Base-catalyzed stereoselective hydrophenoxylation and hydrothiolation of hexafluorobutyne

Article abstract of DOI:10.1016/j.tetlet.2020.151693

Novel base-catalyzed hydrophenoxylation and hydrothiolation of hexafluorobutyne are described. By using an easily available base, a variety of vinyl ethers as well as sulfides are prepared at room temperature through two-phase nucleophilic addition reacti

Full text of DOI:10.1016/j.tetlet.2020.151693

Journal Pre-proofs
Base-catalyzed stereoselective hydrophenoxylation and hydrothiolation of hex-
afluorobutyne
Zhao Bo, Zeng Ji-Jun, Han Sheng, Tu Dong-Huai, Li Jiang-Wei, Zhang Wei,
Lu Jian
PII:
S0040-4039(20)30116-7
DOI:
https://doi.org/10.1016/j.tetlet.2020.151693
TETL 151693
Reference:
Tetrahedron Letters
To appear in:
Received Date:
Revised Date:
Accepted Date:
1 December 2019
22 January 2020
29 January 2020
Please cite this article as: Bo, Z., Ji-Jun, Z., Sheng, H., Dong-Huai, T., Jiang-Wei, L., Wei, Z., Jian, L., Base-catalyzed
stereoselective hydrophenoxylation and hydrothiolation of hexafluorobutyne, Tetrahedron Letters (2020), doi:
https://doi.org/10.1016/j.tetlet.2020.151693
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Base-catalyzed stereoselective
hydrophenoxylation and hydrothiolation of
hexafluorobutyne
Leave this area blank for abstract info.
Zhao Boa , Zeng Ji-Juna , Han Shenga , Tu Dong-Huaia , Li Jiang-Weia , Zhang Wei and Lu Jian
State Key Laboratory of Fluorine & Nitrogen Chemicals, Xi’an Modern Chemistry Research Institute, Xi’an,
710065, China.
F3C
H
Mild reaction conditions
High Z selectivity
100% atom utilization
DBU
Ar
XH
+
F3C
CF3
Ar
X
CF3
X = O, S
X = O, S

1
Tetrahedron
journal homepage: www.elsevier.com
Base-catalyzed stereoselective hydrophenoxylation and hydrothiolation of
hexafluorobutyne
Zhao Boa , Zeng Ji-Juna , Han Shenga , Tu Dong-Huaia , Li Jiang-Weia , Zhang Wei and Lu Jian
a State Key Laboratory of Fluorine & Nitrogen Chemicals, Xi’an Modern Chemistry Research Institute, Xi’an, 710065, China.
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
Novel base-catalyzed hydrophenoxylation and hydrothiolation of hexafluorobutyne are
described. By using an easily available base, a variety of vinyl ethers as well as sulfides are
prepared at room temperature through two-phase nucleophilic addition reaction. Mechanistic
study revealed that the stereoselectivity of vinyl ethers might depend on frontier orbital
interaction under kinetic control.
Available online
2009 Elsevier Ltd. All rights reserved.
Keywords:
Keyword_1 base-catalyzed
Keyword_2 nucleophilic addition
Keyword_3 hydrophenoxylation
Keyword_4 hydrothiolation
Keyword_5
———
 Corresponding author. Tel.: +86-29-88291213; e-mail: lujian204@263.net
 Corresponding author. Tel.: +86-29-88291367; e-mail: zhangwei_204@163.com

2
Tetrahedron
entry catalyst loading (mol%) solvent yield (%)b
1. Introduction
1
Cs2CO3
100
100
100
100
10
10
10
10
10
20
20
20
20
DCM
DCM Trace
N.D.
Vinyl ethers and vinyl sulfides have attracted increasing
2 K3PO4•3H2O
attention since they can serve as important structural component
of natural products, pharmaceuticals and organic materials.1
Within various motifs, trifluoromethylated vinyl ethers represent
ubiquitous synthetic monomers, which have often been employed
in the preparation of valuable fluoropolymers because of their
remarkable properties.2 In search for versatile and stereoselective
methods, considerable efforts have been made on the
development of alternative, mild and environmentally friendly
conditions for formation of C-O or C-S bonds.3 Transition-metal-
catalyzed hydroelementation reactions of carbon-carbon multiple
bonds should be the most straightforward and atom economic
strategy.4
3
4
5
6
7
8
Et2NH
Et3N
Et3N
DBU
DABCO
MTBD
DCM
DCM
DCM Trace
DCM 40
DCM Trace
DCM 30
N.D.
87
9 Quinuclidine
10
DCM Trace
DBU
DBU
DBU
DBU
DCM 95 (93c)
11
12
13
Acetone
THF
toluene
83
80
89
aReaction conditions: 1a (1 mmol), 2a (2-3 mmol), DCM (2
Although direct construction of substituted vinyl compounds
from hydroalkoxylation of internal alkynes has been extensively
studied,5 the analogous reactions of phenols are very rare and
mainly rely on noble metal catalyst.6 Recently, gold catalysis has
become an area of significant interest, particularly in the
synthesis of phenyl vinyl ethers, due to its unique reactivity and
high functional group compatibility.7,8 Despite progress has been
achieved, seeking a new channel to install phenols or thiophenols
into fluorinated alkynes that utilizes easily available catalysts
with high stereoselectivity is appealing and challenging. As part
of our ongoing research on fluorocarbon chemistry, previous
works have indicated that hexafluorobutyne displays good
electrophilicity at C≡C bond.9 Herein, we report a two-phase
hydrophenoxylation and hydrothiolation to generate trifluoro-
vinyl ethers and sulfides through a base-catalyzed nucleophilic
addition in a single isomer.
mL), 25 C, 10 h. Yields determined by H and 19F NMR, 4’-
o
b
1
c
fluoroacetophenone as internal standard. Isolated yields. DBU =
1,8-diazabicyclo
diazabicyclo[2.2.2]octane,
triazabicyclo[4.4.0]decene-5.
[5.4.0]undec-7-ene,
DABCO
= 7-methyl-1,5,7-
=
1,4-
MTBE
Table 2 Scope for Hydrophenoxylation of Hexafluorobutynea
F3C
H
F3C
H
F3C
H
F3C
H
O
O
O
O
CF3
O
CF3
O
CF3
O2N
O
CF3
O
H
b
3d
, 92%
3c, 94%
3a
3b
, 90%
, 93%
F3C
O
H
F3C
O
H
F3C
O
H
F3C
O
H
Br
CF3
Cl
CF3
NC
CF3
F3C
CF3
3h
, 96%
CF3
3f
3g
, 86%
, 65%
3e
, 97%
H
F3C
O
H
F3C
O
H
F3C
H
F3C
O
2. Results and discussion
CF3
CF3
O
O
CF3
3k
1a and 2 were used as the model substrate for the studies.
Some inorganic bases10 were initially screened, with treatment of
cesium carbonate (Cs2CO3) for 10 h at room temperature, desired
product was not obtained (Table 1, entry 1). Due to better
solubility, organic bases might interact with the phenol to weaken
the O-H bond,11 albeit secondary amine complicates the reaction
(Table 1, entry 3), an unanticipated change was achieved by
using triethylamine (Et3N) to give 3a in a decent yield (Table 1,
entry 4). Encouraged by this, the reaction was performed in
catalytic amount of base. Of various nitrogen containing
congeners (Table 1, entry 5-9), DBU was found to be the best
catalyst, 20 mol% catalyst loadings proved superior with optimal
yield in a single Z isomer (Table 1, entry 10). Further screening
of reaction solvents (Table 1, entry 11-13) showed that acetone,
tetrahydrofuran (THF), and toluene result in slightly decreased
yields.
, 91%
CF3
3l
, 99%
F3C
3i
, 94%
3j
, 96%
F3C
H
H
H
O
N
F3C
O
H
O
CF3
N
CF3
O
CF3
CF3
S
3o
3p
3n
, 47%
, 97%
, 76%
3m
, 95%
aReaction conditions: 1 (1 mmol), 2 (2-3 mmol), DCM (2
mL), DBU (10 mol%), 25 C, 10 h, isolated yields, DBU (20
mol%).
o
b
With the optimized conditions in hand, the generality of
hydrophenoxylation was evaluated (Table 2). A series of phenols
bearing functional groups provided moderate to excellent yields
in trans fashion. Common moieties including carbonyl, ester,
cyano were compatible with the addition (3b-3f). As
trifluoromethyl group significantly inactivated O-H bond, a
decreasing in yield was observed (3f). Halides were found to be
quite suitable in the transformations, which might be useful for
further manipulation (3g and 3h). Notably, adducts were afforded
in good to excellent yields regardless of steric effect (3i-3m).
Amino substituent was tolerated, albeit in a somewhat lower
yield, which could attribute to the lone-pair electrons (3n). 2-
naphthol proceeded smoothly, furnished the corresponding
products in a 47% yield (3o). The synthesis of heteroaryl vinyl
ether was noteworthy (3p), which might indicate a broad scope
of this protocol.
Table 1. Optimization of the Reaction Conditionsa
F3C
H
Base / DCM
25 oC / 10 h
O2N
OH
+
F3C
CF3
O2N
O
CF3
2
1a
3a

3
Table 3 Scope for Hydrothiolation of Hexafluorobutynea
unsymmetrical fluoroalkenes (6 and 8), no positional isomer
CF3
F3C
H
F3C
H
F3C
H
was detected, which suggested that regiospecificity was
controlled by electron-effect.12 Less sterically-hindered alkyne
was employed for a tandem nucleophilic addition, which
indicated that nonbonded attraction between -CF3 group and
phenolate anion might facilitate the electron delocalization, cis
configuration was crucial to stabilize the vinyl ether structure.
