Electron donor-acceptor (EDA)-complex enabled SF5Cl addition on alkenes and alkynes

Article abstract of DOI:10.1016/j.jfluchem.2021.109734

A new method for the addition of SF₅Cl on unsaturated compounds was developed, based on the use of an electron donor-acceptor (EDA)-complex and visible light irradiation. The reaction does not require the presence of oxygen to proceed, compared

Full text of DOI:10.1016/j.jfluchem.2021.109734

Journal of Fluorine Chemistry 243 (2021) 109734
Contents lists available at ScienceDirect
Journal of Fluorine Chemistry
journal homepage: www.elsevier.com/locate/fluor
Electron donor-acceptor (EDA)-complex enabled SF5Cl addition on alkenes
and alkynes
´
Audrey Gilbert, Melodie Birepinte, Jean-François Paquin*
´
´
´
PROTEO, CCVC, Departement de chimie, Universite Laval, Quebec, QC, G1V 0A6, Canada
A R T I C L E I N F O
A B S T R A C T
Keywords:
A new method for the addition of SF5Cl on unsaturated compounds was developed, based on the use of an
electron donor-acceptor (EDA)-complex and visible light irradiation. The reaction does not require the presence
of oxygen to proceed, compared to the most-common SF5Cl addition protocols. A total of 19 examples of alkenes
and alkynes were performed, with yields ranging from 31 % to 86 %.
Pentafluorosulfanyl substituent
Chloropentafluorosulfanylation
(EDA)-complexes
Radical addition
Visible-light activation
1. Introduction
necessitate the use of special apparatus [10]. Moreover, the quality and
the concentration of Et3B commercial solutions can largely vary between
In the past decades, the pentafluorosulfanyl (ꢀ SF5) substituent has
attracted more and more attention due to its unique properties. Often
referred to as a "super CF3", the SF5 group shows similar but enhanced
properties when compared to the trifluoromethyl moiety [1]. While the
SF5 group is bulkier and more chemically and thermally stable than its
trifluoromethylated analogue [2], it also induces a stronger dipole
moment (3.44 D for PhSF5 vs. 2.60 D for PhCF3), has a higher
electron-withdrawing capacity (σp = 0.68 vs 0.53 for CF3) as well as a
greater lipophilicity (πp = 1.50 vs. 0.88 for CF3) [3]. These unique
properties account for the increasing occurrence of the penta-
fluorosulfanyl substituent in many fields of organic chemistry, including
medicinal chemistry [4], agrochemistry [5] and material sciences [6].
While the interest toward the SF5 group is increasing, the synthetic
methods to introduce it into organic molecules remain rare. In order to
incorporate the SF5 moiety on aliphatic substrates, Dolbier’s protocol for
the radical addition of SF5X (X = Cl, Br) on unsaturated compounds,
using Et3B as the radical initiator, has emerged as the most versatile one
(Scheme 1A, top) [7]. This method allows the synthesis of a wide range
of aliphatic pentafluorosulfanylated compounds with high yields and
without the need for special apparatus such as microreactors or auto-
claves. It has shown to be compatible with functional groups such as
allylsilanes [8], in addition of being useful for the synthesis of a wide
range of SF5-containing building blocks of interest [9]. However, the use
of Et3B represents a drawback to the reaction. Et3B being air-unstable
and pyrophoric, its use in the laboratory can be challenging, or may
suppliers, therefore limiting the reproducibility of the reactions. In order
to address these issues, we recently reported an alternative reaction to
the Dolbier’s method, using air-stable amine-borane complexes as
radical initiators (Scheme 1A, bottom) [11]. This allowed the SF5Cl
radical addition on several alkenes and alkynes without the use of Et3B.
Nonetheless, the reaction still requires the presence of oxygen for the
initiation of the radical chain, a parameter that can be hard to control.
Indeed, in 2016, Curran and coworker reported a kinetic theory
regarding the use of the Et3B/O2 system as a radical initiator [12]. While
some reactions can be easily initiated with Et3B and small or limited
amount of oxygen, some other Et3B-initiated processes necessitate a
large excess of oxygen to either initiate, or simply keep running. This
difference can be explained by the autooxidation mechanism of Et3B, in
competition with the desired chain-propagation reaction [13]. In a
low-oxygen system, all the steps in the target chain must be faster than
the autooxidation chain. The latter is therefore overrun by the desired
radical chain reaction. Since the reaction of alkyl radicals with oxygen
are typically fast, a low concentration in oxygen can favor the reaction of
•
ethyl radical Et with the desired substrate rather than O2, thus favoring
the desired reaction. It is likely the case with Dolbier’s protocol for the
SF5Cl addition on unsaturated compounds, since only 10 mol% of Et3B
and the residual air in solvent is sufficient for the reaction to occur. In
contrast, with the high-oxygen reaction, the autooxidation of Et3B is
more productive than the target chain reaction, resulting in the need of a
high amount of Et3B and large excess of oxygen for the desired reaction
* Corresponding author.
