Copper-mediated oxidative pentafluoroethylthiolation of aryl boronic acids with TMSC2F5 and elemental sulfur

Article abstract of DOI:10.1016/j.jfluchem.2017.07.008

A copper-mediated oxidative pentafluoroethylthiolation of aryl boronic acids with TMSC₂F₅ and S₈ was developed. This reaction provides a new access to various aryl pentafluoroethyl thioethers. The use of 2-fluoropyridine as the ligand and the ability to carry out the reaction at 70 °C are key features of this oxidative coupling reaction.

Full text of DOI:10.1016/j.jfluchem.2017.07.008

Accepted Manuscript
Title: Copper-mediated oxidative pentafluoroethylthiolation of
aryl boronic acids with TMSC2F5 and elemental sulfur
Authors: Jia-Xiang Xiang, Xiu-Hua Xu, Feng-Ling Qing
PII:
S0022-1139(17)30290-7
DOI:
Reference:
http://dx.doi.org/doi:10.1016/j.jfluchem.2017.07.008
FLUOR 9016
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28-6-2017
18-7-2017
18-7-2017
Please cite this article as: Jia-Xiang Xiang, Xiu-Hua Xu, Feng-Ling
Qing, Copper-mediated oxidative pentafluoroethylthiolation of aryl
boronic acids with TMSC2F5 and elemental sulfur, Journal of Fluorine
Chemistryhttp://dx.doi.org/10.1016/j.jfluchem.2017.07.008
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Copper-mediated oxidative pentafluoroethylthiolation of aryl boronic acids with
TMSC2F5 and elemental sulfur
Jia-Xiang Xianga, Xiu-Hua Xua, Feng-Ling Qinga,b
aKey Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, University of
Chinese Academy of Sciences, Chinese Academy of Science, 345 Lingling Lu, Shanghai 200032, China
bCollege of Chemistry, Chemical Engineering and Biotechnology, Donghua University, 2999 North
Renmin Lu, Shanghai 201620, China
Tel.: 86-21-54925187; Fax: 86-21-64166128; E-mail: flq@mail.sioc.ac.cn
 Corresponding author. Tel.: +86 21 54925187; fax: +86 21 64166128.
E-mail address: flq@mail.sioc.ac.cn (F.-L. Qing).
1

Graphical Abstract
Research Highlights:
 Oxidative pentafluoroethylthiolation of aryl boronic acids was developed.

The oxidative reaction provided a new access to aryl pentafluoroethyl thioethers.
 The ligand and reaction temperature were crucial to this reaction.
Abstract
A copper-mediated oxidative pentafluoroethylthiolation of aryl boronic acids with TMSC2F5 and S8
was developed. This reaction provides a new access to various aryl pentafluoroethyl thioethers. The use
of 2-fluoropyridine as the ligand and the ability to carry out the reaction at 70 °C are key features of this
oxidative coupling reaction.
Keywords: Pentafluoroethylthiolation; Oxidative coupling reaction; Aryl pentafluoroethyl thioethers;
Boronic Acids; Copper.
2