Previous works had shown that unusual 19F NMR chemical
splitting of trifluoromethyl vinyl moieties, which could
rationalize by strong eletrophilicity and large steric effect,
therefore, Z selectivity could be attributed to frontier orbital
interaction of trifluoromethyl vinyl moiety π* with lone pair Pz
orbital. 13
S
H
S
CF3
H2N
S
CF3
O
S
CF3
CF3
5d
, 89%
5a
5b
, 92%
, 90%
5c
, 53%
F3C
O
O
CF3
F3C
S
H
H
F3C
S
H
S
S
H
Cl
CF3
CF3
Br
CF3
CF3
5h
, 93%
5e
5g
, 69%
, 93%
5f
, 89%
F
CF3
H
F3C
S
H
F3C
F3C
S
H
F
F
S
F
CF3
H
O2N
CF3
CF3
CF3
N
S
CF3
F
b
5l
, 87%
5i
, 22%
5j
, 40%
5k
, 90%
On the basis of control experiments, a plausible reaction
mechanism is proposed (Scheme 2). First, neutral phenol is
ionized under basic condition which triggers the reaction. Second,
nucleophilic addition of phenolate anion A into hexafluorobutyne
affords butenyl anion intermidiate B, followed by protonation
give the desired product and the catalyst is regenerated.
F3C
H
N
S
S
CF3
5m
, 96%
aReaction conditions: 2 (2-3 mmol), 4 (1 mmol), DCM (2 mL),
DBU (10 mol%), 25 C, 10 h, isolated yields. DBU (20 mol%),
acetone (2 mL).
o
b
F3C
H
ArO
In order to further demonstrate the versatile utility of this
approach, investigation was extended to thiophenols 4 (Table 3),
and reactants were also suitable in the same conditions. The
process was applicable to a series of thiolphenols in high yields
with exclusive stereospecificity. Amino derivative was
successfully generated even without protecting group, which was
considered as challenging due to the coordination nature (5c).
Significant drop occurred in the case of 5i, probably ascribe to
the limited nucleophilicity and poor solubility. Addition of 3-
trifluoromethyl or pentafluoro thiophenols into alkyne was
conducted in spite of the reduced electronic density (5j and 5k).
Interestingly, the involvement of heteroaryl thioalcohols
underwent efficiently to provide the corresponding vinyl sulfides
in 87% and 96% yields (5l and 5m).
A
ArO
CF3
F3C
CF3
DBU-H+
DBU
F3C
ArO
ArOH
CF3
B
Scheme 2 Proposed reaction mechanism.
3. Conclusions
In summary, a facile and practical approach for stereoselective
hydrophenoxylation and hydrothiolation was developed. The
nucleophilic addition was expedient to a wide range of substrate
scope under very mild conditions, providing many fluorinated
vinyl ethers and sulfides in moderate to high yields. The low
usage of inexpensive catalyst makes the methodology attractive.
Further application of hexafluorobutyne to other valuable
building blocks is currently underway in our laboratory.
Table 4 Nucleophilic addition of (thio) phenol to fluorinated
substrates
Reactants
Products
F
S
F
F
F
F
Cl
F
Cl
O
H
O
O
H
4. Experimental section
7b, 88%a
7a, 99%a
F
F
δ
Cl
-
+
δ
1
F
General. H, 13C and 19F NMR spectra were recorded on a
F
F
O
F
F
F
S
F
1
6
Cl
Cl
500 MHz. H NMR chemical shifts were determined relative to
Br
H
Br
H
internal (CH3)4Si (TMS) at δ 0.0 or to the signal of the residual
protonated solvent: CDCl3 δ 7.26. 13C NMR chemical shifts were
determined relative to internal TMS at δ 0.0. For the isolated
compounds, 19F NMR chemical shifts were determined relative to
7d, 85%a
7c, 95%a
F
F
O
F
F
F
O
F
CFCl3 at δ 0.0. Data for H, 13C and 19F NMR were recorded as
1
F
+
F
δ
CF3
CF3
CF3
-
δ
Cl
H
O
H
follows: chemical shift (δ, ppm), multiplicity (s = singlet, d =
doublet, t = triplet, m = multiplet, q = quartet, br = broad). High
resolution mass spectra were recorded on an HRMS-TOF
instrument using EI ionization. IR spectra were collected on a
Nicolet IN10 FT-IR spectrometer, and reported in terms of
frequency of absorption (cm-1).
F
9b, 69%b
9a, 83%b
8
CF3
R
Not
Detected
O
O
+
+
δ
δ
F3C
C
δ
CH
-
Reagents. Unless otherwise mentioned, solvents and reagents
are purchased from commercial sources and used as received.
c
R
11a
11b
, 87%
10
CF3
c
, 77%
Reaction conditions: Phenol (1 mmol), aChlorotrifluoroethene (2-
3 mmol), Cs2CO3 (1 mmol), THF (2 mL); Hexafluoropropene
(2-3 mmol), KHCO3 (0.5 mmol), DMF (1 mL);
cTrifluoropropyne (2-3 mmol), K3PO4•3H2O (1 mmol), DMF (1
mL).
Fluorinated building blocks. 1,1,1,4,4,4-hexafluorobutyne is
obtained by dehydrochlorination of 2-chloro-1,1,1,4,4,4-
b
hexafluorobutene.
debromination
Trifluoropropyne
is
obtained
by
of 1,2-dibromo-3,3,3-propene.
Chlorotrifluoroethene and hexafluoropropene are purchased from
commercial sources and used as received.
Several experiments were performed to gain insight into effect
of configuration control (Table 4). Treated phenol with

4
Tetrahedron
Experimental Procedure. The reaction was carried out in
2H, JHH = 8.5 Hz), 6.27 (q, 1H, JHF = 7 Hz). 13C NMR (125 MHz,
CDCl3) δ 157.9, 146.4 (qq, 2JCF = 36.4 Hz, 3JCF = 5 Hz), 127.3 (q,
25 mL Schlenk tube. To a solution of phenol or thiophenol (1
mmol) in DCM (2 mL), DBU was added. The tube was cooling
in liquid nitrogen, then vacuumized and hexafluorobut-2-yne (2-3
mmol) was introduced into the tube, the reaction mixture was
stirred at room temperature for 10 h. The crude product was
purified by column chromatography.
1
3JCF = 3.75 Hz), 124.8, 122.7, 120.8 (q, JCF = 269.6 Hz), 118.8
1
2
3
(q, JCF = 276.4 Hz), 116.4, 112.5 (qq, JCF = 36.9 Hz, JCF = 3.6
Hz). 19F NMR (470.0 MHz, CDCl3) δ -69.8 (s, CF3), -62.3 (s,
CF3), -59.9 (d, JFH = 6.1 Hz, CF3). IR (KBr): 3117, 1616, 1514,
1222, 1162, 861, 651 cm-1. HRMS (EI-TOF): calcd for C11H5F9O
(M+) 324.0197, found 324.0197.
(Z)-1-((1,1,1,4,4,4-hexafluorobut-2-en-2-yl)oxy)-4-
nitrobenzene (3a). White solid, 280 mg, 93%. Mp: 57–59 oC. 1H
NMR (500 MHz, CDCl3) δ 8.21 (d, 2H, JHH = 9.5 Hz), 7.07 (d,
2H, JHH = 9 Hz), 6.28 (q, 1H, JHF = 7 Hz). 13C NMR (125 MHz,
(Z)-1-chloro-4-((1,1,1,4,4,4-hexafluorobut-2-en-2-
1
yl)oxy)benzene (3g). Colorless oil, 250 mg, 86%. H NMR (500
MHz, CDCl3) δ 7.31 (d, 2H, JHH = 9 Hz), 6.97 (d, 2H, JHH = 9
2
3
CDCl3) δ 160.1, 145.9 (qq, JCF = 36.7 Hz, JCF = 5 Hz), 144.3,
Hz), 6.18 (q, 1H, JHF = 7 Hz). 13C NMR (125 MHz, CDCl3) δ
1
1
2
3
126.1, 120.6 (q, JCF = 269.9 Hz), 118.7 (q, JCF = 276.3 Hz),
116.4, 113.4 (qq, 2JCF = 37.1 Hz, 3JCF = 3.5 Hz). 19F NMR (470.0
MHz, CDCl3) δ -69.9 (s, CF3), -59.9 (d, JFH = 7.1 Hz, CF3). IR
(KBr): 3420, 1721, 1531, 1356, 1165, 852, 647 cm-1. HRMS (EI-
TOF): calcd for C10H5F6NO3 (M+) 301.0174, found 301.0174.
154.1, 147.0 (qq, JCF = 35.6 Hz, JCF = 5.1 Hz), 129.9, 129.8,
1
1
121.0 (q, JCF = 269.5 Hz), 118.9 (q, JCF = 276.6 Hz), 117.9,
111.5 (qq, 2JCF = 36.8 Hz, 3JCF = 3.6 Hz). 19F NMR (470.0 MHz,
CDCl3) δ -69.3 (s, CF3), -59.5 (d, JFH = 6.1 Hz, CF3). IR (KBr):
3119, 1700, 1488, 1165, 1096, 832, 651 cm-1. HRMS (EI-TOF):
calcd for C10H5ClF6O (M+) 289.9933, found 289.9933.
(Z)-4-((1,1,1,4,4,4-hexafluorobut-2-en-2-
yl)oxy)benzaldehyde (3b). White solid, 255 mg, 90%. Mp: 56–
59 C. H NMR (500 MHz, CDCl3) δ 9.90 (s, 1H), 7.84 (d, 2H,
JHH = 9 Hz), 7.09 (d, 2H, JHH = 9 Hz), 6.24 (q, 1H, JHF = 7 Hz).
