR (400 MHz, CDCl3) δ 7.07 (s, 1H), 7.47 (d, J =
8.8 Hz, 2H), 7.61 (d, J = 8.8 Hz, 2H). 13C{1H}NMR (100 MHz, CDCl3) δ 132.8 (q, J =
30.9 Hz), 132.5, 131.2, 127.4, 127.0 (q, J = 2.8 Hz), 125.7, 119.1 (q, J = 217.0 Hz), 118.3
(q, J = 255.5 Hz). 19F NMR (470 MHz, CDCl3) δ -69.24 (q, J = 6.2 Hz, 3F); -72.74 (q, J
= 6.2 Hz, 3F). HRMS (EI) m/z: calcd for C10H5BrF6O3S [M+·] 397.9047, found:
397.9044.
(Z)-1-(2-Bromophenyl)-3,3,3-trifluoroprop-1-en-2-yl trifluoromethanesulfonate (2e).
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White solid; yield 66% (1.31 g); mp 34.0 °C - 34.2 °C. H NMR (400 MHz, CDCl3) δ
7.68 (d, J = 8.0 Hz, 1H), 7.61 (d, J = 7.7 Hz, 1H), 7.41 (m, 1H), 7.37 (s, 1H), 7.32 (m,
1H). 13C{1H}NMR (100 MHz, CDCl3) δ 134.2 (q, J = 39.0 Hz), 133.2, 131.9, 130.6,
129.4, 127.8, 127.4 (q, J = 3.7 Hz), 124.3, 118.9 (q, J = 217.1 Hz), 118.2 (q, J = 255.3
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Hz). F NMR (470 MHz, CDCl3) δ -69.77 ~ -69.72 (m, 3F); -73.22 ~ -73.17 (m, 3F).
HRMS (EI) m/z: calcd for C10H5BrF6O3S [M+·] 397.9047, found: 397.9058.
(Z)-1-(4-Methylphenyl)-3,3,3-trifluoroprop-1-en-2-yl trifluoromethanesulfonate (2f).
Colorless oil; yield 66% (1.1 g); 1H NMR (400 MHz, CDCl3) δ 7.50 (d, J = 8.2 Hz, 2H),
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7.26 (d, J = 8.2 Hz, 2H), 7.08 (s, 1H), 2.40 (s, 3H). 13C{1H}NMR (100 MHz, CDCl3) δ
141.8, 131.6 (q, J = 38.6 Hz), 130.0, 129.9, 128.1 (q, J = 3.6 Hz), 125.7, 119.4 (q, J =
270.8 Hz), 118.4 (q, J = 319.2 Hz), 21.4. 19F NMR (470 MHz, CDCl3) δ -68.97 (q, J = 6.2
Hz, 3F); -72.94 (q, J = 6.2 Hz, 3F). HRMS (EI) m/z: calcd for C11H8F6O3S [M+·]
334.0098, found: 334.0104.
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(Z)-1-(3-Methoxyphenyl)-3,3,3-trifluoroprop-1-en-2-yl
trifluoromethanesulfonate
(2g). Colorless oil; yield 79% (1.37 g); 1H NMR (400 MHz, CDCl3) δ 7.37 (t, J = 8.0 Hz,
1H), 7.21 (d, J = 1.1 Hz, 1H), 7.14 (m, 2H), 7.03 (dd, J = 8.0, 2.4 Hz, 1H), 3.85 (s, 3H).
13C{1H}NMR (100 MHz, CDCl3) δ 160.0, 132.4 (q, J = 38.5 Hz), 130.1, 129.7, 128.1 (q,
J = 3.6 Hz), 122.7, 119.2 (q, J = 270.9 Hz), 118.3 (q, J = 319.2 Hz), 117.7, 114.1, 55.2.
19F NMR (470 MHz, CDCl3) δ -69.31 ~ -69.27 (m, 3F); -73.03 ~ -72.99 (m, 3F). HRMS
(EI) m/z: calcd for C11H8F6O4S [M+·] 350.0048, found: 350.0049.
(Z)-1-(Naphthalen-1-yl)-3,3,3-trifluoroprop-1-en-2-yl trifluoromethanesulfonate (2h).
White solid; yield 65% (1.2 g); mp 53.5 °C - 53.7 °C. 1H NMR (500 MHz, CDCl3) δ 7.89
(d, J = 8.3 Hz, 1H), 7.85 (m, 1H), 7.80 (d, J = 8.0 Hz, 1H), 7.70 (s, 1H), 7.66 (d, J = 7.1
Hz, 1H), 7.51 (m, 3H). 13C{1H}NMR (100 MHz, CDCl3) δ 134.6 (q, J = 38.7 Hz), 133.5,
131.2, 131.1, 128.9, 127.9, 127.4, 126.7, 126.6 (dd, J = 6.8 Hz, 3.3 Hz), 119.2 (q, J =
217.0 Hz), 118.2 (q, J = 255.2 Hz). 19F NMR (470 MHz, CDCl3) δ -69.53 ~ -69.50 (m,
3F); -73.48 ~ -73.43 (m, 3F). HRMS (EI) m/z: calcd for C14H8F6O3S [M+·] 370.0098,
found: 370.0099.