1. Introduction
Due to the particular physicochemical effects imparted by fluorine, the incorporation of fluorine-
containing functional groups into organic molecules has emerged as a common strategy in the drug
discovery process [1]. For example, the highly lipophilic trifluoromethylthio group (SCF3, πR = 1.44) is
normally incorporated into bioactive molecules to induce an even higher lipophilicity and membrane
permeability [2]. Consequently, recent years have witnessed a tremendous development in new synthetic
methods of SCF3-containing compounds [3,4]. However, there are a few methods available for
preparation of analogous SC2F5-containing compounds, despite these compounds are potential useful in
pharmaceuticals and agrochemicals [5].
Traditional methods to access pentafluoroethyl thioethers are mainly based on pentafluoroethylation of
thiols [6] or disulfides [7]. However, these methods suffer from the limited availability of sulfur-
containing substrates. Recently, the direct pentafluoroethylthiolation strategies have emerged attractive
approaches to pentafluoroethyl thioethers. In 2015, Billard reported a Friedel-Crafts type
pentafluoroethylthiolation of electron-rich aromatic compounds with electrophilic TsN(Me)SC2F5
(Scheme 1a) [8]. In the same year, Zhang and co-workers disclosed a copper-catalyzed electrophilic
pentafluoroethylthiolation of indole with C2F5SO2Na in the presence of (EtO)2P(O)H and DMSO
(Scheme 1b) [9]. Very recently, a copper-catalyzed Sandmeyer-type pentafluoroethylthiolation of
aromatic and heteroaromatic diazonium salts with nucleophilic Me4NSC2F5 was described by Goossen
for the convenient synthesis of pentafluoroethyl thioethers (Scheme 1c) [10]. Despite the above progress,
there is still great demand for the development of new pentafluoroethylthiolation methods.
In 2012, we have developed the first example of copper-catalyzed oxidative trifluoromethylthiolation
of arylboronic acids using TMSCF3 and S8 at room temperature [11]. Later this three-complement
3

coupling strategy has been employed by different groups for the synthesis of a series of trifluoromethyl
thioethers [12]. Inspired by these results, we envisioned that analogous three-complement oxidative
pentafluoroethylthiolation should be feasible. Herein we describe a copper-mediated oxidative
pentafluoroethylthiolation of arylboronic acids with TMSC2F5 and S8 (Scheme 1d). This reaction
provides a complementary method for preparation of aryl pentafluoroethyl thioethers. Compared with
other pentafluoroethylthiolation strategies, the current one avoids the use of pentafluoroethylthiolating
reagents, which are not commercially available.
2. Results and Discussion
Initially, phenylboronic acid (1a) was chosen as the test substrate to react with S8 (3.0 equiv) and
TMSC2F5 (3.0 equiv) in the presence of K3PO4 (3.0 equiv), Ag2CO3 (2.0 equiv), CuSCN (0.1 equiv),
Phen (0.2 equiv), and 4 Å MS in DMF at room temperature under the oxidative
trifluoromethylthiolation conditions [11] (Table 1, entry 1). To our disappointment, none of the desired
product 2a was detected. When the reaction was performed using stoichiometric amounts of CuSCN and
Phen, PhSC2F5 (2a) was observed in only 3% yield along with the byproduct PhC2F5 in 6% yield (entry
2). Then, CCl4 and CS2 were added to the reaction mixture, respectively, to increase the solubility of S8
in DMF (entries 3 and 4). We hoped that the additive could improve the efficiency of S8. Indeed, the
yield of PhSC2F5 (2a) was slightly improved and the byproduct PhC2F5 was not detected. However, the
yield was not improved when the amount of CS2 was increased (entry 5). Subsequently, the
investigation of different ligands (entries 6-12) revealed that 2-fluoropyridine was optimal affording
product 2a in 28% yield (entry 8). Finally, the reaction temperatures were examined (entries 13-16). To
our delight, the yield of 2a was dramatically increased to 77% when the reaction was carried out at 70
oC (entry 15). Noteworthily, 2a was not formed when the reaction was conducted in the absence of S8
(entry 17), which indicated that S8 was the sole sulfur source of the oxidative pentafluoroethylthiolation.
4