(Z)-1-bromo-4-((1,1,1,4,4,4-hexafluorobut-2-en-2-
yl)oxy)benzene (3h). Colorless oil, 321 mg, 96%. 1H NMR (500
MHz, CDCl3) δ 7.46 (d, 2H, JHH = 9 Hz), 6.91 (d, 2H, JHH = 9
Hz), 6.19 (q, 1H, JHF = 7 Hz). 13C NMR (125 MHz, CDCl3) δ
154.7, 146.9 (qq, 2JCF = 35.6 Hz, 3JCF = 5.1 Hz), 132.8, 120.9 (q,
1JCF = 269.5 Hz), 118.7 (q, 1JCF = 276.8 Hz), 118.3, 117.4, 111.6
(qq, 2JCF = 36.8 Hz, 3JCF = 3.6 Hz). 19F NMR (470.0 MHz, CDCl3)
δ -69.4 (s, CF3), -59.6 (d, JFH = 7.1 Hz, CF3). IR (KBr): 3114,
1700, 1483, 1213, 1165, 826, 647 cm-1. HRMS (EI-TOF): calcd
for C10H5BrF6O (M+) 333.9428, found 333.9429.
o
1
2
13C NMR (125 MHz, CDCl3) δ 190.4, 160.1, 146.2 (qq, JCF
=
36.4 Hz, 3JCF = 5.1 Hz), 132.9, 131.9, 120.8 (q, 1JCF = 269.7 Hz),
118.8 (q, 1JCF = 276.3 Hz), 116.6, 112.8 (qq, 2JCF = 37 Hz, 3JCF
=
3.5 Hz). 19F NMR (470.0 MHz, CDCl3) δ -69.9 (s, CF3), -59.8 (d,
JFH = 6.6 Hz, CF3). IR (KBr): 3105, 1696, 1603, 1270, 1157, 828,
648 cm-1. HRMS (EI-TOF): calcd for C11H6F6O2 (M+) 284.0272,
found 284.0270.
(Z)-1-(4-((1,1,1,4,4,4-hexafluorobut-2-en-2-
(Z)-1-((1,1,1,4,4,4-hexafluorobut-2-en-2-yl)oxy)-4-
methoxybenzene (3i). Colorless oil, 269 mg, 94%. H NMR
1
yl)oxy)phenyl)ethanone (3c). White solid, 280 mg, 94%. Mp:
o
44–47 C. 1H NMR (500 MHz, CDCl3) δ 7.99 (d, 2H, JHH = 9
(500 MHz, CDCl3) δ 6.97 (d, 2H, JHH = 9 Hz), 6.84 (d, 2H, JHH
=
Hz), 7.08 (d, 2H, JHH = 9 Hz), 6.28 (q, 1H, JHF = 7 Hz), 2.59 (s,
9 Hz), 6.06 (q, 1H, JHF = 7.5 Hz), 3.77 (s, 3H). 13C NMR (125
3H). 13C NMR (125 MHz, CDCl3) δ 196.3, 159.1, 146.4 (qq, 2JCF
MHz, CDCl3) δ 156.6, 149.1, 147.9 (qq, JCF = 34.7 Hz, JCF
=
2
3
3
1
1
1
= 36.3 Hz, JCF = 5.1 Hz), 133.6, 130.6, 120.8 (q, JCF = 269.7
Hz), 118.9 (q, 1JCF = 276.4 Hz), 116.0, 112.5 (qq, 2JCF = 36.9 Hz,
3JCF = 3.5 Hz), 26.4. 19F NMR (470.0 MHz, CDCl3) δ -69.8 (s,
CF3), -59.8 (d, JFH = 7.5 Hz, CF3). IR (KBr): 3066, 1689, 1605,
1160, 836, 647, 583 cm-1. HRMS (EI-TOF): calcd for C12H8F6O2
(M+) 298.0428, found 298.0428.
5.1 Hz), 121.3 (q, JCF = 269.3 Hz), 119.1 (q, JCF = 277 Hz),
118.1, 114.7, 109.8 (qq, JCF = 36.5 Hz, JCF = 3.7 Hz), 55.5. 19F
NMR (470.0 MHz, CDCl3) δ -68.8 (s, CF3), -59.2 (d, JFH = 6.6
Hz, CF3). IR (KBr): 2842, 1693, 1501, 1157, 1032, 831, 651 cm-1.
HRMS (EI-TOF): calcd for C11H8F6O2 (M+) 286.0428, found
286.0426.
2
3
(Z)-methyl
4-((1,1,1,4,4,4-hexafluorobut-2-en-2-
(Z)-1-((1,1,1,4,4,4-hexafluorobut-2-en-2-yl)oxy)-4-
methylbenzene (3j). Colorless oil, 259 mg, 96%. H NMR (500
1
yl)oxy)benzoate (3d). White solid, 289 mg, 92%. Mp: 58–61 oC.
1H NMR (500 MHz, CDCl3) δ 8.06 (d, 2H, JHH = 9 Hz), 7.06 (d,
2H, JHH = 9 Hz), 6.26 (q, 1H, JHF = 7 Hz), 3.91 (s, 3H). 13C NMR
(125 MHz, CDCl3) δ 166.1, 159.1, 146.5 (qq, 2JCF = 36.1 Hz, 3JCF
MHz, CDCl3) δ 7.12 (d, 2H, JHH = 8 Hz), 6.91 (d, 2H, JHH = 8.5
Hz), 6.11 (q, 1H, JHF = 7 Hz), 2.31 (s, 3H). 13C NMR (125 MHz,
CDCl3) δ 153.5, 147.5 (qq, 2JCF = 35.3 Hz, 3JCF = 5.1 Hz), 134.2,
130.2, 121.1 (q, 1JCF = 269.4 Hz), 119.1 (q, 1JCF = 277 Hz) 116.5,
= 5 Hz), 131.7, 126.5, 120.8 (q, 1JCF = 269.8 Hz), 118.9 (q, 1JCF
=
276.4 Hz), 115.9, 112.3 (qq, 2JCF = 36.9 Hz, 3JCF = 3.5 Hz), 52.1.
110.5 (qq, JCF = 36.5 Hz, JCF = 3.7 Hz), 20.6. 19F NMR (470.0
MHz, CDCl3) δ -69.1 (s, CF3), -59.4 (d, JFH = 7.1 Hz, CF3). IR
(KBr): 2931, 1695, 1507, 1388, 1159, 860, 650 cm-1. HRMS (EI-
TOF): calcd for C11H8F6O (M+) 270.0479, found 270.0479.
2
3
19F NMR (470.0 MHz, CDCl3) δ -69.8 (s, CF3), -59.8 (d, JFH
=
6.1 Hz, CF3). IR (KBr): 3103, 1732, 1605, 1160, 852, 763, 647
cm-1. HRMS (EI-TOF): calcd for C12H8F6O3 (M+) 314.0378,
found 314.0379.
(Z)-1-((1,1,1,4,4,4-hexafluorobut-2-en-2-yl)oxy)-4-
isopropylbenzene (3k). Colorless oil, 271 mg, 91%. H NMR
(500 MHz, CDCl3) δ 7.18 (d, 2H, JHH = 8.5 Hz), 6.94 (d, 2H, JHH
1
(Z)-4-((1,1,1,4,4,4-hexafluorobut-2-en-2-yl)oxy)benzonitrile
o
1
(3e). White solid, 272 mg, 97%. Mp: 47–49 C. H NMR (500
MHz, CDCl3) δ 7.68 (d, 2H, JHH = 9 Hz), 7.12 (d, 2H, JHH = 9
Hz), 6.33 (q, 1H, JHF = 7.1 Hz). 13C NMR (125 MHz, CDCl3) δ
= 9 Hz), 6.12 (q, 1H, JHF = 7 Hz), 2.88 (m, 1H), 1.23 (d, 6H, JHH
= 7 Hz). 13C NMR (125 MHz, CDCl3) δ 153.6, 147.6 (qq, JCF
=
2
2
3
158.6, 145.9 (qq, JCF = 36.6 Hz, JCF = 5 Hz), 134.3, 120.6 (q,
35.1 Hz, 3JCF = 5.1 Hz), 145.5, 127.6, 121.2 (q, 1JCF = 269.3 Hz),
1JCF = 269.7 Hz), 118.9 (q, 1JCF = 276.3 Hz), 117.9, 116.9, 113.1
119.1 (q, 1JCF = 277 Hz), 116.5, 110.6 (qq, 2JCF = 36.6 Hz, 3JCF
=
2
3
(qq, JCF = 37 Hz, JCF = 3.5 Hz), 108.5. 19F NMR (470.0 MHz,
CDCl3) δ -69.9 (s, CF3), -59.9 (d, JFH = 7.1 Hz, CF3). IR (KBr):
3061, 2235, 1509, 1160, 832, 641, 546 cm-1. HRMS (EI-TOF):
calcd for C11H5F6NO (M+) 281.0275, found 281.0275.
3.7 Hz), 33.4, 23.9. 19F NMR (470.0 MHz, CDCl3) δ -69.0 (s,
CF3), -59.4 (d, JFH = 7.1 Hz, CF3). IR (KBr): 2966, 1700, 1504,
1271, 1213, 1160, 647 cm-1. HRMS (EI-TOF): calcd for
C13H12F6O (M+) 298.0792, found 298.0791.