(Z)-1-([1,1'-Biphenyl]-4-yl)-3,3,3-trifluoroprop-1-en-2-yl trifluoromethanesulfonate
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(2i). White solid; yield 53% (210 mg); mp 79.7 °C - 80.2 °C. 1H NMR (400 MHz, CDCl3)
δ 7.71 (s, 4H), 7.64 (d, J = 7.6 Hz, 2H), 7.49 (t, J = 7.5 Hz, 2H), 7.41 (t, J = 7.3 Hz, 1H),
7.17 (s, 1H). 13C{1H}NMR (100 MHz, CDCl3) δ 143.9, 139.6, 132.1 (q, J = 38.6 Hz),
130.5, 129.0, 128.2, 127.8 (q, J = 3.5 Hz), 127.7, 127.3, 127.2, 119.3 (q, J = 271.1 Hz),
118.3 (q, J = 319.4 Hz). 19F NMR (470 MHz, CDCl3) δ -68.83 (q, J = 5.9 Hz, 3F); -72.65
(q, J = 5.9 Hz, 3F). HRMS (EI) m/z: calcd for C16H10F6O3S [M+·] 396.0255, found:
396.0258.
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(Z)-1-(p-Tolylthio)-3,3,3-trifluoroprop-1-en-2-yl trifluoromethanesulfonate (2j).
Colorless oil; yield 93% (1.69 g); 1H NMR (400 MHz, CDCl3) δ 7.39 (d, J = 8.1 Hz, 2H),
7.22 (d, J = 8.1 Hz, 2H), 7.17 (s, 1H), 2.38 (s, 3H). 13C{1H}NMR (100 MHz, CDCl3) δ
140.1, 133.8 (q, J = 3.4 Hz), 132.1, 130.6, 128.5 (q, J = 40.7 Hz), 127.1, 118.6 (q, J =
231.5 Hz), 118.4 (q, J = 239.7 Hz), 21.0. 19F NMR (470 MHz, CDCl3) δ -68.56 (q, J = 4.2
Hz, 3F); -72.95 (q, J = 4.2 Hz, 3F). HRMS (EI) m/z: calcd for C11H8F6O3S2 [M+·]
365.9819, found: 365.9824.
(Z)-1-Phenoxy-3,3,3-trifluoroprop-1-en-2-yl
trifluoromethanesulfonate
(2k).
Colorless oil; yield 92% (1.54 g); 1H NMR (400 MHz, CDCl3) δ 7.35 (m, 3H), 7.21 (t, J
= 7.4 Hz, 1H), 7.07 (d, J = 8.2 Hz, 2H). 13C{1H}NMR (100 MHz, CDCl3) δ 155.8, 142.3
(q, J = 4.5 Hz), 130.2, 125.8, 121.8 (q, J = 40.1 Hz), 119.9 (q, J = 214.6 Hz), 118.6 (q, J
= 254.9 Hz), 117.2. 19F NMR (470 MHz, CDCl3) δ -68.90 (q, J = 3.5 Hz, 3F); -73.32 (q, J
= 3.5 Hz, 3F). HRMS (EI) m/z: calcd for C10H6F6O4S [M+·] 335.9891, found: 335.9883.
(Z)-4-Phenyl-1,1,1-trifluorobut-2-en-2-yl trifluoromethanesulfonate (2l). Colorless oil;
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yield 78% (520 mg); H NMR (400 MHz, CDCl3) δ 7.36-7.19 (m, 5H), 6.49 (t, J = 7.6
Hz, 1H), 3.68 (d, J = 7.5 Hz, 2H). 13C{1H}NMR (100 MHz, CDCl3) δ 135.7, 134.0 (q, J
= 39.4 Hz), 130.0 (q, J = 3.2 Hz), 129.1, 128.5, 127.5, 118.7 (q, J = 289.7 Hz), 118.4 (q, J
= 299.6 Hz), 32.1. 19F NMR (470 MHz, CDCl3) δ -69.95 ~ -69.91 (m, 3F); -72.90 ~
-72.86 (m, 3F). HRMS (EI) m/z: calcd for C11H8F6O3S [M+·] 334.0098, found: 334.0107.
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(Z)-4-(4-Methoxyphenyl)-1,1,1-trifluorobut-2-en-2-yl
trifluoromethanesulfonate
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(2m). Colorless oil; yield 93% (1.68 g); H NMR (400 MHz, CDCl3) δ 7.12 (d, J = 8.6
Hz, 2H), 6.88 (d, J = 8.6 Hz, 2H), 6.47 (t, J = 7.6 Hz, 1H), 3.80 (s, 3H), 3.62 (dd, J = 7.6,
1.6 Hz, 2H). 13C{1H}NMR (100 Hz, CDCl3) δ 159.0, 133.6 (q, J = 39.3 Hz), 129.6, 127.6,
118.7 (q, J = 288.2 Hz), 118.5 (q, J = 300.9 Hz), 114.4, 55.2, 31.3. 19F NMR (470 MHz,
CDCl3) δ -70.01 (q, J = 4.4 Hz, 3F); -73.07 (q, J = 4.4 Hz, 3F). HRMS (EI) m/z: calcd for
C12H10F6O4S [M+·] 364.0204, found: 364.0208.
