Fluoroalkenylation of boronic acids: Via an oxidative Heck reaction

Article abstract of DOI:10.1039/c9ob00332k

A fluoroalkenylation of boronic acids with fluoroalkyl alkenes has been developed. The Pd-catalyzed oxidative Heck coupling reaction proceeds under an oxygen atmosphere at room temperature, in the absence of a base and/or a ligand, showing excellent practicality of the process. This simple transformation is highly stereoselective to provide only E-isomers. In addition to the general approach using alkenes with functionalized fluoroalkyl reagents, this method, by transferring an aromatic system to the electron-deficient fluoroalkyl alkene, provides an efficient alternative method to yield valuable organofluorines.

Full text of DOI:10.1039/c9ob00332k

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Takeharu Haino et al.
Solvent-induced emission of organogels based on tris(phenylisoxazolyl)
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DOI: 10.1039/C9OB00332K
ARTICLE
Fluoroalkenylation of boronic acids via oxidative Heck reaction
Da Seul Lee and Eun Jin Cho*
Received 00th January 20xx,
Accepted 00th January 20xx
A fluoroalkenylation of boronic acids with fluoroalkyl alkenes has been developed. The Pd-catalyzed oxidative Heck
coupling reaction proceeds under oxygen atmosphere at room temperature, in the absence of base and/or ligand, showing
excellent practicality of the process. This simple transformation is highly stereoselective to provide only E-isomers. In
addition to the general approach using alkenes with functionalized fluoroalkyl reagents, this method, transferring aromatic
system into the electron-deficient fluoroalkyl alkene, provides an efficient alternative way to yield valuable
organofluorines.
DOI: 10.1039/x0xx00000x
reactions using aryl halide or diarylazonium salt as the coupling
partner (Scheme 1b).7 However, these reactions also require
base additives and high temperature. In this backdrop, herein,
Introduction
Fluoroalkylated compounds possess unique characteristics
such as high lipophilicity, bioavailability, and metabolic stability
compared to their non-fluoroalkylated analogues.1 Therefore,
we report a mild and efficient fluoroalkenylation reaction of
arylboronic acid with RF-alkene using the oxidative Heck
coupling process8 (Scheme 1c). This reaction has several
advantages over the previous methods. It uses molecular
oxygen as the oxidant9 and easily available arylboronic acids as
the precursor,10 and can be carried out at room temperature
under ligand-, and base-free conditions. In addition, the
process is highly stereoselective, leading to the formation of
only the E-isomer.
a
wide range of fluoroalkylation reactions have been
developed. The synthesis of fluoroalkylated alkenes, in
particular, has been of great interest.2 The fluoroalkenyl motif
is present in a variety of functional molecules, including
pharmaceuticals. Fluoroalkenyl molecules also serve as
versatile synthetic building blocks owing to the high reactivity
of the unsaturated alkenyl moiety towards a variety of organic
transformations.
Synthesis of fluoroalkylated alkenes has been reported
through many methods. Pd- or Cu-catalyzed traditional
coupling reactions utilized functionalized alkenyl precursors
such as organotin compounds or carboxylic acids with
fluoroalkyl reagents to generate fluoroalkylated alkene
complexes (Scheme 1a).3 Likewise, synthetic protocols for the
reaction of unfunctionalized, simple alkenes with fluoroalkyl
halides have also been developed.4 However, these reactions
require high temperature and use of base or/and ligand
additives. Recent advances in visible light photocatalysis of
unactivated alkenes in the presence of metal- or organo-
photosensitizers enabled the reactions to be carried out under
much milder conditions. However, many of these processes
still require the use of additives such as sacrificial electron
donors or acceptors.5,6
In this regard, the approach using fluoroalkyl alkene (RF-
alkene) instead of activated fluoroalkyl reagent under the mild
conditions is an efficient alternative. There are Pd-catalyzed
Department of Chemistry, Chung-Ang University 84 Heukseok-ro, Dongjak-gu
Seoul 06974, Republic of Korea. E-mail: ejcho@cau.ac.kr
Electronic Supplementary Information (ESI) available: Experimental Procedure,
Characterization data, and NMR spectra (1H, 13C, 19F) of the synthesized
compounds. See DOI: 10.1039/x0xx00000x
Scheme 1. Synthesis of fluoroalkylated alkenes with (a) various fluoroalkyl
reagent and (b) fluoroalkyl alkene, and (c) our strategy.
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none of them showed better reactivity than DMA. Further
screening was performed which showed the best reactivity at
Results and discussion
We began the investigation for the synthesis of
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DOI: 10.1039/C9OB00332K
0.1 M concentration (entries 14 & 15) and the stoichiometry of
2a and Pd(OAc)2 was optimized to 1.2 equiv and 5 mol%,
respectively (entries 16-21). Notably, the optimized reaction
conditions showed that the process is highly practical and mild,
using only molecular oxygen in the presence of Pd(OAc)2, at
room temperature.
fluoroalkenylated compound using phenylboronic acid (1a
)
and nonafluorobutyl ethylene (2a) as model substrates (Table
1). The use of Pd(OAc)2 provided the desired E-selective 3aa in
oxygen-saturated N,N-dimethylacetamide (DMA) solution in
71% yield (entry 1). The oxidative Heck coupling gave
significantly better reactivity with Pd(II) catalyst (entry 1) than
Pd(0) and other transition-metal complexes such as Cu(OAc)2,
which showed very low reactivity, or Ni(OAc)2 which did not
With the optimized conditions in hand, we investigated the
substrate scope of the transformation using different boronic
acid derivatives (
1
) and RF-alkenes (
2) to synthesize a variety of
show any reactivity (entries 2–4). Interestingly, the use of the
fluoroalkenylated compounds (
3
) (Table 2). Regardless of the
ligands, 2,2’-bipyridine and 1,10-phenanthroline (entries 5 & 6),
and increased reaction temperature (entry 7) considerably
lowered the reactivity. A control experiment under argon
atmosphere after freeze-pump-thaw degassing process, clearly
demonstrated the role of molecular oxygen as an oxidant for
the reaction (entry 8). Subsequently, different solvents such as
electron-density on boronic acids, the reactions showed
similar reactivity. Use of substrates with both electron-
donating substituents such as p-tert-butyl (1b), o-methoxy (1c),
p-methoxy (1d), and 3,5-dimethyl (1e) groups and electron-
withdrawing substituents such as p-nitro (1f), m-chloro (1g), p-
chloro (1h), and acetyl (1i) groups led to the formation of the
N,N-dimethylforamide
(DMF),
acetonitrile
(CH3CN),
corresponding coupled products (
Polycyclic aromatic derivatives such as naphthyl
3
) in moderate to good yields.