E-mail address: jean-francois.paquin@chm.ulaval.ca (J.-F. Paquin).
https://doi.org/10.1016/j.jfluchem.2021.109734
Received 14 December 2020; Received in revised form 13 January 2021; Accepted 13 January 2021
Available online 19 January 2021
0022-1139/© 2021 Elsevier B.V. All rights reserved.

A. Gilbert et al.
Journal of Fluorine Chemistry 243 (2021) 109734
to occur. The efficiency of Et3B/O2 initiated reactions is therefore highly
dependant on the concentration of oxygen in the reaction, as well as the
free-radical reaction itself.
tests were performed in order to demonstrate that all the components of
the system are necessary for the desired pentafluorosulfanylation to
occur. Therefore, the reaction was performed without light activation
(entry 3), without the presence of the aldehyde (entry 4) or the amine
(entry 5) and with only light as the initiator (entry 6). In all cases, low
conversions were obtained, and the final compound could not be
detected in the reaction mixture. It was not possible to identify any side-
product resulting from the low conversion, therefore, the conversion
was attributed to degradation products. The reaction conditions
described in entry 1 were chosen as the optimal one.
In a similar vein, we sought to develop new synthetic protocols for
the incorporation of the SF5-moiety on aliphatic derivatives, without
having to rely on an oxygen-based initiation step. In order to do so, we
got inspired by a recent report from Ofuji’s group, in which they per-
formed the photocatalyzed perfluoroalkylation of various olefins and
alkynes, using an electron donor-acceptor (EDA)-complex as the pho-
tocatalyst (Scheme 1B) [14]. EDA-complexes have proven successful
activators or photocatalysts in many perfluoroalkylation reactions [15].
These complexes represent a useful tool for perfluoroalkylation re-
actions, since they are environmentally benign, compared to the use of
metal-based photocatalysts, and provide mild-reaction conditions to
yield the desired perfluoroalkylated derivatives. They are formed in situ
through halogen-bonding of Rfꢀ I reagents and Lewis bases such as
amines, alcohols, thiols, etc., and upon light activation, these complexes
We next performed the reaction on an alkyne substrate, i.e., ben-
zylpropargyl ether (3) (Table 2, entry 1), with the previously chosen
optimal conditions (Table 1, entry 1). Surprisingly, a low yield of 5% of
the desired product was obtained. The reaction was therefore optimized,
and the results are presented in Table 2. First, MeCN, dichloroethane
and Et2O were used as the solvent in the reaction, but none of these
solvents significantly improved the yield of the reaction (entries 2–4). In
the case of DCE (entry 3), a low yield of 14 % was obtained, and the
conversion of 90 % was attributed mainly to degradation. When the
number of equivalents of SF5Cl was increased from 1.5 to 3, slightly
higher yields of 4a were obtained in all tested solvents (entries 6–8),
with the exception of Et2O, in which a full conversion and a good yield of
69 % were obtained (entry 5). These results tend to show that increasing
the initial amount of SF5Cl might have helped having more of the
gaseous SF5Cl in solution, therefore increasing the conversion and yield.
While diluting or concentrating the reaction did not prove beneficial
(entries 9–10), changing the number of equivalents of the diphenyla-
cetaldehyde and pyrrolidine proved to strongly affect the reaction (en-
tries 11–14). Indeed, when the number of equivalents of both aldehyde
and amine were increased, no conversion was observed (entries 11–12),
while reducing the catalytic amounts to 5 mol% led to the moderate
yield of 47 % (entry 13). Moreover, when changing the diphenylace-
taldehyde/pyrrolidine ratio in favor of the pyrrolidine, no final com-
pound was detected in the reaction mixture (entry 14). Finally, the
reaction time was optimized (entries 15–18), and 16 h proved optimal
with a 71 % NMR yield (entry 17). Therefore, these reaction conditions
were chosen as the optimal ones for the evaluation of the scope of
•
can form the desired Rf radical species (Rf) [16]. We therefore hypoth-
esized that this type of reaction could be applied to the use of SF5Cl
instead of Rfꢀ I, in order to obtain the pentafluorosulfanylated de-
rivatives. Herein, we report the first EDA-complex promoted SF5Cl
addition on unsaturated compounds (Scheme 1C).