(Z)-1-((1,1,1,4,4,4-hexafluorobut-2-en-2-yl)oxy)-4-
(trifluoromethyl)benzene (3f). Colorless oil, 211 mg, 65%. H
(Z)-2-((1,1,1,4,4,4-hexafluorobut-2-en-2-yl)oxy)-1,3-
dimethylbenzene (3l). Colorless oil, 284 mg, 99%. H NMR
1
1
NMR (500 MHz, CDCl3) δ 7.63 (d, 2H, JHH = 8.5 Hz), 7.11 (d,
(500 MHz, CDCl3) δ 7.10-7.05 (m, 3H), 5.70 (q, 1H, JHF = 7.5

5
Hz), 2.28 (s, 6H). 13C NMR (125 MHz, CDCl3) δ 150.4, 148.3
(Z)-(1,1,1,4,4,4-hexafluorobut-2-en-2-yl)(p-tolyl)sulfane
2
3
1
(qq, JCF = 33 Hz, JCF = 5.4 Hz), 130.4, 128.9, 126.1, 121.6 (q,
(5b).14 Colorless oil, 263 mg, 92%. H NMR (500 MHz, CDCl3)
δ 7.39 (d, 2H, JHH = 8 Hz), 7.15 (d, 2H, JHH = 8 Hz), 6.57 (q, 1H,
JHF = 7 Hz), 2.35 (s, 3H). 13C NMR (125 MHz, CDCl3) δ 139.9,
138.8 (qq, 2JCF = 32.6 Hz, 3JCF = 4.8 Hz), 133.9, 130.1, 125.9 (qq,
2JCF = 36.3 Hz, 3JCF = 5.3 Hz), 125.2, 121.5 (q, 1JCF = 270.5 Hz),
121.3 (q, 1JCF = 275.6 Hz), 21.2. 19F NMR (470.0 MHz, CDCl3) δ
-63.8 (s, CF3), -58.5 (d, JFH = 6.1 Hz, CF3). IR (KBr): 2934, 1642,
1329, 1261, 1150, 805, 635 cm-1. HRMS (EI-TOF): calcd for
C11H8F6S (M+) 286.0251, found 286.0251.
1JCF = 268.3 Hz), 118.9 (q, 1JCF = 276.6 Hz), 99.8 (qq, 2JCF = 37.9
3
Hz, JCF = 4.6 Hz), 15.9. 19F NMR (470.0 MHz, CDCl3) δ -69.5
(s, CF3), -57.1 (d, JFH = 8.0 Hz, CF3). IR (KBr): 2934, 1688, 1401,
1265, 1156, 862, 771 cm-1. HRMS (EI-TOF): calcd for
C12H10F6O (M+) 284.0636, found 284.0636.
(Z)-2-((1,1,1,4,4,4-hexafluorobut-2-en-2-yl)oxy)-1,1'-
biphenyl (3m). Colorless oil, 315 mg, 95%. 1H NMR (500 MHz,
CDCl3) δ 7.48 (br, 2H), 7.40 (br, 3H), 7.34 (m, 1H), 7.28 (m, 1H),
7.19 (m, 1H), 6.05 (q, 1H, JHF = 7.5 Hz). 13C NMR (125 MHz,
(Z)-4-((1,1,1,4,4,4-hexafluorobut-2-en-2-yl)thio)aniline (5c).
Yellow solid, 152 mg, 53%. Mp: 42–45 oC. 1H NMR (500 MHz,
CDCl3) δ 7.26 (d, 2H, JHH = 8.5 Hz), 6.60 (d, 2H, JHH = 9 Hz),
6.37 (q, 1H, JHF = 7.5 Hz), 4.12 (br, 2H). 13C NMR (125 MHz,
CDCl3) δ 147.2, 139.9 (qq, 2JCF = 31.9 Hz, 3JCF = 4.8 Hz), 136.5,
CDCl3) δ 152.3, 147.1 (qq, 2JCF = 35.4 Hz, 3JCF = 5.1 Hz), 136.9,
1
132.2, 131.7, 129.4, 128.5, 128.2, 127.6, 124.9, 121.2 (q, JCF
=
269.4 Hz), 119.1 (q, 1JCF = 277 Hz), 115.4, 110.4 (qq, 2JCF = 36.8
Hz, JCF = 3.6 Hz). 19F NMR (470.0 MHz, CDCl3) δ -68.9 (s,
3
2
3
1
CF3), -59.3 (d, JFH = 7.1 Hz, CF3). IR (KBr): 3066, 1695, 1483,
1265, 1160, 747, 651 cm-1. HRMS (EI-TOF): calcd for
C16H10F6O (M+) 332.0636, found 336.0637.
123.7 (qq, JCF = 36.1 Hz, JCF = 5.5 Hz), 121.6 (q, JCF = 270.4
Hz), 121.4 (q, JCF = 275.6 Hz), 115.9, 115.9. 19F NMR (470.0
1
1
MHz, CDCl3) δ -63.3 (s, CF3), -58.3 (d, JFH = 7.5 Hz, CF3). H
NMR (500 MHz, DMSO) δ 7.18 (d, 2H, JHH = 8.5 Hz), 7.02 (q,
1H, JHF = 8 Hz), 6.58 (d, 2H, JHH = 8.5 Hz), 5.65 (s, 2H). 13C
NMR (125 MHz, DMSO) δ 151.4, 139.4 (qq, 2JCF = 31.3 Hz, 3JCF
= 4.9 Hz), 136.6, 124.3 (qq, 2JCF = 34.9 Hz, 3JCF = 5.4 Hz), 122.4
(Z)-3-((1,1,1,4,4,4-hexafluorobut-2-en-2-yl)oxy)-N,N-
dimethylaniline (3n). Colorless oil, 227 mg, 76%. 1H NMR (500
MHz, CDCl3) δ 7.15 (m, 1H), 6.49 (m, 1H), 6.36 (m, 1H), 6.32
(m, 1H), 6.12 (q, 1H, JHF = 7.5 Hz), 2.94 (s, 6H). 13C NMR (125
(q, 1JCF = 270.5 Hz), 121.8 (q, 1JCF = 275.9 Hz), 114.9, 109.9. 19
F
2
3
MHz, CDCl3) δ 156.7, 151.8, 147.4 (qq, JCF = 35.1 Hz, JCF
=
NMR (470.0 MHz, DMSO) δ -61.8 (s, CF3), -57.4 (d, JFH = 8.0
Hz, CF3). IR (KBr): 3336, 1890, 1630, 1259, 1151, 827, 642 cm-1.
HRMS (EI-TOF): calcd for C10H7F6NS (M+) 287.0203, found
287.0203.
5.1 Hz), 129.8, 121.2 (q, 1JCF = 269.4 Hz), 119.1 (q, 1JCF = 277.1
2
3
Hz), 110.7 (qq, JCF = 36.6 Hz, JCF = 3.6 Hz), 108.5, 103.6,
100.8, 40.3. 19F NMR (470.0 MHz, CDCl3) δ -68.9 (s, CF3), -59.4
(d, JFH = 7.5 Hz, CF3). IR (KBr): 2897, 1621, 1277, 1160, 995,
826, 647 cm-1. HRMS (EI-TOF): calcd for C12H11F6NO (M+)
299.0745, found 299.0747.
(Z)-(1,1,1,4,4,4-hexafluorobut-2-en-2-yl)(naphthalen-2-
o
yl)sulfane (5d). White solid, 287 mg, 89%. Mp: 34–35 C. 1H
NMR (500 MHz, CDCl3) δ 8.01 (m, 1H), 7.81 (br, 3H), 7.50 (br,
(Z)-1-((1,1,1,4,4,4-hexafluorobut-2-en-2-
yl)oxy)naphthalene (3o). Colorless oil, 144 mg, 47%. H NMR
3H), 6.69 (q, 1H, JHF = 7.5 Hz). 13C NMR (125 MHz, CDCl3) δ
1
2
3
138.2 (qq, JCF = 33 Hz, JCF = 4.9 Hz), 136.4, 133.5, 133.3,
(500 MHz, CDCl3) δ 8.20 (m, 1H), 7.84 (m, 1H), 7.63 (br, 1H),
7.54 (m, 2H), 7.36 (br, 1H), 6.95 (br, 1H), 6.27 (q, 1H, JHF = 7
Hz). 13C NMR (125 MHz, CDCl3) δ 151.6, 147.5 (qq, 2JCF = 35.6
3
133.2, 129.6, 129.1, 127.8, 127.4, 127.1 (q, JCF = 5 Hz), 127.0,
126.2, 121.5 (q, 1JCF = 270.5 Hz), 121.4 (q, 1JCF = 275.6 Hz). 19
F
NMR (470.0 MHz, CDCl3) δ -63.9 (s, CF3), -58.4 (d, JFH = 7 Hz,
CF3). IR (KBr): 3066, 1647, 1261, 1154, 816, 641, 476 cm-1.
HRMS (EI-TOF): calcd for C14H8F6S (M+) 322.0251, found
322.0251.
3
Hz, JCF = 5.1 Hz), 134.8, 127.7, 127.1, 126.5, 125.1, 125.1,
1
1
124.5, 121.4, 121.2 (q, JCF = 269.5 Hz), 119.1 (q, JCF = 276.9
2
3
Hz), 111.6 (qq, JCF = 36.6 Hz, JCF = 3.5 Hz), 109.5. 19F NMR
(470.0 MHz, CDCl3) δ -69.0 (s, CF3), -59.6 (d, JFH = 7.1 Hz, CF3).
IR (KBr): 3066, 1695, 1393, 1271, 1160, 773, 651 cm-1. HRMS
(EI-TOF): calcd for C14H8F6O (M+) 306.0479, found 306.0479.
(Z)-(1,1,1,4,4,4-hexafluorobut-2-en-2-yl)(4-
methylbenzyl)sulfane (5e). Colorless oil, 207 mg, 69%. 1H
NMR (500 MHz, CDCl3) δ 7.20 (d, 2H, JHH = 8 Hz), 7.13 (d, 2H,
JHH = 8 Hz), 6.52 (q, 1H, JHF = 7.5 Hz), 4.10 (s, 2H), 2.33 (s, 3H).