(Z)-4-(p-Tolyl)-1,1,1-trifluorobut-2-en-2-yl trifluoromethanesulfonate (2n). Colorless
oil; yield 72% (1.25 g); 1H NMR (400 MHz, CDCl3) δ 7.22 (d, J = 7.7 Hz, 2H), 7.16 (d, J
= 7.7 Hz, 2H), 6.54 (t, J = 7.6 Hz, 1H), 3.71 (d, J = 7.6 Hz, 2H), 2.40 (s, 3H).
13C{1H}NMR (100 MHz, CDCl3) δ 137.2, 133.8 (q, J = 39.3 Hz), 132.6, 130.3 (dd, J =
5.9 Hz, 2.8 Hz), 129.8, 128.4, 118.7 (q, J = 230.0 Hz), 118.1 (q, J = 241.4 Hz), 31.8, 20.9.
19F NMR (470 MHz, CDCl3) δ -70.01 (m, 3F); -73.10 ~ -73.04 (m, 3F). HRMS (EI) m/z:
calcd for C12H10F6O3S [M+·] 348.0255, found: 348.0257.
(Z)-4-(3-Chlorophenyl)-1,1,1-trifluorobut-2-en-2-yl trifluoromethanesulfonate (2o).
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Colorless oil; yield 74% (1.36 g); H NMR (400 MHz, CDCl3) δ 7.29 - 7.28 (m, 2H),
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7.22 (s, 1H), 7.13 - 7.10 (m, 1H), 6.48 (t, J = 7.5 Hz, 1H), 3.68 (dd, J = 7.5, 1.6 Hz, 2H).
13C{1H}NMR (100 MHz, CDCl3) δ 137.6, 134.9, 134.4 (q, J = 31.3 Hz), 130.3, 129.0 (q,
J = 3.2 Hz), 128.6, 127.7, 126.6, 118.6 (q, J = 233.4 Hz), 118.4 (q, J = 238.1 Hz), 31.7.
19F NMR (470 MHz, CDCl3) δ -70.15 (m, 3F); -73.06 ~ -73.00 (m, 3F). HRMS (EI) m/z:
calcd for C11H7O3F6ClS [M+·] 367.9709, found: 367.9703.
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(Z)-4-(Furan-2-yl)-1,1,1-trifluorobut-2-en-2-yl
trifluoromethanesulfonate
(2p).
Colorless oil; yield 67% (1.08 g); 1H NMR (400 MHz, CDCl3) δ 7.37 (d, J = 1.6 Hz, 1H),
6.56 (t, J = 7.4 Hz, 1H), 6.34 (dd, J = 2.9, 2.1 Hz, 1H), 6.18 (d, J = 3.2 Hz, 1H), 3.73 (d, J
= 7.4 Hz, 2H). 13C{1H}NMR (100 MHz, CDCl3) δ 148.6, 142.3, 134.6 (q, J = 39.5 Hz),
126.9 (q, J = 2.6 Hz), 118.6 (q, J = 233.5 Hz), 118.4 (q, J = 237.8 Hz), 110.5, 107.2, 25.0.
19F NMR (470 MHz, CDCl3) δ -70.41 (m, 3F); -73.27 ~ -73.24 (m, 3F). HRMS (EI) m/z:
calcd for C9H6F6O4S [M+·] 323.9891, found: 323.9886.
(Z)-1,1,1-Trifluorotridec-2-en-2-yl trifluoromethanesulfonate (2q). Colorless oil; yield
74% (563 mg); 1H NMR (500 MHz, CDCl3) δ 6.25 (t, J = 7.7 Hz, 1H), 2.26 (m, 2H), 1.42
(m, 2H), 1.25 (m, 14H), 0.80 (t, J = 6.9 Hz, 3H). 13C{1H}NMR (100 MHz, CDCl3) δ
133.9 (q, J = 39.1 Hz), 131.2 (q, J = 2.9 Hz), 118.7 (q, J = 228.0 Hz), 118.4 (q, J = 243.0
Hz), 31.8, 29.5, 29.4, 29.2, 29.1, 29.0, 27.7, 26.0, 22.6, 13.8. 19F NMR (470 MHz, CDCl3)
δ -70.27 ~ -70.26 (m, 3F); -73.51 ~ -73.44 (m, 3F). HRMS (EI) m/z: calcd for
C14H22F6O3S [M+·] 384.1194, found: 384.1189.
General procedure for the preparation of trifluoromethylated diarylethylenes (3).
Under Ar atmosphere, a mixture of 2 (0.5 mmol), tributyl tin compound (0.75 mmol),
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Pd(PPh3)2Cl2 (10% mmol), LiCl (20% mmol) in dry Toluene (3 mL) was heated to
100 °C for 6-12 h. After reaction completed (monitored by TLC and GC analysis), the
reaction was quenched with water. The aqueous layer was separated and extracted with
EtOAc. The combined organic extracts were washed with brine, aqueous KF solution,
dried over MgSO4 and solvent was removed under reduced pressure. The crude product
was purified by column chromatography on silica gel to afford the target material.