2. Results and discussion
4-Phenyl-1-butene (1) was chosen as the model substrate for the
optimization, and was submitted to similar reaction conditions reported
in Ofuji’s article, i.e., 1.5 equivalent of SF5Cl (instead of 1.1 equivalent
of the Rfꢀ I reagent), 10 mol% of diphenylacetaldehyde and pyrrolidine,
in dichloromethane at room temperature for 16 h with a 23 W light bulb
irradiation (entry 1). To our delight, a 90 % NMR yield of the desired
compound 2a was obtained. The reaction was then performed with
other solvents (THF, Et2O, MeCN, toluene, EtOAc, 1,4-dioxane and
hexane), but none of them yielded the desired product in higher yield
(data not shown). When trying to decrease the reaction time from 16 to
3 h, a lower conversion of 22 % was observed and only traces amount of
the desired compound were obtained (entry 2). Finally, some control
Scheme 1. Previous and present works on the SF5Cl radical addition on unsaturated compounds.
2

A. Gilbert et al.
Journal of Fluorine Chemistry 243 (2021) 109734
Table 1
Optimization of the SF5Cl addition on 4-phenyl-1-butene 1.
Entry
Solvent
x equiv.
y equiv.
time (h)
Conversion (%)a
Yield (%)a
1
2
3
4
5
6
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
0.1
0.1
0.1
0
0.1
0.1
0.1
0.1
0
16
3
100
22
36
37
26
32
90 (78)b
traces
16
16
16
16
0c
0
0.1
0
0
0
0
a
Estimated by 1H and 19F NMR using 2-fluoro-4-nitrotoluene as an internal standard.
b
c
Isolated yield.
Reaction performed without light activation.
alkynes.
With the optimized conditions in hand, a series of alkenes and al-
the reaction was performed on allyl benzyl ether, a moderate yield of 56
% of compound 2h was obtained. Interestingly, two styrene derivatives
i.e., styrene and tert-butyl styrene were tolerated in the reaction, and
afforded compounds 2i and 2j with 52 % and 46 % yield respectively.
Styrene derivatives have shown to polymerize in SF5Cl radical additions,
but this did not prove to be a problem in our conditions, since no sign of
polymerization was detected in the crude reaction mixture [11].
Moreover, several aliphatic derivatives were also investigated in our
(EDA)-complex enabled SF5Cl addition. When 9-decen-1-ol was tested in
the reaction, an excellent NMR yield of 90 % was obtained, but the final
compound 2k could not be isolated from the reaction mixture. None-
theless, this result is of interest, considering that free alcohols are not
tolerated in the Et3B-initiated SF5Cl addition [7]. When the alcohol
group was next protected with an acetate group, a NMR yield of 74 %
was obtained, and 53 % of the product 2l was isolated. Finally, the
bromine-containing aliphatic derivative 2m was also tolerated in the
reaction condition, with a 74 % NMR yield and a 51 % isolated yield.
Some compounds proved unproductive in our EDA-complex medi-
ated SF5Cl. First, methyl acrylate was tested in the reaction, and deriv-
ative 2n could not be detected in the reaction mixture. A similar result
was obtained when N-allylaniline was submitted to the reaction condi-
tions, since no trace of compound 2o could be detected. These results are
not surprising, considering that these substrates are also not tolerated in
Dolbier’s protocol for the addition of SF5Cl [7]. However, the acid
kynes were submitted to the reaction. First, the alkene scope is depicted
in Scheme 2. Both the isolated yields and the NMR yields are shown,
since it was observed that in a few cases, purification proved problem-
atic, leading to considerably lower isolated yields than the NMR ones.
For example, a 90 % NMR yield of the model substrate 2a was obtained,
but only 78 % could be isolated from the reaction mixture. The reaction
leads to several unidentified side products, which rendered some puri-
fications laborious. First, a series of aromatic esters were submitted to
the reaction conditions. The vinyl benzoate addition product 2b led to
an excellent NMR yield of 88 % and a moderate isolated yield of 66 %.