(Z)-2-((1,1,1,4,4,4-hexafluorobut-2-en-2-
yl)oxy)benzo[d]thiazole (3p). White solid, 303 mg, 97%. Mp:
2
3
13C NMR (125 MHz, CDCl3) δ 138.2 (qq, JCF = 33.5 Hz, JCF
=
o
1
85–87 C. H NMR (500 MHz, CDCl3) δ 7.45 (m, 1H), 7.33 (m,
2
4.9 Hz), 137.9, 131.8, 129.5, 129.1, 125.9 (qq, JCF = 36.1 Hz,
3JCF = 5.6 Hz), 121.7 (q, 1JCF = 274.9 Hz), 121.4 (q, 1JCF = 270.3
Hz), 38.3, 21.1. 19F NMR (470.0 MHz, CDCl3) δ -64.7 (s, CF3), -
59.1 (d, JFH = 6.1 Hz, CF3). IR (KBr): 2927, 1631, 1362, 1259,
1152, 964, 673 cm-1. HRMS (EI-TOF): calcd for C12H10F6S (M+)
300.0407, found 300.0408.
1H), 7.24 (m, 1H), 7.01 (q, 1H, JHF = 6.5 Hz), 6.91 (m, 1H).13C
2
NMR (125 MHz, CDCl3) δ 168.3, 135.5, 132.1 (qq, JCF = 37.6
Hz, 3JCF = 4.9 Hz), 129.0 (qq, 2JCF = 37 Hz, 3JCF = 3.6 Hz), 127.0,
1
1
124.6, 123.0, 122.4, 120.1 (q, JCF = 271.3 Hz), 119.9 (q, JCF
=
276.4 Hz), 111.1. 19F NMR (470.0 MHz, CDCl3) δ -68.9 (s, CF3),
-62.4 (d, JFH = 5.6 Hz, CF3). IR (KBr): 3061, 1687, 1470, 1208,
1151, 857, 739 cm-1. HRMS (EI-TOF): calcd for C11H5F6NOS
(M+) 312.9996, found 312.9997.
(Z)-(4-chlorophenyl)(1,1,1,4,4,4-hexafluorobut-2-en-2-
yl)sulfane (5f). Colorless oil, 272 mg, 89%. 1H NMR (500 MHz,
CDCl3) δ 7.42 (d, 2H, JHH = 8.5 Hz), 7.33 (d, 2H, JHH = 8.5 Hz),
6.66 (q, 1H, JHF = 7 Hz). 13C NMR (125 MHz, CDCl3) δ 137.7
(qq, 2JCF = 33.1 Hz, 3JCF = 4.8 Hz), 136.7, 136.0, 129.6, 127.5 (qq,
2JCF = 36.3 Hz, 3JCF = 5.1 Hz), 127.4, 121.3 (q, 1JCF = 270.6 Hz),
121.2 (q, 1JCF = 275.5 Hz). 19F NMR (470.0 MHz, CDCl3) δ -64.0
(s, CF3), -58.5 (d, JFH = 7.5 Hz, CF3). IR (KBr): 3082, 1642, 1478,
1261, 1154, 826, 641 cm-1. HRMS (EI-TOF): calcd for
C10H5ClF6S (M+) 305.9705, found 305.9705.
(Z)-(1,1,1,4,4,4-hexafluorobut-2-en-2-yl)(4-
methoxyphenyl)sulfane (5a). Colorless oil, 272 mg, 90%. (E/Z
1
= 1/30) H NMR (500 MHz, CDCl3) δ 7.49 (d, 2H, JHH = 9 Hz),
6.90 (d, 2H, JHH = 9 Hz), 6.53 (q, 1H, JHF = 7.5 Hz), 3.84 (s, 3H).
13C NMR (125 MHz, CDCl3) δ 161.1, 139.5 (qq, 2JCF = 32.3 Hz,
2
3
3JCF = 4.8 Hz), 136.4, 124.5 (qq, JCF = 36.4 Hz, JCF = 5.3 Hz),
1
1
121.6 (q, JCF = 270.4 Hz), 121.4 (q, JCF = 275.6 Hz), 118.6,
114.9, 55.3. 19F NMR (470.0 MHz, CDCl3) δ -63.5 (s, CF3), -58.4
(d, JFH = 5.6 Hz, CF3). IR (KBr): 2946, 1594, 1496, 1292, 1150,
1032, 830 cm-1. HRMS (EI-TOF): calcd for C11H8F6OS (M+)
302.0200, found 302.0200.
(Z)-(4-bromophenyl)(1,1,1,4,4,4-hexafluorobut-2-en-2-
yl)sulfane (5g). Colorless oil, 326 mg, 93%. 1H NMR (500 MHz,
CDCl3) δ 7.48 (d, 2H, JHH = 8.5 Hz), 7.34 (d, 2H, JHH = 8.5 Hz),
6.67 (q, 1H, JHF = 7 Hz). 13C NMR (125 MHz, CDCl3) δ 137.6

6
Tetrahedron
2
3
(qq, JCF = 33.3 Hz, JCF = 4.8 Hz), 134.8, 132.6, 128.2, 124.1,
NMR (500 MHz, CDCl3) δ 7.98 (m, 1H), 7.80 (m, 1H), 7.47 (m,
2
3
1
127.8 (qq, JCF = 36.3 Hz, JCF = 5 Hz), 121.4 (q, JCF = 270.5
Hz), 121.4 (q, 1JCF = 275.5 Hz). 19F NMR (470.0 MHz, CDCl3) δ
-64.1 (s, CF3), -58.6 (d, JFH = 7.5 Hz, CF3). IR (KBr): 3082, 1642,
1329, 1255, 1154, 816, 635 cm-1. HRMS (EI-TOF): calcd for
C10H5BrF6S (M+) 349.9200, found 349.9200.
1H), 7.39 (m, 1H), 7.06 (q, 1H, JHF = 7 Hz). 13C NMR (125 MHz,
CDCl3) δ 158.6, 153.1, 136.6, 134.2 (qq, JCF = 36.6 Hz, JCF
4.5 Hz), 132.9 (qq, JCF = 35.6 Hz, JCF = 4.9 Hz), 126.7, 125.7,
123.1, 121.1, 121.1 (q, JCF = 274.9 Hz), 120.7 (q, JCF = 271.4
Hz). 19F NMR (470.0 MHz, CDCl3) δ -66.2 (s, CF3), -59.2 (d, JFH
= 5.6 Hz, CF3). IR (KBr): 3068, 1426, 1259, 1156, 995, 856, 639
cm-1. HRMS (EI-TOF): calcd for C11H5F6NS2 (M+) 328.9768,
found 328.9768.
2
3
=
2
3
1
1
(Z)-methyl
2-((1,1,1,4,4,4-hexafluorobut-2-en-2-
yl)thio)benzoate (5h). White solid, 307 mg, 93%. Mp: 57–60 oC.
1H NMR (500 MHz, CDCl3) δ 7.93 (m, 1H), 7.38 (m, 1H), 7.24
(m, 1H), 7.14 (m, 1H), 6.92 (q, 1H, JHF = 6.5 Hz), 3.88 (s, 3H).
13C NMR (125 MHz, CDCl3) δ 166.5, 136.9 (qq, 2JCF = 33.8 Hz,
1-(2-chloro-1,1,2-trifluoroethoxy)-4-methoxybenzene
(7a).15 Colorless oil, 240 mg, 99%. 1H NMR (500 MHz, CDCl3) δ
7.13 (d, 2H, 3JHH = 9 Hz), 6.88 (d, 2H, 3JHH = 9 Hz), 6.24 (dt, 1H,
3JCF = 5 Hz), 135.4, 133.3 (qq, JCF = 36.1 Hz, JCF = 4.6 Hz),
2
3
1
3
132.6, 131.4, 129.2, 128.8, 126.7, 121.6 (q, JCF = 275.3 Hz),
2JHF = 48 Hz, JHF = 4 Hz), 3.79 (s, 3H). 13C NMR (125 MHz,
121.1 (q, 1JCF = 271 Hz), 52.5. 19F NMR (470.0 MHz, CDCl3) δ -
65.4 (s, CF3), -59.3 (d, JFH = 7.1 Hz, CF3). IR (KBr): 2963, 1718,
1467, 1260, 1145, 855, 638 cm-1. HRMS (EI-TOF): calcd for
C12H8F6O2S (M+) 330.0149, found 330.0148.
CDCl3) δ 157.9, 142.4, 123.0, 118.3 (td, JCF = 267.9 Hz, JCF =
1
2
25.5 Hz), 114.6, 95.1 (dt, 1JCF = 250.3 Hz, 2JCF = 41.6 Hz), 55.6.
19F NMR (470.0 MHz, CDCl3) δ -83.9 ～-84.6 (dd, 2F, JFF
=
3
3
2
37.6 Hz, JFF = 10.8 Hz), -153.3 ～ 153.6 (dt, 1F, JFH = 48.4
Hz,3JFF = 12.2 Hz). IR (KBr): 2939, 1597, 1508, 1193, 1088, 842,
542 cm-1. HRMS (EI-TOF): calcd for C9H8ClF3O2 (M+) 240.0165,
found 240.0166.