(E)-1,2-Diphenyl-3,3,3-trifluoroprop-1-ene (3a). Colorless oil; yield 89% (110 mg); 1H
NMR (400 MHz, CDCl3) δ 7.39 - 7.37 (m, 3H), 7.30 - 7.28 (m, 2H), 7.24 - 7.12 (m, 4H),
7.00 (d, J = 7.2 Hz, 2H). 13C{1H}NMR (100 MHz, CDCl3) δ 133.6, 133.2 (q, J = 5.9 Hz),
132.8, 130.3 (q, J = 29.3 Hz), 130.1, 129.9, 129.0, 128.9, 128.8, 128.3, 123.8 (q, J =
271.6 Hz). 19F NMR (377 MHz, CDCl3) δ -66.30. HRMS (EI) m/z: calcd for C15H11F3
[M+·] 248.0813, found: 248.0820. The spectroscopic data correspond to previously
reported date.17b
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(E)-1-Phenyl-2-(4-methylphenyl)-3,3,3-trifluoroprop-1-ene (3b).17c Colorless oil; yield
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84% (110 mg); H NMR (400 MHz, CDCl3) δ 7.25 - 7.20 (m, 8H), 7.08 (d, J = 7.2 Hz,
2H), 2.42 (s, 3H). 13C{1H}NMR (100 MHz, CDCl3) δ 138.7, 133.8, 133.0 (q, J = 5.9 Hz),
130.4 (q, J = 29.3 Hz), 130.1, 129.7, 128.8, 128.3, 124.0 (q, J = 273.2 Hz), 21.4. 19F
NMR (377 MHz, CDCl3) δ -66.32. HRMS (EI) m/z: calcd for C16H13F3 [M+·] 262.0969,
found: 262.0979.
(E)-1-Phenyl-2-(3-methoxylphenyl)-3,3,3-trifluoroprop-1-ene (3c). Colorless oil; yield
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87% (120 mg); H NMR (400 MHz, CDCl3) δ 7.28 (t, J = 7.9 Hz, 1H), 7.20 - 7.13 (m,
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4H), 7.03 (d, J = 7.5 Hz, 2H), 6.93 - 6.84 (m, 3H), 3.73 (s, 3H). 13C{1H}NMR (100 MHz,
CDCl3) δ 160.0, 134.0, 133.6, 133.3 (q, J = 5.9 Hz), 130.1 (q, J = 29.4 Hz), 129.0, 128.4,
123.9 (q, J = 273.3 Hz), 122.3, 115.3, 114.6, 55.2. 19F NMR (377 MHz, CDCl3) δ -66.17.
HRMS (EI) m/z: calcd for C16H13F3O [M+·] 278.0918, found: 278.0923.
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(E)-1-Phenyl-2-(4-methoxylphenyl)-3,3,3-trifluoroprop-1-ene (3d).17c Colorless oil;
yield 87% (120 mg); 1H NMR (400 MHz, CDCl3) δ 7.21 - 7.13 (m, 6H), 7.03 (d, J = 7.5
Hz, 2H), 6.90 (d, J = 8.6 Hz, 2H), 3.80 (s, 3H). 13C{1H}NMR (100 MHz, CDCl3) δ 160.0,
133.8, 133.0 (q, J = 5.8 Hz), 131.2, 130.1, 130.0 (q, J = 29.3 Hz), 128.9, 128.3, 124.8,
124.0 (q, J = 273.2 Hz), 114.5, 55.2. 19F NMR (377 MHz, CDCl3) δ -66.39. HRMS (EI)
m/z: calcd for C16H13F3O [M+·] 278.0918, found: 278.0923.
(E)-1-Phenyl-2-(4-chlorophenyl)-3,3,3-trifluoroprop-1-ene (3e).17c White solid; yield
85% (120 mg); mp 63.1°C - 63.2 °C. 1H NMR (400 MHz, CDCl3) δ 7.36 (d, J = 8.4 Hz,
2H), 7.24 - 7.16 (m, 6H), 7.01 (d, J = 7.8 Hz, 2H). 13C{1H}NMR (100 MHz, CDCl3) δ
135.0, 133.8 (q, J = 5.8 Hz), 133.2, 131.4, 131.1, 130.0, 129.2 (q, J = 20.0 Hz), 129.1,
129.0, 128.4, 123.6 (q, J = 271.6 Hz). 19F NMR (470 MHz, CDCl3) δ -65.79. HRMS (EI)
m/z: calcd for C15H10F3Cl [M+·] 282.0423, found: 282.0426.
(E)-1-Phenyl-2-(4-formylphenyl)-3,3,3-trifluoroprop-1-ene (3f). White solid; yield
1
72% (100 mg); mp 46.9 °C - 47.1°C. H NMR (400 MHz, CDCl3) δ 10.04 (s, 1H), 7.90
(d, J = 8.2 Hz, 2H), 7.48 (d, J = 8.2 Hz, 2H), 7.32 (s, 1H), 7.25 - 7.15 (m, 3H), 7.00 (d, J
= 7.4 Hz, 2H). 13C{1H}NMR (100 MHz, CDCl3) δ 191.7, 139.1, 134.4 (q, J = 5.8 Hz),
132.9, 130.8, 130.2, 130.0, 129.4, 129.0, 128.5, 123.5 (q, J = 273.4 Hz). 19F NMR (470
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MHz, CDCl3) δ -65.24. HRMS (EI) m/z: calcd for C16H11F3O [M+·] 276.0762, found:
276.0772.
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(E)-1-Phenyl-2-allyl-3,3,3-trifluoroprop-1-ene (3g). Colorless oil; yield 100% (106 mg).