With the optimized reaction conditions in hand (Table 1, Entry 15), we next investigated the
substrate scope of this transformation. As shown in Table 2, both electron-rich and electron-deficient
boronic acids (1b-1m) were transformed into the corresponding pentafluoroethyl thioethers in moderate
to high yields. A series of functionalities including ether, thioether, ester, sulfone, nitro, and halides
were well tolerated. The oxidative pentafluoroethylthiolation of meta-substituted boronic acid 1m gave
2m in 47% yield. In the cases of ortho-substituted substrates, the yields were much lower probably due
to the steric hindrance. Furthermore, dibenzo[b,d]thiophen-4-ylboronic acid (1n) and naphthalen-2-
ylboronic acid (1o) underwent the reaction smoothly to give the desired products (2n and 2o) in
moderate yields.
We
also
successfully
extended
the
oxidative
pentafluoroethylthiolation
for
heptafluoropropylthiolation. For example, treatment of aryl boronic acids 1c and 1l with
TMSCF2CF2CF3 under the optimized reaction conditions afforded the corresponding heptafluoropropyl
thioethers 3c and 3l in moderate yields, respectively (Scheme 2).
3. Conclusion
In conclusion, we have developed a new method for the preparation of aryl pentafluoroethyl ethers
by oxidative coupling reactions. The reaction of aryl boronic acids with TMSC2F5 and S8 in the in the
o
presence of Ag2CO3, CuSCN, 2-fluoropyridine, K3PO4, and CS2 in DMF at 70 C afforded the
corresponding aryl pentafluoroethyl thioethers in moderate to high yields. Furthermore, the extension of
this oxidative coupling reaction to heptafluoropropylthiolation is also investigated.
4. Experimental Section
4.1. General information
1H NMR (TMS as the internal standard) and 19F NMR spectra were recorded on a Bruker
5

AM400spectrometer. 13C NMR was recorded on a Bruker AM400 spectrometer. Chemical shifts (δ) are
reported in ppm, and coupling constants (J) are in Hertz (Hz). The following abbreviations were used to
explain the multiplicities: s = singlet, d = doublet, t = triplet, q =quartet, m = multiplet. HRMS using EI
were obtained on a GC-TOF mass spectrometer. Reactions were performed under an atmosphere of
nitrogen using glassware that was flame-dried under vacuum. All reagents were used as received from
commercial sources or prepared as described in references. DMF was distilled under reduced pressure
from CaH2 and stored with 4 Å molecular sieves. Cuprous thiocyanate, anhydrous potassium phosphate
and powdered 4Å molecular sieves were stored in a nitrogen-filled glove box.
4.2. General procedure for oxidative pentafluoroethylthiolation and heptafluoropropylthiolation of aryl
boronic acids
In a glove box, an over-dried 50 mL Schlenk tube equipped with a magnetic stir bar was charged with
4Å molecular sieves (250.0 mg) and K3PO4 (382.1 mg, 1.8 mmol, 3.0 equiv). The vessel was sealed
with a septum and flame-dried under vacuum. After the tube was cooled to room temperature, CuSCN
(73.0 mg, 0.6 mmol, 1.0 equiv), 2-fluoropyridine (57 μL, 0.6 mmol, 1.0 equiv), S8 (60.0 mg, 1.8 mmol,
6.0 equiv), aryl boronic acid (0.6 mmol, 1.0 equiv) and Ag2CO3 (330.9 mg, 1.2 mmol, 2.0 eqiuv) were
added to the tube in a glove box. The tube was then evacuated and backfilled with N2. Freshly distilled
DMF (25 mL) and CS2 (37 μL, 0.6 mmol, 1.0 eqiuv) were then added to the reaction tube, followed by
the addition of TMSCF2CF3 (324 μL, 1.8 mmol, 3.0 equiv) or TMSCF2CF2CF3 (345 μL, 1.8 mmol, 3.0
equiv) after 30 min. Then, the reaction mixture was then placed under a balloon of N2 and was stirred
vigorously for 24 h. Benzotrifluoride (75 μL, 0.6 mmol) was added as an internal standard, and the yield
of the crude reaction was measured by 19F NMR before working up. The reaction solution was filtered
by Celite on silica, eluted with diethyl ether, washed with brine and concentrated. The residue was
purified with silica gel column chromatography to provide pure product.
4.2.1. (Perfluoroethyl)(phenyl)sulfane (2a). Compound 2a was prepared following the general procedure
19
19
in 78% F NMR yield starting from phenylboronic acid (73.2 mg, 0.6 mmol). F NMR (376 MHz,
6