(Z)-(1,1,1,4,4,4-hexafluorobut-2-en-2-yl)(4-
nitrophenyl)sulfane (5i). Yellow oil, 70 mg, 22%. 1H NMR (500
MHz, CDCl3) δ 8.13 (d, 2H, JHH = 9 Hz), 7.47 (d, 2H, JHH = 9
Hz), 6.88 (q, 1H, JHF = 7 Hz). 13C NMR (125 MHz, CDCl3) δ
147.7, 139.0, 135.2 (qq, 2JCF = 34.3 Hz, 3JCF = 4.9 Hz), 132.2 (qq,
(2-chloro-1,1,2-trifluoroethyl)(4-methoxyphenyl)sulfane
(7b).16 Colorless oil, 226 mg, 88%. H NMR (500 MHz, CDCl3)
1
2JCF = 36.5 Hz, JCF = 4.8 Hz), 131.3, 124.4, 121.3 (q, JCF
=
δ 7.56 (d, JHH = 8.8 Hz, 2H), 6.92 (d, JHH = 8.9 Hz, 2H), 6.10
3
1
3
3
275.3 Hz), 120.9 (q, JCF = 271.1 Hz). 19F NMR (470.0 MHz,
CDCl3) δ -65.1 (s, CF3), -58.9 (d, JFH = 6.6 Hz, CF3). IR (KBr):
3075, 1524, 1345, 1257, 1154, 854, 745 cm-1. HRMS (EI-TOF):
calcd for C10H5F6NO2S (M+) 316.9945, found 316.9946.
(ddd, 2JHF = 48.3 Hz, 3JHF = 8.0 Hz, 3JHF = 4.0 Hz, 1H). 13C NMR
1
1
(125 MHz, CDCl3) δ 161.8, 138.7, 123.8 (dt, JCF = 284.9 Hz,
2JCF = 27.1 Hz), 115.1, 114.4, 97.0 (ddd, JCF = 252.5 Hz, JCF
=
1
2
38.5 Hz, 2JCF = 33.6 Hz), 55.4. 19F NMR (470.0 MHz, CDCl3) δ -
2
3
85.6 ～-86.6 (dd, 1F, JFF = 221.4 Hz, JFF = 19.3 Hz), -90.4 ～-
(Z)-(1,1,1,4,4,4-hexafluorobut-2-en-2-yl)(3-
2
3
3
91.5 (ddd, 1F, JFF = 221.8 Hz, JFF = 17.9 Hz, JFH = 8.0 Hz), -
147.4 ～-147.8 (dt, 1F, 2JFH = 47.9 Hz,3JFF = 19.3 Hz). IR (KBr):
2944, 1593, 1254, 1176, 1088, 994, 530 cm-1. HRMS (EI-TOF):
calcd for C9H8ClF3OS (M+) 255.9936, found 255.9937.
(trifluoromethyl)phenyl)sulfane (5j). Colorless oil, 122 mg,
1
40%. H NMR (500 MHz, CDCl3) δ 7.65 (s, 1H), 7.57 (m, 2H),
7.41 (m, 1H), 6.67 (q, 1H, JHF = 7 Hz). 13C NMR (125 MHz,
2
3
CDCl3) δ 136.9 (qq, JCF = 33.6 Hz, JCF = 4.9 Hz), 136.1, 132.0
2
3
(q, JCF = 32.9 Hz), 130.8, 129.9, 129.6 (q, JCF = 3.6 Hz), 128.9
1-bromo-4-(2-chloro-1,1,2-trifluoroethoxy)benzene (7c).17
(qq, 2JCF = 36.4 Hz, 3JCF = 5 Hz), 126.1 (q, 3JCF = 3.8 Hz), 122.3,
Colorless oil, 274 mg, 95%. H NMR (500 MHz, CDCl3) δ 7.50
1
121.2 (q, JCF = 270.6 Hz), 121.1 (q, JCF = 275.5 Hz). 19F NMR
(470.0 MHz, CDCl3) δ -64.4 (s, CF3), -63.0 (s, CF3), -58.7 (d, JFH
= 7.1 Hz, CF3). IR (KBr): 2596, 1642, 1424, 1258, 1073, 798,
638 cm-1. HRMS (EI-TOF): calcd for C11H5F9S (M+) 339.9968,
found 339.9969.
(d, 3JHH = 8.5 Hz, 2H), 7.10 (d, 3JHH = 9.0 Hz, 2H), 6.25 (dt, 2JHF
1
1
= 48.1 Hz, JHF = 4.0 Hz, 1H). 13C NMR (125 MHz, CDCl3) δ
3
148.1, 132.8, 123.5, 119.8, 118.2 (dt, 1JCF = 271.5 Hz, 2JCF = 26.0
Hz), 94.9 (dt, JCF = 252.0 Hz, JCF = 41.5 Hz). 19F NMR (470.0
1
2
3
3
MHz, CDCl3) δ -83.8 ～-84.6 (dd, 2F, JFF = 22.09 Hz, JFF
=
11.75 Hz), -153.4～-153.7 (dt, 1F, 2JFH = 48.4 Hz,3JFF = 11.8 Hz).
IR (KBr): 2995, 1892, 1468, 1198, 1088, 843, 493 cm-1. HRMS
(EI-TOF): calcd for C8H5BrClF3O (M+) 287.9164, found
287.9164.
(Z)-(1,1,1,4,4,4-hexafluorobut-2-en-2-
yl)(perfluorophenyl)sulfane (5k). Colorless oil, 326 mg, 90%.
1H NMR (500 MHz, CDCl3) δ 6.68 (q, 1H, JHF =7.5 Hz). 13C
NMR (125 MHz, CDCl3) δ 148.9 (m), 146.9 (m), 144.3 (m),
142.3 (m), 138.8 (m), 136.8 (m), 134.6 (qq, 2JCF = 33.6 Hz, 3JCF
=
(4-bromophenyl)(2-chloro-1,1,2-trifluoroethyl)sulfane (7d).
2
3
1
1
4.4 Hz), 127.1 (qq, JCF = 37.4 Hz, JCF = 5.3 Hz), 121.1 (q, JCF
Colorless oil, 259 mg, 85%. H NMR (500 MHz, CDCl3) δ 7.55
1
3
3
= 270.8 Hz), 120.8 (q, JCF = 275.1 Hz), 102.7 (m). 19F NMR
(d, JHH = 8.5 Hz, 2H), 7.50 (d, JHH = 8.5 Hz, 2H), 6.13 (ddd,
(470.0 MHz, CDCl3) δ -159.9 (m, 2F), -147.9 (t, 1F, JFF = 20.7
2JHF = 48.4 Hz, 3JHF = 7.2 Hz, 3JHF = 4.1 Hz, 1H). 13C NMR (125
1
Hz), -130.8 (d, 2F, JFF = 19.7 Hz), -64.9 (s, CF3), -59.4 (d, JFH
=
MHz, CDCl3) δ 138.3, 132.7, 125.9, 123.8 (td, JCF = 284.4 Hz,
3.8 Hz, CF3). IR (KBr): 3087, 1642, 1517, 1257, 1195, 863, 638
cm-1. HRMS (EI-TOF): calcd for C10HF11S (M+) 361.9623, found
361.9622.
2JCF = 27.6 Hz), 123.1, 97.0 (ddd, 1JCF = 252.9 Hz, 2JCF = 37.8 Hz,
2JCF = 34.4 Hz). 19F NMR (470.0 MHz, CDCl3) δ -83.8 ～-85.3
(dd, 1F, 2JFF = 220.0 Hz, 3JFF = 19.3 Hz), -88.1 ～-89.0 (ddd, 1F,
2JFF = 219.5 Hz, JFF = 17.4 Hz, JFH = 6.6 Hz), -147.2 ～-147.7
(dt, 1F, JFH = 47.9 Hz, JFF = 18.8 Hz). IR (KBr): 2988, 1474,
1086, 993, 820, 764, 490 cm-1. HRMS (EI-TOF): calcd for
C8H5BrClF3S (M+) 303.8936, found 303.8935.
3
3
(Z)-2-((1,1,1,4,4,4-hexafluorobut-2-en-2-yl)thio)pyridine
(5l). Red oil, 237 mg, 87%. H NMR (500 MHz, CDCl3) δ 8.38
2
3
1
(m, 1H), 7.52 (m, 1H), 7.19 (m, 1H), 7.06 (m, 1H), 6.91 (q, 1H,
JHF = 6.5 Hz). 13C NMR (125 MHz, CDCl3) δ 154.5, 150.2, 137.1,
134.1 (qq, 2JCF = 34.8 Hz, 3JCF = 5 Hz), 133.0 (qq, 2JCF = 36.1 Hz,
3JCF = 4.6 Hz), 123.1, 121.8, 121.5 (q, 1JCF = 274.5 Hz), 121.0 (q,
1JCF = 270.9 Hz). 19F NMR (470.0 MHz, CDCl3) δ -66.4 (s, CF3),
-59.5 (d, JFH = 6.1 Hz, CF3). IR (KBr): 3074, 1577, 1453, 1261,
1153, 856, 639 cm-1. HRMS (EI-TOF): calcd for C9H5F6NS (M+)
273.0047, found 273.0042.
1-(1,1,2,3,3,3-hexafluoropropoxy)-4-methoxybenzene
(9a).18 Colorless oil, 227 mg, 83%. 1H NMR (500 MHz, CDCl3) δ
3
3
7.10 (d, JHH = 9.0 Hz, 2H), 6.87 (d, JHH = 9.0 Hz, 2H), 5.06 ～
4.87 (m, 1H), 3.79 (s, 3H). 13C NMR (125 MHz, CDCl3) δ 148.0,
142.0, 123.1, 122.1～115.2 (m), 114.6, 86.5～83.3 (m), 55.5. 19
F
NMR (470.0 MHz, CDCl3) δ -75.0 (q, 3F, J = 8.9 Hz), -77.4 ～-
2
2
78.0 (dm, 1F, JFF = 147.1 Hz), -79.5 ～-80.0 (dm, 1F, JFF
=
(Z)-2-((1,1,1,4,4,4-hexafluorobut-2-en-2-
147.1 Hz), -211.4 ～-211.6 (m, 1F). IR (KBr): 3009, 1508, 1291,
1
yl)thio)benzo[d]thiazole (5m). Yellow oil, 316 mg, 96%. H

7
3
82, 1035, 840, 777, 1092 cm-1. HRMS (EI-TOF): calcd for
C10H8F6O2 (M+) 274.0428, found 274.0429.