1H NMR (400 MHz, CDCl3) δ 7.40 - 7.33 (m, 5H), 7.18 (s, 1H), 5.96 - 5.87 (m, 1H), 5.17
(dd, J = 4.2, 1.5 Hz, 1H), 5.14 (dd, J = 3.1, 1.5 Hz, 1H), 3.16 (d, J = 5.8 Hz, 2H).
13C{1H}NMR (100 MHz, CDCl3) δ 134.2, 134.1, 133.7 (q, J = 6.2 Hz), 129.0, 128.6,
128.5, 128.1, 124.4 (q, J = 241.2 Hz), 116.9, 30.7. 19F NMR (377 MHz, CDCl3) δ -67.02.
HRMS (EI) m/z: calcd for C12H11F3 [M+·] 212.0813, found: 212.0822.
(E)-1-(3-Methoxylphenyl)-2-(4-methoxyphenyl)-3,3,3-trifluoroprop-1-ene
(3h).
1
Colorless oil; yield 98% (150 mg). H NMR (400 MHz, CDCl3) δ 7.22 (d, J = 8.6 Hz,
2H), 7.16 (d, J = 1.4 Hz, 1H), 7.10 (m, 1H), 6.92 (d, J = 8.6 Hz, 2H), 6.76 (dd, J = 8.2,
2.5 Hz, 1H), 6.67 (d, J = 7.6 Hz, 1H), 6.54 (s, 1H), 3.82 (s, 3H), 3.54 (s, 3H).
13C{1H}NMR (100 MHz, CDCl3) δ 159.0, 158.2, 134.0, 131.9 (q, J = 5.7 Hz), 130.1,
129.1 (q, J = 29.3 Hz), 128.2, 123.8, 122.9 (q, J = 273.2 Hz), 121.9, 114.3, 113.4, 54.2,
53.8. 19F NMR (377 MHz, CDCl3) δ -66.55. HRMS (EI) m/z: calcd for C17H15F3O2 [M+·]
308.1024, found: 308.1018.
(E)-1-(4-Chlorophenyl)-2-(4-methoxylphenyl)-3,3,3-trifluoroprop-1-ene
(3i).29
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Colorless oil; yield 90% (140 mg). H NMR (400 MHz, CDCl3) δ 7.17 (d, J = 8.4 Hz,
2H), 7.14 - 7.12 (m, 3H), 6.95 (d, J = 8.4 Hz, 2H), 6.90 (d, J = 8.7 Hz, 2H), 3.81 (s, 3H).
13C{1H}NMR (100 MHz, CDCl3) δ 160.1, 134.7, 132.3, 131.7 (q, J = 5.9 Hz), 131.3,
131.0, 130.7 (q, J = 29.5 Hz), 128.6, 124.3, 123.8 (q, J = 273.3 Hz), 114.6, 55.2. 19F
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NMR (377 MHz, CDCl3) δ -66.56. HRMS (EI) m/z: calcd for C16H12ClF3O [M+·]
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312.0529, found: 312.0536.
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(E)-1-(3-Chlorophenyl)-2-(4-methoxylphenyl)-3,3,3-trifluoroprop-1-ene
(3j).
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Colorless oil; yield 71% (110 mg). H NMR (400 MHz, CDCl3) δ 7.19 - 7.15 (m, 3H),
7.11 (s, 1H), 7.08 - 7.04 (m, 2H), 6.91 - 6.86 (m, 3H), 3.80 (s, 3H). 13C{1H}NMR (100
MHz, CDCl3) δ 160.2, 135.6, 134.2, 131.6 (q, J = 5.9 Hz), 131.5 (q, J = 9.8 Hz), 131.0,
130.0, 129.5, 128.8, 127.9, 124.1, 123.7 (q, J = 273.5 Hz), 114.6, 55.2. 19F NMR (470
MHz, CDCl3) δ -66.19. HRMS (EI) m/z: calcd for C16H12ClF3O [M+·] 312.0529, found:
312.0538.
(E)-1-(4-Methylphenyl)-2-(4-methoxyphenyl)-3,3,3-trifluoroprop-1-ene
(3k).
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Colorless oil; yield 89% (130 mg). H NMR (400 MHz, CDCl3) δ 7.20 (d, J = 8.6 Hz,
2H), 7.15 (s, 1H), 6.98 (d, J = 8.6 Hz, 2H), 6.93 - 6.90 (m, 4H), 3.84 (s, 3H), 2.27 (s, 3H).
13C{1H}NMR (100 MHz, CDCl3) δ 158.9, 137.9, 131.9 (q, J = 5.6 Hz), 130.1, 129.9,
129.0, 128.0 (q, J = 33.6 Hz), 124.0, 123.0 (qd, J = 273.2, 1.5 Hz), 113.4, 54.1, 20.1. 19F
NMR (470 MHz, CDCl3) δ -65.91. HRMS (EI) m/z: calcd for C17H15F3O [M+·] 292.1075,
found: 292.1076.