When the aliphatic chain was increased such as with substrate 2c, the
same yield of 88 % was obtained by NMR analysis, but the purification
step proved easier and a good isolated yield of 81 % was obtained. Next,
the electronic nature of the phenyl group was varied, either with an
electron-donating group such as methoxy (2d) or an electron-
withdrawing substituent such as fluorine (2e), and no particular effect
on the yield was observed, since these products were obtained in 78 %
and 69 % isolated yields respectively. When the reaction was performed
with the 2-naphtoate derivative, compound 2f was isolated with a
moderate yield of 48 %. The use of an aliphatic ester led to a similar
NMR yield of 78 %, but purification proved particularly problematic
with that substrate, and only 31 % of product 2g could be isolated. When
Table 2
Optimization of the SF5Cl addition on benzylpropargyl ether 3.
Entry
Solvent
[Conc.] (M)
x equiv.
y equiv.
z equiv.
Time (h)
Conversion (%)a
Yield (%)a
1
CH2Cl2
MeCN
DCE
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.05
0.4
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
1.5
1.5
1.5
1.5
3.0
3.0
3.0
3.0
3.0
3.0
3.0
3.0
3.0
3.0
3.0
3.0
3.0
3.0
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.2
1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.2
1
18
18
18
18
18
18
18
18
18
18
18
18
18
18
4
6
5
2
0
0
3
90
10
100
57
60
30
64
32
0
14
8
4
Et2O
Et2O
dioxane
THF
5
69
32
25
13
29
14
0
6
7
8
EtOAc
Et2O
Et2O
Et2O
Et2O
Et2O
Et2O
Et2O
Et2O
Et2O
Et2O
9
10
11
12
13
14
15
16
17
18
0
0
0.05
0.1
0.1
0.1
0.1
0.1
0.05
1
63
0
47
0
0.1
0.1
0.1
0.1
95
96
100
100
45
66
71
54
6
16
24
a
Estimated by 1H and 19F NMR using 2-fluoro-4-nitrotoluene as an internal standard.
3

A. Gilbert et al.
Journal of Fluorine Chemistry 243 (2021) 109734
Scheme 2. Alkene scope of the EDA-complex mediated SF5Cl addition. Unless noted otherwise, isolated yields are reported. aYield estimated by 19F NMR analysis of
the crude mixture using 2-fluoro-4-nitrotoluene as an internal standard. b51:49 diastereoisomeric mixture.
derivative 2p was only obtained in 10 % NMR yield in our method even
though this substrate can be easily obtained in the Et3B-mediated pro-
tocol [17]. This result may be due to an acid-base reaction between the
substrate and pyrrolidine, which almost shut down the activation step.
Moreover, the amide derivative 2q could also not be obtained with our
reaction conditions, while amides are tolerated in Dolbier’s protocol
[18]. At the moment, we hypothesized that the reason for this result
might come from a competition between the amide and the enamine in
the formation of the EDA-complex though more elaborate experiments
are required in order to confirm this hypothesis.
the purification step. The model substrate benzyl 3-butynyl ether led to
66 % of compound 4a. When 4-phenyl-1-butyne and 5-phenyl-1-pen-
tyne were submitted to the reaction conditions, compounds 4b and 4c
were obtained in good yields, respectively 80 % and 84 %. Surprisingly,
compound 4c was obtained as a stereoisomeric mixture (Z/E = 75:25).
This compound is the only one who did not show a complete stereo-
selectivity in favor of the Z isomer in the reaction, and the reason for that
remains unclear. The presence of the E isomer in the SF5Cl radical
addition on alkynes has, to the best of our knowledge, never been re-
ported in the literature. The ester derivative 4d was also obtained in a
good yield of 81 %, as well as the derivative with a one-carbon smaller
aliphatic chain 4e, which was obtained with a 72 % yield. Moreover,
adding an electron-donating substituent on the phenyl ring proved
Next, a series of alkynes were submitted in the optimized reaction
conditions (Scheme 3). In general, alkyne substrates led to slightly
higher yields than the alkenes, and no sign of side reactions complicated
Scheme 3. Alkyne scope of the EDA-complex mediated SF5Cl addition. Unless noted otherwise, isolated yields are reported. aYield estimated by 19F NMR analysis of
the crude mixture using 2-fluoro-4-nitrotoluene as an internal standard.