13C NMR (125 MHz, CDCl3) δ 156.6, 150.8, 150.3 (q, JCF
=
1
2
5.4 Hz), 123.0 (q, JCF = 267.6 Hz), 118.5, 114.8, 98.3 (q, JCF
=
=
35 Hz), 55.7. 19F NMR (470.0 MHz, CDCl3) δ -57.5 (d, JFH
3
1-chloro-4-(1,1,2,3,3,3-hexafluoropropoxy)benzene
(9b).
7.5 Hz, CF3). IR (KBr): 3010, 2956, 1274, 1151, 1046, 892, 833
cm-1. HRMS (EI-TOF): calcd for C10H9F3O2 (M+) 218.0555,
found 218.0555.
1
Colorless oil, 202 mg, 69%. H NMR (500 MHz, CDCl3) δ 7.35
(d, 3JHH = 9.0 Hz, 2H), 7.15 (d, 3JHH = 8.5 Hz, 2H), 5.08 ～4.90
(m, 1H). 13C NMR (125 MHz, CDCl3) δ 147.1, 132.3, 129.8,
123.2, 121.8～115.2 (m), 84.2～83.2 (m). 19F NMR (470.0 MHz,
(Z)-1-chloro-4-((3,3,3-trifluoroprop-1-en-1-yl)oxy)benzene
(11b).9c Colorless oil, 171 mg, 77%. 1H NMR (500 MHz, CDCl3)
CDCl3) δ -75.0 (q, 3F, J = 9.4 Hz), -77.4 ～-78.0 (dm, 1F, 2JFF
=
147.1 Hz), -79.5 ～-80.1 (dm, 1F, 2JFF = 146.6 Hz), -211.4 ～-
211.5 (m, 1F). IR (KBr): 2926, 1761, 1490, 1386, 1291, 1195,
1092 cm-1. HRMS (EI-TOF): calcd for C9H5ClF6O (M+)
277.9933, found 277.9931.
δ 7.33 (d, JHH = 9 Hz, 2H), 7.00 (d, JHH = 9 Hz, 2H), 6.68 (d,
3
3
3JHH = 7 Hz, 1H), 5.04 (m, 1H). 13C NMR (125 MHz, CDCl3) δ
3
1
155.1, 148.7 (q, JCF = 5.4 Hz), 129.9, 122.7 (q, JCF = 268 Hz),
118.6, 100.0 (q, 2JCF = 35.3 Hz). 19F NMR (470.0 MHz, CDCl3) δ
3
-57.7 (d, JFH = 8.0 Hz, CF3). IR (KBr): 3025, 1650, 1274, 1220,
(Z)-1-methoxy-4-((3,3,3-trifluoroprop-1-en-1-
1153, 890, 833 cm-1. HRMS (EI-TOF): calcd for C9H6ClF3O (M+)
222.0059, found 222.0061.
1
yl)oxy)benzene (11a).9c Colorless oil, 190 mg, 87%. H NMR
(500 MHz, CDCl3) δ 6.98 (d, 3JHH = 9 Hz, 2H), 6.86 (d, 3JHH = 9
3
Hz, 2H), 6.65 (d, JHH = 7 Hz, 1H), 4.93 (m, 1H), 3.78 (s, 3H).
(h) J. Limberger, B.C. Leal, D.F. Back, J. Dupont, A.L. Monteiro,
Adv. Synth. Catal. 354 (2012) 1429;
Acknowledgments
(i) L. Debien, B. Quiclet-Sire, S.S. Zard, Org. Lett. 14 (2012)
5118;
(j) E.J. Cho, S.L. Buchwald, Org. Lett. 13 (2011) 6552;
(k) R. Maeda, K. Ooyama, R. Anno, M. Shiosaki, T. Azema, T.
Hanamoto, Org. Lett. 12 (2010) 2548.
The authors gratefully acknowledge the financial support of
Key Research & Development Plan in Shaanxi Province of China
(2019ZGLGY06-01), and Xi’an Science & Technology Plan
Project (GXYD 12.1).
4.
(a) R. Castarlenas, A. Di Giuseppe, J.J. Pérez-Torrente, L.A. Oro,
Angew. Chem. Int. Ed. 52 (2013) 211;
(b) M.J. Pouy, S.A. Delp, J. Uddin, V.M. Ramdeen, N.A.
Cochrane, G.C. Fortman, T.B. Gunnoe, T.R. Cundari, M. Sabat,
W.H. Myers, ACS Catal. 2 (2012) 2182;
(c) C.J. Weiss, T.J. Marks, J. Am. Chem. Soc. 132 (2010) 10533;
(d) C.J. Weiss, S.D. Wobser, T.J. Marks, J. Am. Chem. Soc. 131
(2009) 2062;
Conflicts of interest
There are no conflicts to declare.
References
(e) J. Kim, W. Jeong, Y.H. Rhee, Org. Lett. 19 (2017) 242;
(f) J. Chen, S.K. Goforth, B.A. McKeown, T.B. Gunnoe, Dalton
Trans. 46 (2017) 2884;
(g) Z.–T. Liu, Y.–H. Wang, F.–L. Zhu, X.–P. Hu, Org. Lett. 18
(2016) 1190;
(h) C. Yang, K. Zhang, Z. Wu, H. Yao, A. Lin, Org. Lett. 18
(2016) 5332;
(i) H. Murayama, K. Nagao, H. Ohmiya, M. Sawamura, Org. Lett.
17 (2015) 2039;
1.
(a) H. Wang, Q. Lu, C.–W. Chiang, Y. Luo, J. Zhou, G. Wang, A.
Lei, Angew. Chem. Int. Ed. 56 (2017) 595;
(b) Z.–B. Zhu, S.F. Kirsch, Chem. Commun. 49 (2013) 2272;
(c) Y. Li, A. Studer, Org. Lett. 19 (2017) 666;
(d) Y.–M. Lin, G.–P. Lu, R.–K. Wang, W.–B. Yi, Org. Lett. 19
(2017) 1100;
(e) J.R. Schmink, S.A. Baker Dockrey, T. Zhang, N. Chebet, A.
Van Venrooy, M. Sexton, S.I. Lew, S. Chou, A. Okazaki, Org.
Lett. 18 (2016) 6360;
(f) S. Lin, S.D. Lies, C.S. Gravatt, T.P. Yoon, Org. Lett. 19 (2017)
368;
(g) Y. Huang, J. Ding, C. Wu, H. Zheng, Z. Weng, J. Org. Chem.
80 (2015) 2912;
(h) M.S. Kabir, M. Lorenz, M.L. Van Linn, O.A. Namjoshi, S.
Ara, J.M. Cook, J. Org. Chem. 75 (2010) 3626;
(i) T. Hanamot, R. Anno, K. Yamada, K. Ryu, R. Maeda, K. Aoi,
H. Furuno, Tetrahedron 65 (2009) 2757;
(j) Y. Zhang, D. Wu, Z. Weng, Org. Chem. Front. 4 (2017) 2226.
(a) G. Couture, B. Campagne, A. Alaaeddine, B. Améduri, Polym.
Chem. 4 (2013) 1960;
(b) E. Girard, T. Tassaing, C. Ladavière, J.–D. Marty, M.
Destarac, Macromolecules 45 (2012) 9674;
(c) G. Kostov, M. Holan, B. Ameduri, M.H. Hung,
Macromolecules 45 (2012) 7375;
(d) C. Boyer, B. Ameduri, M.H. Hung, Macromolecules 43 (2010)
3652;
(e) A. Meskini, M. Raihane, Macromolecules 42 (2009) 3532;
(f) D. Valade, F. Boschet, B. Améduri, Macromolecules 42 (2009)
7689;
(g) E. Boz, A.J. Nemeth, K.B. Wagener, Macromolecules 41
(2008) 1647;
(h) B. Baradie, M.S. Shoichet, Macromolecules 38 (2005) 5560.
(a) A.N. Desnoyer, J.A. Love, Chem. Soc. Rev. 46 (2017) 197;
(b) T. Gensch, F.J.R. Klauck, F. Glorius, Angew. Chem. Int. Ed.
55 (2016) 11287;
(c) L. Jiang, J. Qian, W. Yi, G. Lu, C. Cai, W. Zhang, Angew.
Chem. Int. Ed. 54 (2015) 14965;
(d) X. Zeng, S. Liu, Z. Shi, B. Xu, Org. Lett. 18 (2016) 4770;
(e) D. Kundu, M. Tripathy, P. Maity, B.C. Ranu, Chem. Eur. J. 21
(2015) 8727;
(f) D. Kundu, P. Maity, B.C. Ranu, Org. Lett. 16 (2014) 1040;
(g) S.N. Riduan, J.Y. Ying, Y. Zhang, Org. Lett. 14 (2012) 1780;
(j) C. Brinkmann, A.G.M. Barrett, M.S. Hill, P.A. Procopiou, S.
Reid, Organometallics 31 (2012) 7287.
5.
(a) A. Zhdanko, M.E. Maier, ACS Catal. 5 (2015) 5994;
(b) J.A. Goodwin, A. Aponick, Chem. Commun. 51 (2015) 8730;
(c) A. Zhdanko, M.E. Maier, ACS Catal. 4 (2014) 2770;
(d) X. Yu, S.Y. Seo, T.J. Marks, J. Am. Chem. Soc. 129 (2007)
7244;
(e) Z.J. Wang, C.J. Brown, R.G. Bergman, K.N. Raymond, F.D.