(E)-1-(4-Phenyl)phenyl-2-(4-methoxylphenyl)-3,3,3-trifluoroprop-1-ene (3l). Pale
yellow soild; yield 100% (190 mg); mp 95.7 °C - 96.1 °C. 1H NMR (400 MHz, CDCl3) δ
7.53 (d, J = 7.4 Hz, 2H), 7.43 - 7.39 (m, 4H), 7.35 - 7.31 (m, 1H), 7.26 - 7.22 (m, 3H),
7.11 (d, J = 8.3 Hz, 2H), 6.94 (d, J = 8.3 Hz, 2H), 3.84 (s, 1H). 13C{1H}NMR (100 MHz,
CDCl3) δ 158.9, 140.4, 139.1, 131.7, 131.5 (q, J = 5.8 Hz), 130.1, 129.5, 128.8 (q, J =
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29.3 Hz), 127.8, 126.6, 125.9, 125.8, 123.8, 122.9 (q, J = 273.2 Hz), 113.5, 54.2.19F
NMR (470 MHz, CDCl3) δ -65.95. HRMS (EI) m/z: calcd for C22H17F3O [M+·] 354.1232,
found: 354.1242.
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(E)-1-Naphthyl-2-(4-methoxylphenyl)-3,3,3-trifluoroprop-1-ene (3m). Yellow soild;
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yield 92% (150 mg); mp 72.1 °C - 72.2 °C. H NMR (400 MHz, CDCl3) δ 8.03 (d, J =
8.3 Hz, 1H), 7.84 (d, J = 9.3 Hz, 2H), 7.71 (d, J = 8.2 Hz, 1H), 7.59 - 7.50 (m, 2H), 7.22 -
7.18 (m, 1H), 7.12 (d, J = 8.7 Hz, 2H), 7.03 (d, J = 7.2 Hz, 1H), 6.73 (d, J = 8.7 Hz, 2H),
3.74 (s, 3H). 13C{1H}NMR (100 MHz, CDCl3) δ 159.6, 133.4, 132.6 (q, J = 29.0 Hz),
131.9, 131.4 (q, J = 6.0 Hz), 131.3, 131.1, 128.7, 128.6, 127.9, 126.6, 126.2, 125.2, 124.5,
124.0 (q, J = 273.7 Hz), 113.9, 55.1. 19F NMR (470 MHz, CDCl3) δ -65.03. HRMS (EI)
m/z: calcd for C20H15F3O [M+·] 328.1075, found: 328.1074.
(E)-4-Phenyl-2-(4-methoxylphenyl)-1,1,1-trifluorobut-2-ene (3n). Colorless oil; yield
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68% (596 mg). H NMR (400 MHz, CDCl3) δ 7.31 - 7.28 (m, 2H), 7.24 - 7.20 (m, 3H),
7.11 (d, J = 7.2 Hz, 2H), 6.95 (d, J = 8.7 Hz, 2H), 6.57 (td, J = 7.6, 1.6 Hz,1H), 3.83 (s,
3H), 3.35 (dd, J = 7.6, 1.9 Hz, 2H). 13C{1H}NMR (100 MHz, CDCl3) δ 159.8, 138.6,
134.6 (q, J = 5.5 Hz), 131.5 (q, J = 29.5 Hz), 131.0, 128.8, 128.4, 126.6, 124.1, 123.6 (q,
J = 273.0 Hz), 114.0, 55.3, 34.5. 19F NMR (377 MHz, CDCl3) δ -66.38. HRMS (EI) m/z:
calcd for C17H15F3O [M+·] 292.1075, found: 292.1083.
(E)-2-(4-Methoxylphenyl)-1,1,1-trifluorotridec-2-ene (3o). Colorless oil; yield 65%
1
(110 mg). H NMR (400 MHz, CDCl3) δ 7.16 (d, J = 8.5 Hz, 2H), 6.92 (d, J = 8.5 Hz,
2H), 6.39 (t, J = 7.5 Hz, 1H), 3.82 (s, 3H), 2.03 - 1.98 (m, 2H), 1.40 - 1.23 (m, 16H), 0.89
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(t, J = 6.7 Hz, 3H). 13C{1H}NMR (100 MHz, CDCl3) δ 159.5, 136.7 (q, J = 5.4 Hz),
130.9, 130.6 (q, J = 29.2 Hz), 124.7, 113.8, 55.2, 31.9, 29.6, 29.5, 29.3, 29.1, 28.8, 28.3,
22.7, 14.1. 19F NMR (377 MHz, CDCl3) δ -66.26. HRMS (EI) m/z: calcd for C20H29F3O
[M+·] 342.2171, found: 342.2169.
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(E)-1-(4-Chlorophenyl)-2-(3-methoxylphenyl)-3,3,3-trifluoroprop-1-ene
(3p).
1
Colorless oil; yield 84% (130 mg). H NMR (400 MHz, CDCl3) δ 7.33 - 7.29 (m, 1H),
7.15 - 7.13 (m, 3H), 6.97 - 6.93 (m, 3H), 6.85 - 6.81 (m, 2H), 3.77 (s, 3H). 13C{1H}NMR
(100 MHz, CDCl3) δ 159.0, 133.8, 132.5, 130.9, 130.8 (q, J = 5.9 Hz), 130.2, 129.7 (q, J
= 29.5 Hz), 129.2, 127.5, 122.6 (q, J = 273.3 Hz), 121.0, 114.2, 113.5, 54.1.19F NMR
(470 MHz, CDCl3) δ -66.43. HRMS (EI) m/z: calcd for C16H12F3OCl [M+·] 312.0529,
found: 312.0533.