4

A. Gilbert et al.
Journal of Fluorine Chemistry 243 (2021) 109734
beneficial to the reaction, since compound 4f could be obtained with an
86 % yield. A moderate yield of 51 % was afforded with the adamantane-
containing ester derivative 4g. Finally, the (EDA)-complex enabled
SF5Cl addition was performed on phenylacetylene. The formation of the
desired compound 4h has been shown to be in competition with the
formation of the 2:1 addition product in Dolbier’s protocol [7]. How-
ever, in our reaction conditions, no sign of the 2:1 addition product was
detected, and the desired compound 4h could be afforded with a 51 %
NMR yield and a 33 % isolated yield. The difference between the NMR
and the isolated yield was attributed to the volatility of compound 4h.
A plausible mechanism, based on Ofuji and coworkers’ work [14],
for the (EDA)-complex SF5Cl addition on olefins and alkynes is depicted
in Scheme 4. We hypothesized that the SF5Cl addition would undergo a
similar pathway than with the perfluoroalkylated reagents. First,
following the formation of the enamine from the reaction between 2,
2-diphenylacetaldehyde and pyrrolidine, the (EDA)-complex could be
formed through halogen-bonding of the chlorine atom from SF5Cl and
the nitrogen atom of the enamine. Upon light irradiation, the (EDA)--
4. Experimental
4.1. General information
All reactions were carried out under an argon atmosphere with dry
solvents. All commercially available compounds were used as received.
SF5Cl was purchased at SynQuest Labs inc. and was condensed at a
known concentration in hexanes. This solution was then used for the
SF5Cl additions and could be stored for several months in a -35 ◦C
freezer. Thin-layer chromatography (TLC) analysis of reaction mixtures
was performed using Silicycle silica gel 60 Å F254 TLC plates, and
visualized under UV or by staining with potassium permanganate. Flash
column chromatography was carried out on Silicycle silica gel 60 Å,
230–400 mesh. 1H, 13C and 19F NMR spectra were recorded in CDCl3 at
room temperature using an Agilent DD2 500 or a Varian Inova 400
spectrometer. 1H and 13C NMR chemical shifts are reported in ppm
downfield of tetramethylsilane and are respectively referenced to tet-
ramethylsilane (δ =0.00 ppm) and residual solvent (δ =77.16 ppm). For
19F NMR, calibration was performed using a unified scale [19]. Multi-
plicities are reported using the following abbreviations: s = singlet,
d = doublet, t = triplet, q = quartet, p = pentet, sext = sextet,
m = multiplet, bs = broad signal. High-resolution mass spectra were
obtained on a LC/MS–TOF Agilent 6210 using electrospray ionization
(ESI). GC–MS analyses were performed on a Thermo Trace ULTRA
GCMS equipped with an Agilent J&W HP-1 capillary column, an ITQ
900 mass selective detector (EI) or (CI) using the following method:
40 ◦C for 1 min then 10 ◦C/min until 330 ◦C. Infrared spectra were
recorded using an ABB MB3000 FT-IR spectrometer. The melting points
(m.p.) were recorded on a MPA100 apparatus using the following
method: 40 ◦C–200 ◦C at 2 ◦C/min.
•
complex would next collapse to generate the desired radical species SF5,
the radical cationic enamine and the chlorine anion. The starting
•
enamine could be regenerated by the expulsion of a chlorine radical Cl ,
•
while the SF5 could add on the alkene to generate the penta-
fluorosulfanylated radical intermediate. The latter could either combine
•
with the Cl generated for the recovery of the starting enamine, or
propagate the reaction by the activation of another SF5Cl equivalent,
therefore leading to a free-radical mechanism. While more studies need
to be performed to further increase our understanding of the reaction
mechanism, and possibly exclude one of the two plausible pathways, it is
still noteworthy that no oxygen is involved in the mechanism, which
represents an advantage compared to both the Et3B and the
DICAB-initiated SF5Cl additions on alkenes and alkynes [7,11].
4.2. Synthesis of the starting material
3. Conclusion
4.2.1. Dec-9-en-1-yl benzoate
In conclusion, we have reported the first (EDA)-complex mediated
SF5Cl addition on unsaturated compounds. A total of 19 examples were
performed, with yields going from 31 % to 86 %. Functional groups such
as ethers, esters, alcohols and bromine were tolerated in the reaction,
while methyl acrylate, acid derivatives and nitrogen-containing func-
tional groups did not afford the desired SF5Cl addition products. Alkyne
derivatives showed to be slightly superior to alkenes substrates. Overall,
this method represents an oxygen-free alternative to the most common
SF5Cl addition reaction conditions.