Toste, J. Am. Chem. Soc. 133 (2011) 7358;
(f) H. Shigehisa, T. Aoki, S. Yamaguchi, N. Shimizu, K. Hiroya,
J. Am. Chem. Soc. 135 (2013) 10306;
(g) D.–M. Cui, Z.–L. Zheng, C. Zhang, J. Org. Chem. 74 (2009)
1426;
(h) V. Belting, N. Krause, Org. Lett. 8 (2006) 4489;
(i) M.S. Hadfield, A.–L. Lee, Org. Lett. 12 (2010) 484.
(a) C.A. Smith, S.E. Motika, L. Wojtas, X. Shi, Chem. Commun.
53 (2017) 2315;
(b) A.B. Pritzius, B. Breit, Angew. Chem. Int. Ed. 54 (2015) 3121;
(c) M.R. Kuram, M. Bhanuchandra, A.K. Sahoo, Angew. Chem.
Int. Ed. 52 (2013) 4607;
(d) M. Beller, J. Seayad, A. Tillack, H. Jiao Angew. Chem. Int.
Ed. 43 (2004) 3368;
2.
6.
(e) L. Palacios, M.J. Artigas, V. Polo, F.J. Lahoz, R. Castarlenas,
J.J. Pérez-Torrente, L.A. Oro, ACS Catal. 3 (2013) 2910;
(f) A.A. Trifonov, I.V. Basalovb, A.A. Kisselb, Dalton Trans. 45
(2016) 19172;
(g) S.D. Wobser, T.J. Marks, Organometallics 32 (2013) 2517;
(h) T. Tamai, A. Ogawa, J. Org. Chem. 79 (2014) 5028;
(i) J. Yang, A. Sabarre, L.R. Fraser, B.O. Patrick, J.A. Love, J.
Org. Chem. 74 (2009) 182;
3.
(j) A. Kondoh, H. Yorimitsu, K. Oshima, Org. Lett. 9 (2007) 1383.
(a) J. Miró, C. Del Pozo, Chem. Rev. 116 (2016) 11924;
(b) S. Dupuy, D. Gasperini, S.P. Nolan, ACS Catal. 5 (2015) 6918;
7.

8
Tetrahedron
(c) Y. Zhu, W. Zhou, E.M. Petryna, B.R. Rogers, C.S. Day, A.C.
Jones, ACS Catal. 6 (2016) 7357;
11. (a) H.G. Yayla, H. Wang, K.T. Tarantino, H.S. Orbe, R.R.
Knowles, J. Am. Chem. Soc. 138 (2016) 10794;
(b) D.B. Grotjahn, Y. Gong, A.G. DiPasquale, L.N. Zakharov,
A.L. Rheingold, Organometallics 25 (2006) 5693;
(c) M. Deponti, S.I. Kozhushkov, D.S. Yufit, L. Ackermann, Org.
Biomol. Chem. 11 (2013) 142;
(d) K.D. Hesp, M. Stradiotto, J. Am. Chem. Soc. 132 (2010)
18026;
(e) M.R. Fructos, M.M. Díaz-Requejo, P.J. Pérez, Chem.
Commun. 52 (2016) 7326;
(f) T. Tamai, K. Fujiwara, S. Higashimae, A. Nomoto, A. Ogawa,
Org. Lett. 18 (2016) 2114;
(d) M. Jiménez-Tenorio, M.C. Puerta, P. Valerga, Inorg. Chem. 50
(2011) 12399.
(g) A. Gómez-Suárez, Y. Oonishi, A.R. Martin, S.V.C.
Vummaleti, D.J. Nelson, D.B. Cordes, A.M.Z. Slawin, L. Cavallo,
S.P. Nolan, A. Poater, Chem. Eur. J. 22 (2016) 1125.
(a) M.R. Kuram, M. Bhanuchandra, A.K. Sahoo, J. Org. Chem. 75
(2010) 2247;
(b) Y. Oonishi, A. Gómez-Suárez, A.R. Martin, S.P. Nolan,
Angew. Chem. Int. Ed. 52 (2013) 9767;
(c) F. Lazreg, S. Guidone, A. Gómez-Herrera, F. Nahra, C.S.J.
Cazin, Dalton Trans. 46 (2017) 2439;
(a) I. Morales-Becerril, M. Flores-Álamo, A. Tlahuext-Aca, A.
Arévalo, J.J. García, Organometallics 33 (2014) 6796;
(b) B. Zhao, Y. Li, D.–H. Tu, W. Zhang, Z.–T. Liu, J. Lu,
Tetrahedron Lett. 57 (2016) 4345;
(c) K. Dai, K. Wang, Y. Li, J.–G. Chen, Z.–W. Liu, J. Lu, Z.–T.
Liu, J. Org. Chem. 82 (2017) 4721.
12. (a) C.–C. Li, X.–J. Dai, H. Wang, D. Zhu, J. Gao, C.–J. Li, Org.
Lett. 20 (2018) 3801;
(b) V. Maslivetc, C. Barrett, N.A. Aksenov, M. Rubinaa, M.
Rubin, Org. Biomol. Chem. 16 (2018) 285;
(c) S. Keereewan, D. Soorukram, C. Kuhakarn, V. Reutrakul, M.
Pohmakotr, Eur. J. Org. Chem. 3 (2018) 295;
(d) S. Sultana, J.–J. Shim, S.H. Kim, Y.R. Lee, Org. Biomol.
Chem. 16 (2018) 6749;
(e) Y. Takahashi, R. Yoshii, T. Sato, N. Chida, Org. Lett. 20 (2018)
5705;
(f) M.–G. Zhou, R.–H. Dai, S.–K. Tian, Chem. Commun. 54
(2018) 6036.
8.
9.
13. (a) C.L. Bumgardner, J.E. Bunch, M.-H. Whangbo, Tetrahedron
Lett. 27 (1986) 1883;
(b) S.–L. Zhang, H.–X. Wan, W.–F. Bie Org. Lett. 19 (2017) 6372;
(c) N.D. Epiotis, D. Bjorkist, L. Bjorkist, S. Sarkanen, J. Am.
Chem. Soc. 95 (1973) 7558;
10. (a) A. Kondoh, K. Takami, H. Yorimitsu, K. Oshima, J. Org.
Chem. 70 (2005) 6468;
(b) M.T. Herrero, J.D. Sarralde, R. SanMartin, L. Bravo, E.
Domínguez, Adv. Synth. Catal. 354 (2012) 3054;
(c) G. Martinez-Ariza, M. Ayaz, S.A. Roberts, W.A. Rabanal-
León, R. Arratia-Pérez, C. Hulme, Angew. Chem. Int. Ed. 54
(2015) 11672;
(d) K.B. Zou, X.H. Yin, W.Q. Liu, R.H. Qiu, R.X. Li, L.L. Shao,
Y.H. Li, X.H. Xu, R.H. Yang Synthetic Communications 39 (2009)
2464;
(d) F. Bemardi, N.D. Epiotis, R.L. Yates, H.B. Schlegel, J. Am.
Chem. Soc. 98 (1976) 2385;
(e) P.V.R. Schleyer, J.D. Dill, J.A. Pople, W.J. Hehre, Tetrahedron
22 (1977) 2497.
14. R.D. Chambers, A.R. Edwards, Tetrahedron 54 (1998) 4949.
15. C. Wakselman, M. Tordeux, J. Org. Chem. 50 (1985) 4047.
16. C.M. Timperley, M.J. Waters, J.A. Greenall, Journal of Fluorine
Chemistry 127 (2006) 249.
(e) F. Lima, U.K. Sharma, L. Grunenberg, D. Saha, S. Johannsen,
J. Sedelmeier, E.V. Van der Eycken, S.V. Ley, Angew. Chem. Int.
Ed. 56 (2017) 15136;
(f) K.J. Schwarz, C.M. Pearson, G.A. Cintron-Rosado, P. Liu,
T.N. Snaddon, Angew. Chem. Int. Ed. 57 (2018) 7800;
(g) J. Song, Z.-J. Zhang, S.–S. Chen, T. Fan, L.–Z. Gong, J. Am.
Chem. Soc. 140 (2018) 3177;
17. M.M. Kremlev, A.I. Mushta, L.I. Moklyarchuk, Russian Journal
of Organic Chemistry 39 (2003) 1125.
18. X.M. Du, B.H. Yang, C.M. Hu, Acta Chimica Sinica 44 (1986)
604.
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(h) Y.–J. Yu, F.–L. Zhang, J. Cheng, J.–H. Hei, W.–T. Deng, Y.–
F. Wang, Org. Lett. 20 (2018) 24.
Graphical Abstract
Highlights




Two-phase reaction
Mild reaction conditions
High Z selectivity
100% Atom utilization
Conflict of interest statement
We declare that we have no financial and personal
relationships with other people or organizations that
can inappropriately influence our work, there is no
professional or other personal interest of any nature
or kind in any product, service and/or company that
could be construed as influencing the position
presented in, or the review of, the manuscript
entitled, “Base catalyzed stereoselective
hydrophenoxylation and hydrothiolation of
hexafluorobutyne”.

1
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template box below.
Base-catalyzed stereoselective
hydrophenoxylation and hydrothiolation of
hexafluorobutyne
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Zhao Boa , Zeng Ji-Juna , Han Shenga , Tu Dong-Huaia , Li Jiang-Weia , Zhang Wei and Lu Jian
State Key Laboratory of Fluorine & Nitrogen Chemicals, Xi’an Modern Chemistry Research Institute, Xi’an,
710065, China.
F3C
H
Mild reaction conditions
High Z selectivity
100% atom utilization
DBU
Ar
XH
+
F3C
CF3
Ar
X
CF3
X = O, S
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X = O, S