1j),
dimethylsulfoxide (DMSO), dichloromethane (DCM) and 2,2,2-
trifluoroethanol (TFE) were screened (entries 9-13). However,
(
phenanthrenyl (1k), and pyrenyl (1l) were also suitable
substrates, but the reaction in these cases required the use of
a ligand and higher temperature to improve the reaction
efficiency. In general, along with the desired cross-coupled
Table 1. Optimization for fluoroalkenylation of boronic acidsa
compound 3, diaryl compound, formed by homo-coupling of
the boronic acid, was also produced as a side product. In
addition, benzene derivatives, generated from the boronic acid
substrate, were also detected as minor side products. With
regards to the fluoroalkyl alkene partner, C6F13- (2b) and C8F17-
(
2c) alkenes worked as well as C4F9-ethylene (2a).11 Moreover,
the transformation was amenable to gram-scale synthesis
under the optimized reaction conditions, where product 3aa
was prepared on a 10 mmol scale with a yield similar to that of
the 0.7 mmol scale reaction (Scheme 2).
The reaction was selective with unsubstituted
perfluoroalkylated alkenes. Resubjection of isolated 3aa did
not provide the second Heck product and gave only
homocoupling product of 1a with mostly recovered 3aa
(Scheme 3).
Difluoroalkenylation of 1,4-benzenediboronic acid
(1m),
which has two reaction sites, was also tried, but it furnished
the di-coupled product (3ma) in only 15% yield along with
several side products (Scheme 4a). On the other hand, the
reaction of 4-bromo-3,3,4,4-tetrafluoro-1-butene (2d), which
has two different functional reaction sites (alkenyl vs bromide),
afforded the Heck product (3ad) in 43% yield without
formation of the Suzuki product (3ad’), indicating that the
Heck coupling preferentially proceed over Suzuki coupling
under the conditions (Scheme 4b).
Vinyl boronic acid derivatives were not suitable substrates for
the transformation. Reactions of (E)-styrylboronic acid (1n
and 1-phenylvinyl boronic acid (1o) did not proceed well under
the conditions to give homo-coupled products, and 7,
)
6
respectively, along with trace amount of the Heck product
(Scheme 5).
aAll the reactions were carried out on a 0.1 mmol scale. bYields were determined
The use of the boronic acid moiety was found to be essential
for this transformation; consequently, the transformation did
by 19F NMR spectrometry using
α,α,α -trifluorotoluene as the internal standard.
cDegassed by freeze-pump-thaw cycling.
2 | J. Name., 2012, 00, 1-3
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Table 2. Substrate scope for fluoroalkenylation of boronic acids.a
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DOI: 10.1039/C9OB00332K
a All reactions were carried out on a 0.7 mmol scale. b Isolated yield or 19F NMR yields (using
α,α,α-trifluorotoluene as the internal standard) owing to the volatility of
the products. cThe reaction of 1f was conducted in the presence of 3 mol% 2,2’-bipyridine at 80 °C. dThe reactions of 1j
, 1k, and 1l were conducted in the presence of
3 mol% 1,10-phenanthroline at 80 °C.
syn orientation, to produce the reaction intermediate
stereoselective manner. Subsequent -hydride elimination in
results in the desired E-stereoselective fluoroalkenylated
compound and the Pd(II) hydride complex . Reductive
elimination of generates Pd(0), which is oxidized by
B, in a
β
B
3
C
C
molecular oxygen9 to regenerate Pd(II) species. Hydrogen
peroxide is formed during the oxidation, which was proved by
using hydrogen peroxide determination strip.
Scheme 2. Gram-scale reaction of 1a and 2a.
Scheme 3. Reaction of 3aa for the second Heck reaction.
not proceed when the less Lewis acidic phenylboronic ester (9)
was used.12 In addition, the reactions of chloro- (10), bromo-
(11), and iodobenzene (12) did not provide the cross-coupled
product 3aa, which further proved that halogens are not
suitable precursors for this transformation (Scheme 6).7b
The proposed mechanism for the fluoroalkenylation of
arylboronic acids with fluoroalkyl alkenes is shown in Scheme 7.
The cycle begins with transmetalation between boronic acid
and Pd(OAc)2. The Pd complex then forms a -complex with
alkene and the alkene inserts itself in the Pd-C bond, in the
1
Scheme 4. Reactions of (a) 1,4-benzenediboronic acid (1m) and (b) 4-bromo-3,3,4,4-
tetrafluoro-1-butene (2d).

2
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catalyzed oxidative Heck reaction, which proceeds at room
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DOI: 10.1039/C9OB00332K
temperature under ligand- and base-free conditions. In
addition, the reaction is highly stereoselective to provide only
E-isomers.
Experimental
General reagent information
Palladium acetate and N,N-dimethylacetamide (DMA) were
purchased from Sigma-Aldrich chemical company. Fluoroalkyl
ethylenes and commercially available boronic acid derivatives
were purchased from Sigma-Aldrich, Alfa Aesar, TCI, Combi-
Blocks, or Ark pharm companies. Flash column
chromatography was performed using ZEOCHEM ZEOprep
silicagel 60 (60-200 mesh).
General analytical information
Scheme 5. Reactions with vinylboronic acids
The synthesized fluoroalkenylated compounds were
characterized by 1H NMR, 13C NMR, 19F NMR, and FT-IR
spectroscopy. NMR spectra were recorded on a Varian 600
1
MHz instrument (600 MHz for H NMR, 151 MHz for 13C NMR,
and 564 MHz for 19F NMR). Copies of H, 13C, and 19F NMR
1
spectra can be found at the end of the Supporting Information.
1H NMR experiments are reported in units, parts per million
(ppm), and were measured relative to residual chloroform
(7.26 ppm) or acetone (2.09 ppm) in the deuterated solvent.
13C NMR spectra are reported in ppm relative to
deuterochloroform (77.23 ppm) or deuterated acetone
1
(205.87 ppm), and all were obtained with H decoupling. 19F
NMR spectra are reported in ppm, and all were taken
composite pulse decoupling (CPD) mode. Coupling constants
were reported in Hz. FT-IR spectra were recorded on a Nicolet
6700 Thermo Scientific FT-IR spectrometer. Reactions were
monitored by 19F NMR spectrometry and thin layer
chromatography. Mass spectral data of all unknown
compounds were obtained from the Korea Basic Science
Institute (Daegu) on a Jeol JMS 700 high resolution mass
spectrometer.
Scheme 6. Unsuccessful fluoroalkenylation with other precursors
Experimental Procedure
Synthesis of Fluoroalkenylated Compound (3)
An oven-dried reaction flask equipped with a magnetic stir bar
was charged with boronic acid derivative
1 (0.7 mmol) and 3–6
mol% of Pd(OAc)2 in DMA (7 mL). Molecular oxygen was
bubbled through the reaction mixture for 2 min, and then
fluoroalkyl alkene
2 (0.84 mmol) was added, and it was
allowed to stir for 12–15 h at room temperature. The reaction
progress was monitored by thin layer chromatography or 19F
NMR spectroscopy. After completion, the mixture solution was
concentrated using a rotary evaporator (carefully evaporated
using a vacuum controller owing to the volatility of the
fluoroalkenylated product) and purified using silica gel flash
column chromatography using petroleum ether as the eluent
Scheme 7. Proposed mechanism.
to afford the corresponding fluoroalkenylated compound 3.