CDCl3): δ ppm -83.22 (t, 3F, J = 3.8 Hz), -92.41 (q, 2F, J = 3.8 Hz). This assignment matched with that
previously published [7d].
4.2.2. (4-(Tert-butyl)phenyl)(perfluoroethyl)sulfane (2b). Compound 2b was prepared following the
general procedure in 65% yield starting from (4-(tert-butyl)phenyl)boronic acid (106.8 mg, 0.6 mmol) as
a yellow liquid. 1H NMR (400 MHz, CDCl3): δ ppm 7.59 (d, 2H, J = 8.0 Hz), 7.45 (d, 2H, J = 8.0 Hz),
1.35 (s, 9H). 19F NMR (376 MHz, CDCl3): δ ppm -82.57 (t, 3F, J = 3.8 Hz), -92.03 (q, 2F, J = 3.8 Hz).
13C NMR (100 MHz, CDCl3): δ ppm 154.6, 137.0, 126.5, 120.2 (tq, J = 289.0 Hz, 40.0 Hz), 119.2 (t, J
= 3.0 Hz), 118.8 (qt, J = 285.0 Hz, 37.0 Hz), 34.9, 30.1. IR (KBr) υmax 2925, 1472, 1216, 1008, 961, 815
cm-1. MS (EI): m/z 284. HRMS: Calculated for C12H13F5S: 284.0658; Found: 284.0669.
4.2.3. (4-Methoxyphenyl)(perfluoroethyl)sulfane (2c). Compound 2c was prepared following the
general procedure in 77% yield starting from (4-methoxyphenyl)boronic acid (91.2 mg, 0.6 mmol) as a
1
yellow liquid. H NMR (400 MHz, CDCl3): δ ppm 7.58 (d, 2H, J = 8.0 Hz), 6.94 (d, 2H, J = 8.0 Hz),
3.82 (s, 3H). 19F NMR (376 MHz, CDCl3): δ ppm -82.56 (t, 3F, J = 3.8 Hz), -92.89 (q, 2F, J = 3.8 Hz).
13C NMR (100 MHz, CDCl3): δ ppm 162.0, 138.9, 120.0 (tq, J = 287.0 Hz, 40.0 Hz), 118.8 (qt, J =
286.1 Hz, 37.0 Hz), 114.9, 113.1 (t, J = 3.0 Hz), 55.3. IR (KBr) υmax 2965, 2361, 1497, 1275, 1105, 962,
830, 764 cm-1. MS (EI): m/z 258. HRMS: Calculated for C9H7F5OS: 258.0132; Found: 258.0132.
4.2.4. Methyl(4-((perfluoroethyl)thio)phenyl)sulfane (2d). Compound 2d was prepared following the
general procedure in 52% yield starting from (4-(methylthio)phenyl)boronic acid (100.8 mg, 0.6 mmol)
1
as a yellow liquid. H NMR (400 MHz, CDCl3): δ ppm 7.51 (d, 2H, J = 8.0 Hz), 7.22 (d, 2H, J = 7.6
Hz), 2.48 (s, 3H). 19F NMR (376 MHz, CDCl3): δ ppm -82.48 (t, 3F, J = 3.8 Hz), -92.32 (q, 2F, J = 3.8
Hz). 13C NMR (100 MHz, CDCl3): δ ppm 143.6, 137.4, 126.2, 120.0 (tq, J = 287.0 Hz, 40.0 Hz), 118.8
(qt, J = 285.0 Hz, 37.0 Hz), 117.91 (t, J = 3.0 Hz), 14.9. IR (KBr) υmax 1475, 1331, 1107, 961, 919 cm-1.
MS (EI): m/z 274. HRMS: Calculated for C9H7F5S2: 273.9909; Found: 273.9917.
7