(E)-1-(4-Chlorophenyl)-2-(4-methylphenyl)-3,3,3-trifluoroprop-1-ene (3q). White
solid; yield 95% (800 mg); mp 56.2 °C - 56.4 °C. 1H NMR (400 MHz, CDCl3) δ 7.20 (d,
J = 8.0 Hz, 2H), 7.16 - 7.13 (m, 5H), 6.95 (d, J = 8.0 Hz, 2H), 2.39 (s, 3H). 13C{1H}NMR
(100 MHz, CDCl3) δ 139.0, 134.8, 132.3, 131.7 (q, J = 5.9 Hz), 131.3, 131.1 (q, J = 29.5
Hz), 129.9, 129.6, 129.3, 128.6, 123.8 (q, J = 273.3 Hz), 21.3. 19F NMR (470 MHz,
CDCl3) δ -65.98. HRMS (EI) m/z: calcd for C16H12F3Cl [M+·] 296.0580, found: 296.0582.
(E)-1-(4-Methylphenyl)-2-(3-methoxylphenyl)-3,3,3-trifluoroprop-1-ene
(3r).
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Colorless oil; yield 76% (110 mg). H NMR (400 MHz, CDCl3) δ 7.32-7.28 (m, 1H),
7.17 (d, J = 1.5 Hz, 1H), 6.98 - 6.92 (m, 5H), 6.88 - 6.84 (m, 2H), 3.77 (s, 3H), 2.27 (s,
3H). 13C{1H}NMR (100 MHz, CDCl3) δ 160.0, 139.2, 134.3, 133.1 (q, J = 5.9 Hz), 130.7,
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130.1, 129.1 (d, J = 22.3 Hz), 123.9 (q, J = 273.1 Hz), 115.3, 114.4, 55.2, 21.2.19F NMR
(470 MHz, CDCl3) δ -66.13. HRMS (EI) m/z: calcd for C17H15OF3 [M+·] 292.1075, found:
292.1078.
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(E)-1-(4-Methylphenyl)-2-phenyl-3,3,3-trifluoroprop-1-ene (3s). Colorless oil; yield
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78% (102 mg). H NMR (400 MHz, CDCl3) δ 7.40 - 7.39 (m, 3H), 7.31 - 7.28 (m, 2H),
7.18 (s, 1H), 6.96 (d, J = 8.1 Hz, 2H), 6.89 (d, J = 8.1 Hz, 2H), 2.26 (s, 3H).
13C{1H}NMR (100 MHz, CDCl3) δ 139.2, 133.1 (q, J = 5.9 Hz), 133.0, 130.7, 130.1,
130.0, 129.3 (q, J = 29.2 Hz), 129.1, 129.0, 128.7, 124.0 (q, J = 273.1 Hz), 21.3.19F NMR
(470 MHz, CDCl3) δ -65.63. HRMS (EI) m/z: calcd for C16H13F3 [M+·] 262.0969, found:
262.0973. The spectroscopic data correspond to previously reported date.30
General procedure for the preparation of trifluoromethylated enynes (4).
Under Ar atmosphere, a solution of 2 (1.25 mmol or 2.5 mmol), alkyne (1.1 eq),
Pd(PPh3)2Cl2 (10% mmol), CuI (20% mmol), Et3N (3.0 eq) in dry THF (5 mL) at room
temperature for 12 h. After reaction completed (monitored by TLC), the reaction was
quenched with water. The aqueous layer was separated and extracted with EtOAc. The
combined organic extracts were washed with brine, dried over MgSO4 and solvent was
removed under reduced pressure. The crude product was purified by column
chromatography on silica gel to afford the target material.
(E)-1-(4-Bromophenyl)-4-phenyl-2-trifluoromethylbut-1-en-3-yne (4a). Yellow soild;
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Yield 77% (336 mg); mp 72.3 °C - 72.7 °C. H NMR (400 MHz, CDCl3) δ 7.84 (d, J =
8.5 Hz, 2H), 7.57 (d, J = 8.5 Hz, 2H), 7.53 - 7.50 (m, 2H), 7.40 - 7.36 (m, 3H), 7.20 (s,
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1H). 13C{1H}NMR (100 MHz, CDCl3) δ 136.9 (q, J = 4.7 Hz), 132.4, 131.9, 131.7, 131.1,
129.5, 128.6, 124.7, 122.4 (q, J = 273.5 Hz), 121.0, 112.7 (q, J = 33.7 Hz), 99.5, 81.9. 19F
NMR (470 MHz, CDCl3) δ -65.75. HRMS (EI) m/z: calcd for C17H10F3Br [M+·] 349.9918,
found: 349.9916.
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(E)-1-(4-Bromophenyl)-4-(4-methylphenyl)-2-trifluoromethylbut-1-en-3-yne
(4b).
Yellow soild; yield 91% (830 mg); mp 70.6 °C - 71.0 °C. 1H NMR (400 MHz, CDCl3) δ
7.84 (d, J = 8.5 Hz, 2H), 7.56 (d, J = 8.5 Hz, 2H), 7.41 (d, J = 8.1 Hz, 2H), 7.19 (d, J =
8.1 Hz, 2H), 7.18 (s, 1H), 2.39 (s, 3H). 13C{1H}NMR (100 MHz, CDCl3) δ 139.9, 136.4
(q, J = 4.8 Hz), 132.5, 131.8, 131.7, 131.1, 129.4, 124.6, 122.4 (q, J = 273.7 Hz), 118.9,
112.8 (q, J = 33.7 Hz), 99.9, 81.5 (q, J = 1.4 Hz), 21.6. 19F NMR (470 MHz, CDCl3) δ
-65.76. HRMS (EI) m/z: calcd for C18H12BrF3 [M+·] 364.0074, found: 364.0068.