Conclusions
In summary, we developed a mild and efficient method for
fluoroalkenylation of arylboronic acid derivatives through a Pd-
Analytic Data for Fluoroalkenylated Compound (3)
4 | J. Name., 2012, 00, 1-3
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(E)-(6,6,6,6,6,6,6,6,6-nonafluoro-6λ12-hexa-1-en-3,5-diyn-1-
yl)benzene, 3aa3i: colorless oil; 1H NMR (600 MHz, CDCl3)
9H); 13C NMR (151 MHz, CDCl3) δ 153.97, 139.73 (t, J = 9.3 Hz),
131.07, 127.70, 126.16, 113.68 (t, J = 22.9 Hz), 35.09, 31.37
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DOI: 10.1039/C9OB00332K
δ
7.50 – 7.46 (m, 2H), 7.44 – 7.38 (m, 3H), 7.18 (dt, J = 16.1, 2.3 (carbon peaks of –C8F17 are omitted due to complicated C-F
Hz, 1H), 6.21 (dt, J = 16.1, 12.3 Hz, 1H).; 13C NMR (151 MHz, splitting); 19F NMR (564 MHz, CDCl3) δ -80.89 (3F), -110.98 (2F),
CDCl3) δ 140.01 (t, J = 10.1 Hz), 133.77, 130.42, 129.19, 127.87, -121.42 (2F), -121.98 (m, 4F), -122.77 (2F), -123.29 (2F), -
114.48 (t, J = 23.0 Hz). (carbon peaks of –C4F9 are omitted due 126.19 (2F); IR (neat): νmax = 3035, 2968, 1657, 1241, 1209,
to complicated C-F splitting); 19F NMR (564 MHz, CDCl3) δ - 974, 816 cm-1; Rf 0.73 (Petroleum ether).
81.06 (3F), -111.35 (2F), -124.14 (2F), -125.73 (2F); IR (neat)
:
(E)-1-methoxy-2-(6,6,6,6,6,6,6,6,6-nonafluoro-6λ12-hexa-1-
νmax = 2969, 1677, 1239, 1204, 973 cm-1; Rf 0.42 (Petroleum en-3,5-diyn-1-yl)benzene, 3ca13: colorless oil; 1H NMR (600
ether).
(E)-(8,8,8,8,8,8,8,8,8,8,8,8,8-tridecafluoro-8λ16-octa-1-en-
MHz, CDCl3) δ 7.47 - 7.44 (m, 2H), 7.36 (dd, J = 7.6, 7.5 Hz, 1H),
6.98 (dd, J = 8.3, 7.6 Hz, 1H), 6.93 (d, J = 8.3 Hz, 1H), 6.33 (dt, J
3,5,7-triyn-1-yl)benzene, 3ab3i: colorless oil; 1H NMR (600 MHz, = 16.1, 12.6 Hz, 1H), 3.89 (s, 3H); 13C NMR (151 MHz, CDCl3)
δ
CDCl3) δ 7.51 - 7.47 (m, 2H), 7.44 - 7.39 (m, 3H), 7.19 (dt, J = 158.21, 135.40 (t, J = 9.4 Hz), 131.53, 128.98, 122.74, 120.96,
16.1, 2.1 Hz, 1H), 6.22 (dt, J = 16.1, 12.4 Hz, 1H); 13C NMR (151 114.95 (t, J = 23.1 Hz), 111.41, 55.73 (carbon peaks of –C4F9 are
MHz, CDCl3) δ 140.00 (t, J = 9.6 Hz), 133.84, 130.42, 129.20, omitted due to complicated C-F splitting); 19F NMR (564 MHz,
127.88, 114.63 (t, J = 23.1 Hz) (carbon peaks of –C6F13 are CDCl3) δ -81.06 (3F), -111.19 (2F), -124.12 (2F), -125.70 (2F); IR
omitted due to complicated C-F splitting); 19F NMR (564 MHz, (neat): νmax = 2925, 1620, 1234, 913, 745 cm-1; Rf 0.71
CDCl3) δ -80.99 (3F), -111.22 (2F), -121.69 (2F), -122.95 (2F), - (Petroleum ether/Ether, 8/1).
123.33 (2F), -126.28 (2F); IR (neat): νmax = 3034, 1658, 1240,
1200, 973 cm-1; Rf 0.38 (Petroleum ether).
(E)-(10,10,10,10,10,10,10,10,10,10,10,10,10-tridecafluoro-
(E)-1-methoxy-3-(6,6,6,6,6,6,6,6,6-nonafluoro-6λ12-hexa-1-
en-3,5-diyn-1-yl)benzene, 3da13: colorless oil; 1H NMR (600
MHz, CDCl3) δ 7.32 (dd, J = 8.1, 7.7 Hz, 1H), 7.15 (d, J = 16.1 Hz,
10λ16-deca-1-en-3,5,7,9-tetrayn-1-yl)benzene, 3ac3i: colorless 1H), 7.07 (d, J = 7.7 Hz, 1H), 6.99 (s, 1H), 6.95 (d, J = 8.1 Hz, 1H),
oil; 1H NMR (600 MHz, CDCl3) δ 7.51 – 7.46 (m, 2H), 7.44 – 6.19 (dt, J = 16.1, 12.3 Hz, 1H), 3.84 (s, 3H); 13C NMR (151 MHz,
7.38 (m, 3H), 7.19 (d, J = 16.0 Hz, 1H), 6.20 (dt, J = 16.0, 12.3 Hz, CDCl3) δ 160.23, 139.96 (t, J = 9.5 Hz), 135.12, 130.22, 120.43,
1H); 13C NMR (151 MHz, CDCl3) δ 139.97 (t, J = 9.3 Hz), 133.82, 116.09, 114.78 (t, J = 23.1 Hz), 113.10, 55.57 (carbon peaks of
130.41, 129.19, 127.87, 114.63 (t, J = 23.1 Hz) (carbon peaks of –C4F9 are omitted due to complicated C-F splitting); 19F NMR
–C8F17 are omitted due to complicated C-F splitting); 19F NMR (564 MHz, CDCl3) δ -81.06 (3F), -111.34 (2F), -124.12 (2F), -
(564 MHz, CDCl3) δ -80.93 (3F), -111.19 (2F), -121.45 (2F), - 125.72 (2F); IR (neat): νmax = 3008, 2961, 1659, 1234, 974, 748
122.00 (m, 4F), -122.81 (2F), -123.26 (2F), -126.22 (m, 2F); IR cm-1; Rf 0.86 (Petroleum ether/Ether, 8/1).