4.2.5. [1,1'-Biphenyl]-4-yl(perfluoroethyl)sulfane (2e). Compound 2e was prepared following the
general procedure in 60% yield starting from [1,1'-biphenyl]-4-ylboronic acid (118.6 mg, 0.6 mmol) as a
white solid. Mp 49-50 °C. 1H NMR (400 MHz, CDCl3): δ ppm 7.73 (d, 2H, J = 12.0 Hz), 7.65-7.60 (m,
19
4H), 7.49 (d, 2H, J = 8.0 Hz), 7.42 (d, 1H, J = 8.0 Hz). F NMR (376 MHz, CDCl3): δ ppm -82.44 (t,
13
3F, J = 3.8 Hz), -92.82 (q, 2F, J = 3.8 Hz). C NMR (100 MHz, CDCl3): δ ppm 144.1, 138.6, 137.6,
129.0, 128.2, 128.1, 127.2, 121.4 (t, J = 3.0 Hz), 120.4 (tq, J = 285.0 Hz, 40.0 Hz), 118.8 (qt, J = 286.0
Hz, 37.0 Hz). IR (KBr) υmax 1480, 1207, 1008, 963, 750, 720 cm-1. MS (EI): m/z 304. HRMS:
Calculated for C14H9F5S: 304.0345; Found: 304.0335.
4.2.6. Ethyl 4-((perfluoroethyl)thio)benzoate (2f). Compound 2f was prepared following the general
procedure in 58% yield starting from (4-(ethoxycarbonyl)phenyl)boronic acid (116.4 mg, 0.6 mmol) as a
1
yellow liquid. H NMR (400 MHz, CDCl3): δ ppm 8.07 (d, 2H, J = 8.0 Hz), 7.71 (d, 2H, J = 8.0 Hz),
4.39 (q, 2H, J = 8.0 Hz), 1.39 (t, 3H, J = 8.0 Hz). 19F NMR (376 MHz, CDCl3): δ ppm -82.62 (t, 3F, J =
13
3.8 Hz), -90.34 (q, 2F, J = 3.8 Hz). C NMR (100 MHz, CDCl3): δ ppm 165.5, 136.6, 132.8, 130.2,
128.0 (t, J = 3.0 Hz), 120.1 (tq, J = 285.0 Hz, 40.0 Hz), 118.7 (qt, J = 286.0 Hz, 37.0 Hz), 61.4, 14.2. IR
(KBr) υmax 2986, 1728, 1216, 1105, 764, 724 cm-1. MS (EI): m/z 301. HRMS: Calculated for
C11H10F5O2S: 301.0316; Found: 301.0317.
4.2.7. 4-((Perfluoroethyl)thio)benzonitrile (2g). Compound 2g was prepared following the general
procedure in 50% yield starting from (4-cyanophenyl)boronic acid (88.2 mg, 0.6 mmol) as a yellow
liquid. 1H NMR (400 MHz, CDCl3): δ ppm 7.78 (d, 2H, J = 8.0 Hz), 7.72 (d, 2H, J = 8.0 Hz). 19F NMR
13
(376 MHz, CDCl3): δ ppm -82.57 (t, 3F, J = 3.8 Hz), -91.01 (q, 2F, J = 3.8 Hz). C NMR (100 MHz,
CDCl3): δ ppm 137.2, 132.8, 128.9 (t, J = 3.0 Hz), 119.9 (tq, J = 289.0 Hz, 41.0 Hz), 118.4 (qt, J =
285.0 Hz, 36.0 Hz), 117.5, 115.0. MS (EI): m/z 253. HRMS: Calculated for C5H4F5SN: 252.9985;
Found: 252.9979.
4.2.8. (4-(Methylsulfonyl)phenyl)(perfluoroethyl)sulfane (2h). Compound 2h was prepared following the
general procedure in 68% yield starting from (4-(methylsulfonyl)phenyl)boronic acid (120.0 mg, 0.6
8