Following the procedure described by Kang and coworkers [20],
dec-9-en-1-ol (0.58 mL, 3.28 mmol, 2 equiv.) was added to a solution of
benzoic acid (200 mg, 1.64 mmol, 1 equiv.) in dry dichloromethane
(3.6 mL, 0.45 M) at room temperature under argon. 4-Dimethylamino-
pyridine (20 mg, 0.16 mmol, 0.1 equiv.) was then added, and the reac-
tion mixture was cooled to 0 ◦C and stirred for 15 min. N,
N’-dicyclohexylcarbodiimide (676 mg, 3.28 mmol, 2 equiv.) was then
added, and the reaction mixture was warmed to room temperature and
stirred overnight. The reaction mixture was next filtrated, and the
filtrate was concentrated under reduced pressure. The crude mixture
was purified by flash chromatography on silica gel using hexane/di-
chloromethane (70:30) as the eluent to afford the title compound as a
colorless oil (413.7 mg, 1.59 mmol, 97 %).
1H NMR (500 MHz, CDCl3): δ (ppm) = 8.06 – 8.02 (m, 2 H), 7.58 –
7.52 (m, 1 H), 7.47 – 7.40 (m, 2 H), 5.81 (ddt, J = 16.9, 10.2, 6.7 Hz,
1 H), 4.99 (ddt, J = 17.1, 2.2, 1.6 Hz, 1 H), 4.93 (ddt, J = 10.2, 2.3,
1.2 Hz, 1 H), 4.31 (t, J =6.7 Hz, 2 H), 2.13 – 1.92 (m, 2 H), 1.84 – 1.66
(m, 2 H), 1.49 – 1.17 (m, 10 H); 13C NMR (126 MHz, CDCl3): δ
(ppm) = 166.7, 139.2, 132.8, 130.5, 129.5, 128.3, 114.2, 65.1, 33.8,
29.4, 29.2, 29.0, 28.9, 28.7, 26.0; HRMS-ESI (+) m/z calcd for C17H25O2
[M+H]+ 261.1849 found 261.1859; IR (ATR, Diamond):
(cmꢀ 1) = 2926, 2854, 1718, 1452, 1269, 1111, 993, 708.
ν
4.2.2. Allyl 4-methoxybenzoate
Following the procedure described by Mereddy and coworkers [21],
Na2CO3 (418 mg, 3.94 mmol, 3 equiv.) was added to a solution of
4-methoxybenzoic acid (200 mg, 1.31 mmol, 1 equiv.) in dry DMSO
(3.3 mL, 0.4 M). The reaction mixture was stirred at room temperature
for 15 min before allyl bromide (0.11 mL, 1.31 mmol, 1 equiv.) was
added. The reaction was stirred for 2 h at room temperature. Water was
then added, and the mixture was extracted with Et2O (3x) and washed
with a saturated solution of NaHCO3. The organic layers were combined,
Scheme 4. Proposed mechanism for the (EDA)-complex mediated SF5Cl addi-
tion on unsaturated compounds.
5

A. Gilbert et al.
Journal of Fluorine Chemistry 243 (2021) 109734
dried over MgSO4, filtered and concentrated under reduced pressure.
The crude mixture was next purified by flash chromatography on silica
gel using hexane/EtOAc (90:10) as the eluent to afford the title com-
pound as a colorless oil (178.4 mg, 0.93 mmol, 71 %). 1H NMR
(500 MHz, CDCl3): δ (ppm) = 8.06 – 7.97 (m, 2 H), 6.96 – 6.87 (m, 2 H),
6.04 (ddt, J = 17.2, 10.5, 5.6 Hz, 1 H), 5.40 (dq, J = 17.2, 1.6 Hz, 1 H),
5.28 (dq, J = 10.4, 1.3 Hz, 1 H), 4.80 (dt, J = 5.6, 1.5 Hz, 2 H), 3.86 (s,
3 H). Analytical data were identical to those previously reported [22].
4.57 (s, 2 H), 3.60 (t, J = 6.8 Hz, 2 H), 2.50 (dt, J = 2.8, 6.8 Hz, 2 H), 1.98
(t, J = 2.8 Hz, 1 H). Analytical data were identical to those previously
reported [26].