(neat): νmax = 3035, 1659, 1243, 1205, 973 cm-1; Rf 0.69
(Petroleum ether).
(E)-1-(tert-butyl)-4-(6,6,6,6,6,6,6,6,6-nonafluoro-6λ12-hexa-
(E)-1-methoxy-3-(8,8,8,8,8,8,8,8,8,8,8,8,8-tridecafluoro-8λ16-
octa-1-en-3,5,7-triyn-1-yl)benzene, 3db: colorless oil; 1H NMR
(600 MHz, CDCl3) δ 7.32 (dd, J = 8.1, 7.8 Hz, 1H), 7.15 (d, J =
1-en-3,5-diyn-1-yl)benzene, 3ba: colorless oil; 1H NMR (600 16.1 Hz, 1H), 7.08 (d, J = 7.8 Hz, 1H), 6.99 (s, 1H), 6.95 (d, J =
MHz, CDCl3) δ 7.47 -7.43 (m, 4H), 7.18 (dt, J = 16.1, 2.3 Hz, 1H), 8.1 Hz, 1H), 6.19 (dt, J = 16.1, 12.3 Hz, 1H), 3.85 (s, 3H); 13C
6.19 (dt, J = 16.1, 12.3 Hz, 1H), 1.36 (s, 9H).; 13C NMR (151 MHz, NMR (151 MHz, CDCl3) δ 160.26, 139.95 (t, J = 9.5 Hz), 135.15,
CDCl3) δ 153.99, 139.79 (t, J = 9.5 Hz), 131.07, 127.71, 126.16, 130.25, 120.46, 116.12, 114.91 (t, J = 22.9 Hz), 113.14, 55.60
13.57 (t, J = 23.0 Hz), 35.09, 31.37 (carbon peaks of –C4F9 are (carbon peaks of –C6F13 are omitted due to complicated C-F
omitted due to complicated C-F splitting); 19F NMR (564 MHz, splitting); 19F NMR (564 MHz, CDCl3) δ -80.82 (3F), -111.13 (2F),
CDCl3) δ -81.15 (3F), -111.18 (2F), -124.18 (2F), -125.75 (2F); IR -121.61 (2F), -122.87 (2F), -123.23 (2F), -126.15 (2F); IR (neat)
:
(neat): νmax = 2967, 2872, 1657, 1214, 975, 733 cm-1; HRMS νmax = 2987, 2901, 1604, 1230, 1066, 1053, 974 cm-1; HRMS
m/z (EI) calc. for C16H15F9 [M+] 378.1030, found 378.1033; Rf m/z (EI) calc. for C15H9F13O [M+] 452.0446, found 452.0443; Rf
0.70 (Petroleum ether).
(E)-1-(tert-butyl)-4-(8,8,8,8,8,8,8,8,8,8,8,8,8-tridecafluoro-
0.77 (Petroleum ether/Ether, 8/1).
(E)-1,3-dimethyl-5-(6,6,6,6,6,6,6,6,6-nonafluoro-6λ12-hexa-
8λ16-octa-1-en-3,5,7-triyn-1-yl)benzene, 3bb4a: colorless oil; 1H 1-en-3,5-diyn-1-yl)benzene, 3ea: colorless oil; 1H NMR (600
NMR (600 MHz, CDCl3) δ 7.49 - 7.45 (m, 4H), 7.21 (dt, J = 16.1, MHz, CDCl3) δ 7.14 - 7.08 (m, 3H), 7.04 (s, 1H), 6.17 (dt, J =
2.1 Hz, 1H), 6.22 (dt, J = 16.1, 12.4 Hz, 1H), 1.38 (s, 9H); 13C 15.9, 12.8 Hz, 1H), 2.34 (s, 6H); 13C NMR (151 MHz, CDCl3)
δ
NMR (151 MHz, CDCl3) δ 154.04, 139.80 (t, J = 9.5 Hz), 131.17, 140.23 (t, J = 9.7 Hz), 138.78, 133.68, 132.12, 125.73, 113.96 (t,
127.75, 126.19, 113.75 (t, J = 23.1 Hz), 35.09, 31.34 (carbon J = 22.8 Hz), 21.37 (carbon peaks of –C4F9 are omitted due to
peaks of –C6F13 are omitted due to complicated C-F splitting); complicated C-F splitting); 19F NMR (564 MHz, CDCl3) δ -81.09
19F NMR (564 MHz, CDCl3) δ -81.12 (3F), -111.09 (2F), -121.71 (3F), -111.25 (2F), -124.19 (2F), -125.73 (2F); IR (neat): νmax
(2F), -123.01 (2F), -123.41 (2F), -126.33 (2F); IR (neat): νmax
3188, 2929, 1589, 1309, 1146, 936 cm-1; HRMS m/z (EI) calc.
3035, 2967, 1657, 1240, 975, 832 cm-1; Rf 0.69 (Petroleum for C14H11F9 [M+] 350.0717, found 350.0714; Rf 0.68
=
=
ether).
(E)-1-(tert-butyl)-4-(10,10,10,10,10,10,10,10,10,10,10,10,10-
tridecafluoro-10λ16-deca-1-en-3,5,7,9-tetrayn-1-yl)benzene,
(Petroleum ether).
(E)-1,3-dimethyl-5-(8,8,8,8,8,8,8,8,8,8,8,8,8-tridecafluoro-
8λ16-octa-1-en-3,5,7-triyn-1-yl)benzene, 3eb: colorless oil; 1H
3bc: off-white solid; 1H NMR (300 MHz, CDCl3) δ 7.45 - 7.41 (m, NMR (600 MHz, CDCl3) δ 7.15 - 7.10 (m, 3H), 7.05 (s, 1H), 6.19
4H), 7.16 (d, J = 16.0 1H), 6.17 (dt, J = 16.0, 12.3 Hz, 1H), 1.34 (s, (dt, J = 16.0, 12.3 Hz, 1H), 2.36 (s, 6H); 13C NMR (151 MHz,
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CDCl3) δ 140.23 (t, J = 9.6 Hz), 138.81, 133.74, 132.14, 125.75, 135.59, 135.36, 130.43, 130.39, 127.74, 126.08, 116.23 (t, J =
View Article Online
DOI: 10.1039/C9OB00332K
114.09 (t, J = 23.1 Hz), 21.33 (carbon peaks of –C6F13 are 23.1 Hz) (carbon peaks of –C8F17 are omitted due to
omitted due to complicated C-F splitting); 19F NMR (564 MHz, complicated C-F splitting); 19F NMR (564 MHz, CDCl3) δ -81.08
CDCl3) δ -80.96 (3F), -111.07 (2F), -121.66 (2F), -122.94 (2F), - (3F), -111.58 (2F), -121.52 (2F), -122.07 (m, 4F), -122.89 (2F), -
123.34 (2F), -126.26 (2F); IR (neat): νmax = 2924, 1657, 1605, 123.26 (2F), -126.33 (2F); IR (neat): νmax = 2974, 1661, 1200,
1237, 1199, 974 cm-1; HRMS m/z (EI) calc. for C16H11F13 [M+] 971, 779, 732 cm-1; HRMS m/z (EI) calc. for C16H6ClF17 [M+]
450.0653, found 450.0651; Rf 0.73 (Petroleum ether).