1
mmol) prepared as a yellow liquid. H NMR (400 MHz, CDCl3): δ ppm 7.99 (q, 2H, J = 8.0 Hz), 7.85
(d, 2H, J = 8.0 Hz), 4.08 (s, 3H). 19F NMR (376 MHz, CDCl3): δ ppm -82.56 (t, 3F, J = 3.8 Hz), -90.87
13
(q, 2F, J = 3.8 Hz). C NMR (100 MHz, CDCl3): δ ppm 143.0, 137.4, 129.8 (t, J = 3.0 Hz), 128.2,
119.9 (tq, J = 285.0 Hz, 40.0 Hz), 118.4 (qt, J = 286.0 Hz, 37.0 Hz), 44.3. IR (KBr) υmax 1320, 1212,
1153, 1107, 778 cm-1. MS (EI): m/z 307. HRMS: Calculated for C9H7F5SO2: 306.9880; Found:
306.9882.
4.2.9. (4-Fluorophenyl)(perfluoroethyl)sulfane (2i). Compound 2i was prepared following the general
procedure in 57% yield, starting from (4-fluorophenyl)boronic acid (84.0 mg, 0.6 mmol). 19F NMR (376
MHz, CDCl3): δ ppm -82.53 (t, 3F, J = 3.8 Hz), -92.91 (q, 2F, J = 1.9 Hz), -109.07 - -109.14 (m, 1F).
This assignment matched with that previously published [10].
4.2.10. (4-Chlorophenyl)(perfluoroethyl)sulfane (2j). Compound 2j was prepared following the general
procedure in 82% yield starting from (4-chlorophenyl)boronic acid (93.8 mg, 0.6 mmol). 19F NMR (376
MHz, CDCl3): δ ppm -82.21 (t, 3F, J = 3.8 Hz), -92.50 (q, 2F, J = 3.8 Hz). This assignment matched
with that previously published [10].
4.2.11. (4-Bromophenyl)(perfluoroethyl)sulfane (2k). Compound 2k was prepared following the general
procedure in 70% yield starting from (4-bromophenyl)boronic acid (120.5 mg, 0.6 mmol) as a yellow
liquid. 1H NMR (400 MHz, CDCl3): δ ppm 7.57 (d, 2H, J = 8.0 Hz), 7.51 (d, 2H, J = 8.0 Hz). 19F NMR
13
(376 MHz, CDCl3): δ ppm -82.53 (t, 3F, J = 3.8 Hz), -92.92 (q, 2F, J = 3.8 Hz). C NMR (100 MHz,
CDCl3): δ ppm 138.5, 132.7, 126.9, 121.8 (t, J = 3.0 Hz), 119.9 (tq, J = 285.0 Hz, 40.0 Hz), 118.4 (qt, J
= 286.0 Hz, 37.0 Hz). IR (KBr) υmax 1475, 1217, 1107, 961, 819 cm-1. MS (EI): m/z 306. HRMS:
Calculated for C8H4BrF5S: 305.9137; Found: 305.9144.
4.2.12. (4-Iodophenyl)(perfluoroethyl)sulfane (2l). Compound 2l was prepared following the general
procedure in 83% yield starting from (4-iodophenyl)boronic acid (148.7 mg, 0.6 mmol) as a yellow
liquid. 1H NMR (400 MHz, CDCl3): δ ppm 7.27 (d, 2H, J = 8.0 Hz), 7.36 (d, 2H, J = 8.0 Hz). 19F NMR
9