(E)-1-(4-Bromophenyl)-4-(3-methylphenyl)-2-trifluoromethylbut-1-en-3-yne
(4c).
Yellow soild; yield 81% (372 mg); mp 60.1 °C - 60.4 °C. 1H NMR (400 MHz, CDCl3) δ
7.85 (d, J = 8.6 Hz, 2H), 7.57 (d, J = 8.6 Hz, 2H), 7.34 - 7.28 (m, 3H), 7.23 - 7.20 (m,
2H), 2.37 (s, 3H). 13C{1H}NMR (100 MHz, CDCl3) δ 138.4, 136.6 (q, J = 4.7 Hz), 132.5,
132.2, 131.9, 131.1, 130.4, 128.9, 128.5, 124.7, 122.4 (q, J = 273.7 Hz), 121.7, 112.7 (q,
J = 33.8 Hz), 99.8, 81.6, 21.2. 19F NMR (470 MHz, CDCl3) δ -65.77. HRMS (EI) m/z:
calcd for C18H12BrF3 [M+·] 364.0074, found: 364.0063.
(E)-1-(4-Bromophenyl)-4-(4-chlorophenyl)-2-trifluoromethylbut-1-en-3-yne (4d).
Yellow soild; yield 80% (385 mg); mp 88.9 °C - 89.3 °C.1H NMR (400 MHz, CDCl3) δ
7.81 (d, J = 8.5 Hz, 2H), 7.58 (d, J = 8.5 Hz, 2H), 7.45 (d, J = 8.5 Hz, 2H), 7.37 (d, J =
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8.5 Hz, 2H), 7.23 (s, 1H). 13C{1H}NMR (100 MHz, CDCl3) δ 137.3 (q, J = 4.8 Hz), 135.7,
132.9, 132.3, 131.9, 131.1, 129.0, 124.9, 122.3 (q, J = 273.7 Hz), 120.3, 112.4 (q, J =
34.0 Hz), 98.1, 82.8 (q, J = 1.4 Hz). 19F NMR (470 MHz, CDCl3) δ -65.70. HRMS (EI)
m/z: calcd for C17H9BrClF3 [M+·] 383.9528, found: 383.9529.
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(E)-1-(4-Bromophenyl)-4-(4-methoxylphenyl)-2-trifluoromethylbut-1-en-3-yne (4e).
Yellow soild; yield 91% (403 mg); mp 72.3 °C - 72.7 °C.1H NMR (400 MHz, CDCl3) δ
7.84 (d, J = 8.5 Hz, 2H), 7.56 (d, J = 8.5 Hz, 2H), 7.46 (d, J = 8.9 Hz, 2H), 7.16 (s, 1H),
6.91 (d, J = 8.9 Hz, 2H), 3.85 (s, 3H). 13C{1H}NMR (100 MHz, CDCl3) δ 160.7, 135.9 (q,
J = 4.8 Hz), 133.3, 132.6, 131.8, 131.1, 124.5, 122.5 (q, J = 273.7 Hz), 114.3, 113.9,
112.8 (q, J = 33.6 Hz), 100.0, 81.1 (q, J = 1.4 Hz), 55.3. 19F NMR (470 MHz, CDCl3) δ
-65.78. HRMS (EI) m/z: calcd for C18H12BrF3O [M+·] 380.0024, found: 380.0032.
(E)-1-(4-Bromophenyl)-4-(3-aminophenyl)-2-trifluoromethylbut-1-en-3-yne
(4f).
Yellow soild; yield 81% (372 mg); mp 96.7 °C - 97.0 °C.1H NMR (400 MHz, CDCl3) δ
7.81 (d, J = 8.5 Hz, 2H), 7.54 (d, J = 8.5 Hz, 2H), 7.17 - 7.13 (m, 2H), 6.91 (d, J = 7.5 Hz,
1H), 6.80 (s, 1H), 6.70 (d, J = 7.5 Hz, 1H), 3.72 (s, 2H). 13C{1H}NMR (100 MHz, CDCl3)
δ 146.5, 136.7 (q, J = 4.7 Hz), 132.4, 131.9, 131.2, 129.6, 124.7, 122.5, 122.4 (q, J =
273.8 Hz), 122.1, 117.6, 116.5, 112.6 (q, J = 33.8 Hz), 99.9, 81.3 (q, J = 1.2 Hz).19F
NMR (470 MHz, CDCl3) δ -65.76. HRMS (EI) m/z: calcd for C17H11BrF3N [M+·]
365.0027, found: 365.0030.
(E)-1-(4-Bromophenyl)-2-trifluoromethyloct-1-en-3-yne (4g). Colorless oil; yield 90%
1
(745 mg). H NMR (400 MHz, CDCl3) δ 7.76 (d, J = 8.6 Hz, 2H), 7.49 (d, J = 8.6 Hz,
ACS Paragon Plus Environment