(E)-1-(10,10,10,10,10,10,10,10,10,10,10,10,10,10,10,10,10-
heptadecafluoro-10λ20-deca-1-en-3,5,7,9-tetrayn-1-yl)-3,5-
555.9887, found 555.9889; Rf 0.71 (Petroleum ether).
(E)-1-chloro-4-(6,6,6,6,6,6,6,6,6-nonafluoro-6λ12-hexa-1-en-
3,5-diyn-1-yl)benzene, 3ha3i: colorless oil; 1H NMR (600 MHz,
dimethylbenzene, 3ec: colorless oil; 1H NMR (600 MHz, CDCl3) CDCl3) δ 7.42 (d, J = 8.6 Hz, 2H), 7.38 (d, J = 8.6 Hz, 2H), 7.13 (dt,
δ 7.15 - 7.10 (m, 3H), 7.05 (s, 1H), 6.19 (dt, J = 16.0, 12.4 Hz, J = 16.2, 2.2 Hz, 1H), 6.18 (dt, J = 16.2, 12.0 Hz, 1H); 13C NMR
1H), 2.35 (s, 6H); 13C NMR (151 MHz, CDCl3) δ 140.22 (t, J = 9.4 (151 MHz, CDCl3) δ 138.74 (t, J = 9.6 Hz), 136.44, 132.21,
Hz), 138.81, 133.77, 132.13, 125.75, 114.13 (t, J = 23.0 Hz), 129.48, 129.07, 115.10 (t, J = 23.3 Hz) (carbon peaks of –C4F9
21.30 (carbon peaks of –C8F17 are omitted due to complicated are omitted due to complicated C-F splitting); 19F NMR (564
C-F splitting); 19F NMR (564 MHz, CDCl3) δ -81.05 (3F), -111.12 MHz, CDCl3) δ -81.04 (3F), -111.47 (2F), -124.09 (2F), -125.72
(2F), -121.48 (2F), -122.04 (m, 4F), -122.86 (2F), -123.33 (2F), - (2F); IR (neat): νmax = 3044, 2927, 1660, 1236, 1206, 974 cm-1;
126.29 (2F); IR (neat): νmax = 2924, 1657, 1241, 1211, 973, 728 Rf 0.62 (Petroleum ether).
cm-1; HRMS m/z (EI) calc. for C18H11F17 [M+] 550.0589, found
550.0593; Rf 0.68 (Petroleum ether).
(E)-1-nitro-4-(6,6,6,6,6,6,6,6,6-nonafluoro-6λ12-hexa-1-en-
(E)-1-chloro-4-(8,8,8,8,8,8,8,8,8,8,8,8,8-tridecafluoro-8λ16-
octa-1-en-3,5,7-triyn-1-yl)benzene, 3hb3i: colorless oil; 1H NMR
(600 MHz, CDCl3) δ 7.42 (d, J = 8.5 Hz, 2H), 7.38 (d, J = 8.5 Hz,
3,5-diyn-1-yl)benzene, 3fa3f: off-white solid; 1H NMR (600 MHz, 2H), 7.13 (d, J = 16.2 Hz, 1H), 6.18 (dt, J = 16.2, 12.0 Hz, 1H); 13C
CDCl3) δ 8.28 (d, J = 8.6 Hz, 2H), 7.65 (d, J = 8.6 Hz, 2H), 7.25 (d, NMR (151 MHz, CDCl3) δ 138.71 (t, J = 9.2 Hz), 136.45, 132.22,
J = 15.9 Hz, 1H), 6.37 (dt, J = 15.9, 11.7 Hz, 1H); 13C NMR (151 129.48, 129.08, 115.21 (t, J = 22.9 Hz) (carbon peaks of –C6F13
MHz, CDCl3) δ 148.88, 139.64, 137.74 (t, J = 9.3 Hz), 128.64, are omitted due to complicated C-F splitting); 19F NMR (564
124.50, 118.95 (t, J = 23.6 Hz) (carbon peaks of –C4F9 are MHz, CDCl3) δ -80.83 (3F), -111.25 (2F), -121.64 (2F), -122.86
omitted due to complicated C-F splitting); 19F NMR (564 MHz, (2F), -123.20 (2F), -126.16 (2F); IR (neat): νmax = 2927, 1660,
CDCl3) δ -81.00 (3F), -112.02 (2F), -123.95 (2F), -125.70 (2F); IR 1240, 1197, 974 cm-1; Rf 0.79 (Petroleum ether).
(neat): νmax = 2916, 1608, 1535, 1349, 1237, 913 cm-1; Rf 0.56
(Petroleum ether/Ether, 8/1).
(E)-1-chloro-3-(6,6,6,6,6,6,6,6,6-nonafluoro-6λ12-hexa-1-en-
(E)-1-(4-(6,6,6,6,6,6,6,6,6-nonafluoro-6λ12-hexa-1-en-3,5-
diyn-1-yl)phenyl)ethan-1-one, 3ia: colorless oil; 1H NMR (300
MHz, CDCl3) δ 7.97 (d, J = 8.3 Hz, 2H), 7.55 (d, J = 8.3 Hz, 2H),
3,5-diyn-1-yl)benzene, 3ga3f: colorless oil; 1H NMR (600 MHz, 7.20 (d, J = 16.1 Hz, 1H), 6.30 (dt, J = 16.1, 12.0 Hz, 1H), 2.60 (s,
CDCl3) δ 7.47 (s, 1H), 7.40 – 7.32 (m, 3H), 7.12 (dt, J = 16.0, 2.2 3H); 13C NMR (151 MHz, CDCl3) δ 197.30, 138.83 (t, J = 9.6 Hz),
Hz, 1H), 6.22 (dt, J = 16.0, 12.1 Hz, 1H); 13C NMR (151 MHz, 138.33, 137.90, 129.09, 127.99, 116.99 (t, J = 23.1 Hz), 26.77
CDCl3) δ 138.66 (t, J = 9.5 Hz), 135.51, 135.31, 130.45, 130.39, (carbon peaks of –C4F9 are omitted due to complicated C-F
127.72, 126.10, 116.07 (t, J = 23.3 Hz) (carbon peaks of –C4F9 splitting); 19F NMR (564 MHz, CDCl3) δ -81.24 (3F), -111.87 (2F),
are omitted due to complicated C-F splitting); 19F NMR (564 -124.17 (2F), -125.87 (2F); IR (neat): νmax = 3033, 2987, 1685,
MHz, CDCl3) δ -81.06 (3F), -111.63 (2F), -124.09 (2F), -125.73 1235, 1207, 974, 816 cm-1; HRMS m/z (EI) calc. for C14H9F9O
(2F); IR (neat): νmax = 3068, 2971, 1661, 1234, 970, 785 cm-1; Rf [M+] 364.0510, found 364.0508; Rf 0.67 (Petroleum
0.67 (Petroleum ether).