13
(376 MHz, CDCl3): δ ppm -82.50 (t, 3F, J = 3.8 Hz), -92.79 (q, 2F, J = 3.8 Hz). C NMR (100 MHz,
CDCl3): δ ppm 138.7, 138.5, 122.57 (t, J = 3.0 Hz), 119.8 (tq, J = 288.0 Hz, 40.0 Hz), 118.6 (qt, J =
285.0 Hz, 36.0 Hz), 98.3. IR (KBr) υmax 2955, 2925, 2375, 1457, 1376, 1024 cm-1. MS (EI): m/z 354.
HRMS: Calculated for C8H4F5IS: 353.8999; Found: 353.9001.
4.2.13. (3-Nitrophenyl)(perfluoroethyl)sulfane (2m). Compound 2m was prepared following the general
procedure in 47% yield starting from (3-nitrophenyl)boronic acid (100.2 mg, 0.6 mmol) as a yellow
liquid. 1H NMR (400 MHz, CDCl3): δ ppm 8.51 (t, 1H, J = 2.0 Hz), 8.38-8.35 (m, 1H), 7.98 (d, 1H, J =
8.0 Hz), 7.64 (t, 1H, J = 8.0 Hz). 19F NMR (376 MHz, CDCl3): δ ppm -82.47 (t, 3F, J = 3.8 Hz), -91.31
(q, 2F, J = 3.8 Hz). 13C NMR (100 MHz, CDCl3): δ ppm 148.5, 142.7, 131.7, 130.4, 126.0, 125.2, 119.9
(tq, J = 288.0 Hz, 40.0 Hz), 118.5 (qt, J = 284.0 Hz, 36.0 Hz). MS (EI): m/z 273.
4.2.14. 4-((Perfluoroethyl)thio)dibenzo[b,d]thiophene (2n). Compound 2n was prepared following the
general procedure in 52% yield starting from dibenzo[b,d]thiophen-4-ylboronic acid (137.2 mg, 0.6
mmol) as a white solid. Mp 71-72 °C. 1H NMR (400 MHz, CDCl3): δ ppm 8.24 (d, 1H, J = 8.0 Hz),
8.09 (q, 1H, J = 2.0 Hz), 7.87 (q, 1H, J = 2.0 Hz), 7.75 (d, 1H, J = 8.0 Hz), 7.51-7.45 (m, 3H). 19F NMR
13
(376 MHz, CDCl3): δ ppm -82.67 (t, 3F, J = 3.8 Hz), -90.65 (d, 2F, J = 3.8 Hz). C NMR (100 MHz,
CDCl3): δ ppm 148.6, 139.3, 136.8, 136.3, 135.5, 127.4, 125.3, 124.8, 124.3, 122.8, 122.0, 120.3 (tq, J
= 288.0 Hz, 40.0 Hz), 118.6 (qt, J = 285.0 Hz, 36.0 Hz), 116.4 (t, J = 3.0 Hz). IR (KBr) υmax 1386, 1250,
1097, 957, 753 cm-1. MS (EI): m/z 334. HRMS: Calculated for C14H7F5S2: 333.9909; Found: 333.9900.
4.2.15. Naphthalen-2-yl(perfluoroethyl)sulfane (2o). Compound 2o was prepared following the general
procedure in 60% yield starting from naphthalen-2-ylboronic acid (103.2 mg, 0.6 mmol) as a yellow
1
19
liquid. H NMR (400 MHz, CDCl3): δ ppm 8.21 (s, 1H), 7.85-7.88 (m, 3H), 7.67-7.54 (m, 3H). F
13
NMR (376 MHz, CDCl3): δ ppm -82.45 (t, 3F, J = 5.6 Hz), -90.62 (q, 2F, J = 1.9 Hz). C NMR (100
MHz, CDCl3): δ ppm 138.0, 134.0, 133.4, 132.5, 129.1, 128.2, 128.0, 127.8, 127.0, 120.4 (tq, J = 288.0
Hz, 40.0 Hz), 119.9 (t, J = 3.0 Hz), 118.8 (qt, J = 285.0 Hz, 37.0 Hz). IR (KBr) υmax 1331, 1101, 964,
859, 749, 477 cm-1. MS (EI): m/z 278. HRMS: Calculated for C12H7F5S: 278.0183; Found: 278.0184.
10

4.2.16. (4-Methoxyphenyl)(perfluoropropyl)sulfane (3c). Compound 3c was prepared following the
general procedure in 70% yield starting from (4-methoxyphenyl)boronic acid (91.2 mg, 0.6 mmol) as a
1
yellow liquid. H NMR (400 MHz, CDCl3): δ ppm 7.55 (d, 2H, J = 8.0 Hz), 6.92 (d, 2H, J = 8.0 Hz),
3.82 (s, 3H). 19F NMR (376 MHz, CDCl3): δ ppm -80.24 (t, 3F, J = 11.4 Hz), -88.75 (qt, 2F, J = 7.6 Hz,
3.8 Hz), -123.78 (t, 2F, J = 3.8 Hz). 13C NMR (100 MHz, CDCl3): δ ppm 162.1, 139.1, 115.0, 112.9 (t, J
= 7.6 Hz), 105.8-125.5 (m), 55.4. IR (KBr) υmax 1471, 1336, 1188, 1116, 1055, 1039, 851, 751 cm-1. MS
(EI): m/z 308. HRMS: Calculated for C10H7F7OS: 308.0106; Found: 308.0107.
4.2.17. (4-Iodophenyl)(perfluoropropyl)sulfane (3l). Compound 3l was prepared following the general
procedure in 51% yield starting from (4-iodophenyl)boronic acid (148.7 mg, 0.6 mmol) as a yellow
liquid. 1H NMR (400 MHz, CDCl3): δ ppm 7.75 (d, 2H, J = 8.0 Hz), 7.86 (d, 2H, J = 8.0 Hz). 19F NMR
(376 MHz, CDCl3): δ ppm -80.16 (t, 3F, J = 11.4 Hz), -87.71 (qt, 2F, J = 7.6 Hz, 3.8 Hz), -123.61 (t, 2F,
J = 1.9 Hz). 13C NMR (100 MHz, CDCl3): δ ppm 138.8, 138.7, 122.5 (t, J = 7.6 Hz), 105.6-125.6 (m),
98.4. IR (KBr) υmax 1593, 1496, 1210, 1113, 1033, 852 cm-1. MS (EI): m/z 404. HRMS: Calculated for
C9H4F7IS: 403.8967; Found: 403.8962.
Acknowledgement. We thank the National Natural Science Foundation of China (21421002, 21332010)
and the Strategic Priority Research Program of the Chinese Academy of Sciences (XDB20000000) for
funding this work.
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15

Scheme 1 Preparation of pentafluoroethyl thioethers by pentafluoroethylthiolation reactions.
Scheme 2 Heptafluoropropylthiolation reactions.
16

Table 1. Optimization of reaction conditions.a
Entry
Ligand
Additive
Temperature
Yield (%)b
1c
2
Phen
Phen
—
—
rt
0
3
rt
rt
3
Phen
CCl4
CS2
CS2
CS2
CS2
CS2
CS2
CS2
CS2
CS2
CS2
CS2
CS2
CS2
CS2
5
4
5d
Phen
rt
17
13
0
Phen
rt
6
—
rt
7
pyridine
rt
24
28
trace
6
8
2-fluoropyridine
3-trifluoromethylpyridine
4-cyanopyridine
2-bromopyrdine
2-methoxypyridine
2-fluoropyridine
2-fluoropyridine
2-fluoropyridine
2-fluoropyridine
2-fluoropyridine
rt
9
rt
10
11
12
13
14
15
16
17e
rt
rt
8
rt
trace
54
62
77
52
0
50 oC
60 oC
70 oC
80 oC
70 oC
aReaction conditions: 1a (0.2 mmol), TMSC2F5 (0.6 mmol), S8 (0.6 mmol), Ag2CO3 (0.4 mmol), CuSCN (0.2 mmol), ligand (0.2
mmol), K3PO4 (0.6 mmol), additive (0.2 mmol), 4 Å MS (50 mg), DMF (8.0 mL), under N2, temperature, 24 h.
bYields were determined by 19F NMR spectroscopy using trifluoromethoxylbenzene as an internal standard.
cCuSCN (0.02 mmol) and Phen (0.04 mmol) were added.
dCS2 (1.0 mmol) was added.
eWithout S8.
17

Table 2. Scope of substrates.a
aReaction conditions: 1 (0.6 mmol), TMSC2F5 (1.8 mmol), S8 (1.8 mmol), Ag2CO3 (1.2 mmol), CuSCN (0.6 mmol), 2-fluoropyridine
(0.6 mmol), K3PO4 (1.8 mmol), CS2 (0.6 mmol), 4 Å MS (250 mg), DMF (25.0 mL), under N2, 70 oC, 24 h, isolated yields.
bYields were determined by 19F NMR spectroscopy using trifluoromethoxylbenzene as an internal standard.
18