(E)-1-chloro-3-(8,8,8,8,8,8,8,8,8,8,8,8,8-tridecafluoro-8λ16-
ether/Ether, 8/1).
(E)-1-(4-(8,8,8,8,8,8,8,8,8,8,8,8,8-tridecafluoro-8λ16-octa-1-
octa-1-en-3,5,7-triyn-1-yl)benzene, 3gb: colorless oil; 1H NMR en-3,5,7-triyn-1-yl)phenyl)ethan-1-one, 3ib7b: off-white solid;
(300 MHz,CDCl3) δ 7.47 (s, 1H), 7.39 – 7.32 (m, 3H), 7.13 (dt, J 1H NMR (600 MHz, CDCl3) δ 7.98 (d, J = 8.3 Hz, 2H), 7.57 (d, J =
= 16.1, 2.1 Hz, 1H), 6.22 (dt, J = 16.1, 12.0 Hz, 1H); 13C NMR 8.3 Hz, 2H), 7.21 (d, J = 16.1 Hz, 1H), 6.31 (dt, J = 16.1, 12.0 Hz,
(151 MHz, CDCl3) δ 138.63 (t, J = 9.7 Hz), 135.53, 135.31, 1H), 2.61 (s, 3H); 13C NMR (151 MHz, CDCl3) δ 197.36, 138.81 (t,
130.45, 130.39, 127.72, 126.11, 116.17 (t, J = 23.4 Hz) (carbon J = 9.5 Hz), 138.35, 137.95, 129.13, 128.03, 117.15 (t, J = 23.3
peaks of –C6F13 are omitted due to complicated C-F splitting); Hz), 26.83 (carbon peaks of –C6F13 are omitted due to
19F NMR (564 MHz, CDCl3) δ -80.84 (3F), -111.43 (2F), -121.62 complicated C-F splitting); 19F NMR (564 MHz, CDCl3) δ -80.95
(2F), -122.88 (2F), -123.21 (2F), -126.18 (2F); IR (neat): νmax
=
(3F), -111.58 (2F), -121.67 (2F), -122.93 (2F), -123.21 (2F), -
2932, 1661, 1240, 971, 781, 725 cm-1; HRMS m/z (EI) calc. for 126.25 (2F); IR (neat): νmax = 3044, 2966, 1725, 1688, 1240,
C14H6ClF13 [M+] 455.9950, found 455.9950; Rf 0.71 (Petroleum 975 cm-1; Rf 0.50 (Petroleum ether/Ether, 8/1).
ether).
(E)-1-chloro-3-
(10,10,10,10,10,10,10,10,10,10,10,10,10,10,10,10,10-
(E)-1-(6,6,6,6,6,6,6,6,6-nonafluoro-6λ12-hexa-1-en-3,5-diyn-
1-yl)naphthalene, 3ja13: colorless oil; 1H NMR (600 MHz, CDCl3)
δ 8.07 (d, J = 8.0 Hz, 1H), 8.02 (d, J = 15.9 Hz, 1H), 7.93 (d, J =
heptadecafluoro-10λ20-deca-1-en-3,5,7,9-tetrayn-1-yl)benzene, 7.7 Hz, 1H), 7.91 (d, J = 7.1 Hz, 1H), 7.67 (d, J = 7.0 Hz, 1H), 7.61
3gc: colorless oil; 1H NMR (600 MHz, CDCl3) δ 7.47 (s, 1H), 7.39 (dd, J = 8.2, 7.0 Hz, 1H), 7.57 (dd, J = 8.2, 7.1 Hz, 1H), 7.51 (dd, J
– 7.32 (m, 3H), 7.12 (d, J = 16.1 Hz, 1H), 6.22 (dt, J = 16.1, 12.2 = 8.0, 7.7 Hz, 1H), 6.31 (dt, J = 15.9, 12.3 Hz, 1H).; 13C NMR
Hz, 1H); 13C NMR (151 MHz, CDCl3) δ 138.62 (t, J = 9.5 Hz), (151 MHz, CDCl3) δ 137.75 (t, J = 9.6 Hz), 133.85, 131.52,
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131.35, 130.61, 129.00, 127.21, 126.57, 125.65, 125.18, 123.37, 130.70, 130.65, 130.03, 129.34, 127.92, 127.40, 127.35, 127.32,
View Article Online
DOI: 10.1039/C9OB00332K
117.59 (t, J = 22.9 Hz) (carbon peaks of –C4F9 are omitted due 126.65, 124.37, 123.51, 122.87, 118.23 (t, J = 22.9 Hz) (carbon
to complicated C-F splitting); 19F NMR (564 MHz, CDCl3) δ - peaks of –C6F13 are omitted due to complicated C-F splitting);
81.06 (3F), -111.28 (2F), -124.10 (2F), -125.63 (2F); IR (neat)
νmax = 3066, 2957, 1654, 1236, 886 cm-1; Rf 0.54 (Petroleum (2F), -122.79 (2F), -123.08 (2F), -126.09 (2F); IR (neat): νmax
ether).
2971, 2923, 1655, 1241, 1202, 971 cm-1; HRMS m/z (EI) calc.
(E)-1-(8,8,8,8,8,8,8,8,8,8,8,8,8-tridecafluoro-8λ16-octa-1-en-
for C22H11F13 [M+] 522.0653, found 522.0652; Rf 0.47
3,5,7-triyn-1-yl)naphthalene, 3jb: colorless oil; 1H NMR (600 (Petroleum ether).
:
19F NMR (564 MHz, CDCl3) δ -80.77 (3F), -111.02 (2F), -121.47
=
MHz, CDCl3) δ 8.07 (d, J = 7.9 Hz, 1H), 8.01 (d, J = 15.6 Hz, 1H),
(E)-1-(8,8,8,8,8,8,8,8,8,8,8,8,8-tridecafluoro-8λ16-octa-1-en-
7.92 (d, J = 7.7 Hz, 1H), 7.90 (d, J = 7.2 Hz, 1H), 7.67 (d, J = 7.0 3,5,7-triyn-1-yl)pyrene, 3la: pale-green oil; 1H NMR (600 MHz,
Hz, 1H), 7.61 (dd, J = 7.7, 7.0 Hz, 1H), 7.56 (dd, J = 7.7, 7.2 Hz, CDCl3) δ 8.35 (d, J = 9.2 Hz, 1H), 8.29 (d, J = 15.9 Hz, 1H), 8.25 -
1H), 7.51 (dd, J = 7.9, 7.7 Hz, 1H), 6.30 (dt, J = 15.6, 12.2 Hz, 8.24 (m, 2H), 8.20 - 8.17 (m, 3H), 8.14 (d, J = 8.8 Hz, 1H), 8.08 -
1H); 13C NMR (151 MHz, CDCl3) δ 137.72 (t, J = 9.4 Hz), 133.86, 8.05 (m, 2H), 6.45 (dt, J = 15.9, 12.2 Hz, 1H); 13C NMR (151
131.53, 131.37, 130.61, 129.00, 127.21, 126.57, 125.65, 125.18, MHz, CDCl3) δ 137.33 (t, J = 9.4 Hz), 132.81, 131.56, 130.91,
123.37, 117.69 (t, J = 22.9 Hz) (carbon peaks of –C6F13 are 129.51, 129.00, 128.80, 127.61, 127.52, 126.59, 126.30, 126.07,
omitted due to complicated C-F splitting); 19F NMR (564 MHz, 125.29, 125.08, 124.84, 124.42, 122.40, 117.10 (t, J = 22.4 Hz)
CDCl3) δ -80.92 (3F), -111.09 (2F), -121.55 (2F), -122.87 (2F), - (carbon peaks of –C4F9 are omitted due to complicated C-F
123.23 (2F), -126.20 (2F); IR (neat): νmax = 3065, 2987, 1653, splitting); 19F NMR (564 MHz, CDCl3) δ -80.95, -110.88, -123.91,
1239, 1201, 972 cm-1; HRMS m/z (EI) calc. for C18H9F13 [M+] -125.55; IR (neat): νmax = 2987, 2901, 1650, 1240, 903, 723 cm-
1
472.0497, found 472.0495; Rf 0.59 (Petroleum ether).
(E)-1-(10,10,10,10,10,10,10,10,10,10,10,10,10,10,10,10,10-
heptadecafluoro-10λ20-deca-1-en-3,5,7,9-tetrayn-1-
; HRMS m/z (EI) calc. for C22H11F9 [M+] 446.0717, found
446.0715; Rf 0.40 (Petroleum ether).
(E)-1-(6,6,6,6,6,6,6,6,6-nonafluoro-6λ12-hexa-1-en-3,5-diyn-
yl)naphthalene, 3jc: off-white solid; m. p. 40-42 °C; 1H NMR 1-yl)pyrene, 3lb: pale-green solid; m. p. 82-85 °C; 1H NMR (600
(600 MHz, CDCl3) δ 8.05 (d, J = 8.0 Hz, 1H), 7.99 (d, J = 15.9 Hz, MHz, CDCl3) δ 8.34 (d, J = 9.2 Hz, 1H), 8.29 (d, J = 15.8 Hz, 1H),
1H), 7.92 (d, J = 8.1 Hz, 1H), 7.90 (d, J = 8.2 Hz, 1H), 7.66 (d, J = 8.26 - 8.23 (m, 2H), 8.21 - 8.18 (m, 3H), 8.13 (d, J = 8.9 Hz, 1H),
7.0 Hz, 1H), 7.59 (dd, J = 7.4, 7.0 Hz, 1H), 7.55 (dd, J = 8.2, 7.4 8.09 - 8.04 (m, 2H), 6.45 (dt, J = 15.8, 12.1 Hz, 1H); 13C NMR
Hz, 1H), 7.50 (dd, J = 8.1, 8.0 Hz, 1H), 6.28 (dt, J = 15.9, 12.1 Hz, (151 MHz, CDCl3) δ 137.32 (t, J = 9.2 Hz), 132.81, 131.56,
1H); 13C NMR (151 MHz, CDCl3) δ 137.69 (t, J = 9.5 Hz), 133.82, 130.91, 129.51, 128.98, 128.79, 127.78, 127.51, 126.59, 126.29,
131.51, 131.33, 130.61, 129.00, 127.22, 126.58, 125.66, 125.19, 126.07, 125.28, 125.08, 124.84, 124.40, 122.39, 117.09 (t, J =
123.37, 117.70 (t, J = 23.7 Hz) (carbon peaks of –C8F17 are 22.5 Hz) (carbon peaks of –C6F13 are omitted due to
omitted due to complicated C-F splitting); 19F NMR (564 MHz, complicated C-F splitting); 19F NMR (564 MHz, CDCl3) δ -80.76
CDCl3) δ -80.78 (3F), -111.02 (2F), -121.28 (2F), -121.88 (m, 4F), (3F), -110.64 (2F), -121.45 (2F), -122.77 (2F), -122.98 (2F), -
-122.70 (2F), -123.14 (2F), -126.10 (2F); IR (neat): νmax = 3081, 126.07 (2F); IR (neat): νmax = 2987, 2901, 1653, 1241, 903, 723
2987, 1661, 1242, 1152, 972 cm-1; HRMS m/z (EI) calc. for cm-1; HRMS m/z (EI) calc. for C24H11F13 [M+] 546.0653, found
C20H9F17 [M+] 572.0433, found 572.0436; Rf 0.54 (Petroleum 546.0656; Rf 0.40 (Petroleum ether).
ether).
(E)-9-(6,6,6,6,6,6,6,6,6-nonafluoro-6λ12-hexa-1-en-3,5-diyn-
Analytic Data for Side Products
1,1'-biphenyl,
: white solid; 1H NMR (600 MHz, CDCl3)
5
δ
1-yl)phenanthrene, 3ka: off-white oil; 1H NMR (600 MHz, 7.61 (d, J = 7.8 Hz, 4H), 7.46 (dd, J = 7.8, 7.6 Hz, 4H), 7.36 (t, J =
CDCl3) δ 8.76 (d, J = 8.1 Hz, 1H), 8.69 (d, J = 8.4 Hz, 1H), 8.06 (d, 7.6 Hz, 2H); 13C NMR (151 MHz, CDCl3) δ 141.46, 128.96,
J = 7.7 Hz, 1H), 8.00 (d, J = 15.6 Hz, 1H), 7.93 (d, J = 7.8 Hz, 1H), 127.46, 127.38.
7.89 (s, 1H), 7.75 – 7.67 (m, 3H), 7.64 (dd, J = 7.8, 7.1 Hz, 1H),
6.37 (dt, J = 15.6, 12.3 Hz, 1H); 13C NMR (151 MHz, CDCl3)
1-((E)-3,3,4,4,5,5,6,6,6-nonafluorohex-1-en-1-yl)-4-((E)-
3,3,4,4,5,6,6,6-octafluoro-5-methylhex-1-en-1-yl)benzene,
δ
138.56 (t, J = 9.3 Hz), 131.31, 131.25, 130.71, 130.65, 130.03, 3ma: white solid; 1H NMR (600 MHz, CDCl3) 7.52 (s, 4H), 7.18
129.34, 127.92, 127.41, 127.36, 127.33, 126.67, 124.38, 123.52, (d, J = 16.1 Hz, 2H), 6.25 (dt, J = 16.1, 12.1 Hz, 2H); 13C NMR
122.87, 118.16 (t, J = 22.5 Hz) (carbon peaks of –C4F9 are (151 MHz, CDCl3) δ 138.94 (t, J = 10.0 Hz), 135.40, 128.43,
omitted due to complicated C-F splitting); 19F NMR (564 MHz, 115.81 (t, J = 23.3 Hz) (carbon peaks of –C4F9 are omitted due
CDCl3) δ -80.96 (3F), -111.26 (2F), -124.02 (2F), -125.57 (2F); IR to complicated C-F splitting); 19F NMR (564 MHz, CDCl3) δ -
(neat): νmax = 2953, 2922, 2852, 1656, 1235, 970 cm-1; HRMS 81.04 (3F), -111.51 (2F), -124.04 (2F), -125.72 (2F).
m/z (EI) calc. for C20H11F9 [M+] 422.0717, found 422.0719; Rf
0.58 (Petroleum ether).
(E)-9-(8,8,8,8,8,8,8,8,8,8,8,8,8-tridecafluoro-8λ16-octa-1-en-
(E)-(4-bromo-3,3,4,4-tetrafluorobut-1-en-1-yl)benzene,
3ad14: colorless oil; 1H NMR (600 MHz, CDCl3) δ 7.49 (m, 2H),
7.41 (m, 3H), 7.20 (d, J = 16.1 Hz, 1H), 6.25 (dt, J = 16.1, 11.8 Hz,
3,5,7-triyn-1-yl)phenanthrene, 3kb: off-white solid; m. p. 68- 1H); 13C NMR (151 MHz, CDCl3) δ 140.02 (t, J = 8.6 Hz), 133.93,
70 °C; 1H NMR (600 MHz, CDCl3) δ 8.75 (d, J = 8.0 Hz, 1H), 8.68 130.30, 129.16, 127.82, 114.56 (t, J = 23.9 Hz) (carbon peaks of
(d, J = 8.2 Hz, 1H), 8.06 (d, J = 8.0 Hz, 1H), 7.99 (d, J = 15.5 Hz, –C2F5 are omitted due to complicated C-F splitting); 19F NMR
1H), 7.93 (d, J = 7.4 Hz, 1H), 7.88 (s, 1H), 7.71 (m, 3H), 7.71 (dd, (564 MHz, CDCl3) δ -65.65 (2F), -109.04 (2F).
J = 7.4, 7.4 Hz, 1H), 6.36 (dt, J = 15.5, 12.0 Hz, 1H); 13C NMR
(1E,3E)-1,4-diphenylbuta-1,3-diene, 615: white solid; 1H NMR
(151 MHz, CDCl3) δ 138.53 (t, J = 9.4 Hz), 131.31, 131.24, (600 MHz, CDCl3) δ 7.45 (d, J = 7.7 Hz, 4H), 7.34 (dd, J = 7.7, 7.4
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Organic & Biomolecular Chemistry
Page 8 of 8
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Journal Name
974; (b) S. Barata-Vallejo, S. M. Bonesi and A. VPieowsAtirtgicole, OOnrlinge.
Biomol. Chem., 2015, 13, 11153-1118D3O; I(:c1)0.T1.03C9h/Cat9tOeBrj0e0e3,32NK.
Iqbal, Y. You and E. J. Cho, Acc. Chem. Res., 2016, 49, 2284-
Hz, 4H), 7.24 (t, J = 7.4 Hz, 2H), 6.97 (d, J = 11.9 Hz, 2H), 6.69 (d,
J = 11.9 Hz, 2H); 13C NMR (151 MHz, CDCl3) δ 137.58, 133.04,
129.47, 128.87, 127.78, 126.60.
2294; (d) X. Pan, H. Xia and J. Wu, Org. Chem. Front., 2016, 3,
buta-1,3-diene-2,3-diyldibenzene, 716: white solid; 1H NMR
(600 MHz, CDCl3) δ 7.39 (d, J = 7.7 Hz, 4H), 7.27 (dd, J = 7.7, 7.4
Hz, 4H), 7.22 (t, J = 7.4 Hz, 2H), 5.54 (d, J = 1.6 Hz, 2H), 5.3 (d, J
= 1.6 Hz, 2H); 1H NMR (600 MHz, (CD3)2CO) δ 7.44 (d, J = 7.6
Hz, 4H), 7.31 (dd, J = 7.6, 7.2 Hz, 4H), 7.27 (t, J = 7.2 Hz, 2H),
5.64 (d, J = 1.7 Hz, 2H), 5.37 (d, J = 1.7 Hz, 2H);13C NMR (151
MHz, CDCl3) δ 150.06, 140.42, 128.38, 127.71, 116.57, 110.24.
13C NMR (151 MHz, (CD3)2CO) δ 150.86, 140.57, 128.88,
128.26, 127.94, 116.20.
1163-1185; (e) Visible Light Photocatalysis in Organic
Chemistry, ed. C. R. J. Stephenson, T. R. Yoon and D. W. C.
MacMillan, John Wiley & Sons, 2018.
Visible light-induced synthesis of fluoroalkyl alkenes from
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6
N. Iqbal, S. Park and E. J. Cho, Chem. Commun., 2014, 50
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styrene, 8 δ
: colorless liquid; 1H NMR (600 MHz, (CD3)2CO)
Asian J. Org. Chem., 2017, 6, 436-440; (f) G.-R. Park, J. Moon
7.51 (d, J = 7.6 Hz, 2H), 7.39 (dd, J = 7.6 , 7.5 Hz, 2H), 7.31 (t, J =
7.5 Hz, 1H), 6.81 (dd, J = 17.7, 10.9 Hz, 1H), 5.86 (d, J = 17.7 Hz,
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7
8
1H), 5.29 (d, J = 10.9 Hz, 1H); 13C NMR (151 MHz, (CD3)2CO)
δ
138.38, 137.76, 129.28, 128.57, 126.92, 114.01.
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Conflicts of interest
There are no conflicts to declare.
Gormisky and M. C. White, J. Am. Chem. Soc., 2013, 135
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Acknowledgements
We gratefully acknowledge the National Research Foundation
of Korea [NRF-2012M3A7B4049657, NRF-2014-011165, and
NRF-2017R1A2B2004082].
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8 | J. Name., 2012, 00, 1-3
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