4.2.7. Pent-4-yn-1-yl benzoate
Following the procedure described by Gilmour and coworkers [27],
pent-4-yl-1-ol (0.93 mL, 10 mmol, 1 equiv.) and benzoyl chloride
(1.3 mL, 11 mmol, 1.1 equiv.) were dissolved in Et2O (15 mL, 0.67 M).
Et3N (1.5 mL, 11 mmol, 1.1 equiv.) was added slowly and the reaction
mixture was stirred for 24 h. The reaction mixture was diluted with
EtOAc and H2O, and the aqueous layer was extracted with EtOAc. The
combined organic layers were washed with H2O and brine, dried over
MgSO4 and filtered. The solvent was removed in vacuo and the crude
mixture was purified by flash chromatography on silica gel using hex-
ane/EtOAc (98:2) as the eluent to afford the title compound as a
colorless oil (1.3 g, 7.3 mmol, 73 %). 1H NMR (400 MHz, CDCl3): δ
(ppm) = 8.06 – 8.03 (m, 2 H), 7.58 – 7.54 (m, 1 H), 7.46 – 7.42 (m, 2 H),
4.43 (t, J =6.3 Hz, 2 H), 2.39 (td, J = 7.0, 2.7 Hz, 2 H), 2.04 – 1.98 (m,
3 H). Analytical data were identical to those previously reported [28,
29].
4.2.3. Allyl 4-fluorobenzoate
Following the procedure described by Mereddy and coworkers [21],
Na2CO3 (454 mg, 4.28 mmol, 3 equiv.) was added to a solution of 4-flu-
orobenzoic acid (200 mg, 1.43 mmol, 1 equiv.) in DMSO (3.6 mL,
0.4 M). The reaction mixture was stirred at room temperature for 15 min
before allyl bromide (0.12 mL, 1.43 mmol, 1 equiv.) was added. The
reaction was stirred for 2 h at room temperature. Water was then added,
and the mixture was extracted with Et2O (3x) and washed with a satu-
rated solution of NaHCO3. The organic layers were combined, dried over
MgSO4, filtered and concentrated under reduced pressure. The crude
mixture was next purified by flash chromatography on silica gel using
hexane/EtOAc (90:10) as the eluent to afford the title compound as a
colorless oil (185.6 mg, 1.03 mmol, 72 %). 1H NMR (500 MHz, CDCl3): δ
(ppm) = 8.11 – 8.05 (m, 2 H), 7.15 – 7.07 (m, 2 H), 6.04 (ddt, J = 17.2,
10.5, 5.7 Hz, 1 H), 5.41 (dq, J = 17.2, 1.5 Hz, 1 H), 5.30 (dq, J = 10.5,
1.3 Hz, 1 H), 4.82 (dt, J = 5.7, 1.4 Hz, 2 H); 13C NMR (126 MHz, CDCl3):
δ (ppm) = 165.8 (d, J =253.7 Hz), 165.3, 132.2 (d, J =9.3 Hz), 132.1,
126.4 (d, J =3.0 Hz), 118.4, 115.5 (d, J =22.0 Hz), 65.7; 19F NMR
(470 MHz, CDCl3): δ (ppm) = -105.61 – -105.76 (m, 1 F); GC–MS (CI)
[23]: m/z calcd for C10H10FO2 [M+H]+ 181.07 found 181.00; IR (ATR,
4.2.8. But-3-yn-1-yl benzoate
Following the procedure described by Gilmour and coworkers [27],
but-3-yl-1-ol (0.38 mL, 5.0 mmol, 1 equiv.) and benzoyl chloride
(0.87 mL, 7.5 mmol, 1.5 equiv.) were dissolved in Et2O (15 mL, 0.3 M).
Et3N (1.0 mL, 7.5 mmol, 1.5 equiv.) was added slowly, and the reaction
mixture was stirred for 15 h. The reaction mixture was diluted with
EtOAc and H2O, and the aqueous layer was extracted with EtOAc. The
combined organic layers were washed with H2O and brine, dried over
MgSO4 and filtered. The solvent was removed in vacuo and the crude
mixture was purified by flash chromatography on silica gel using hex-
ane/EtOAc (98:2) as the eluent to afford the title compound as a
colorless oil (0.40 g, 2.3 mmol, 45 %). 1H NMR (400 MHz, CDCl3): δ
(ppm) = 8.08 ꢀ 8.05 (m, 2 H), 7.59 ‒ 7.55 (m, 1 H), 7.47 ‒ 7.43 (m, 2 H),
4.43 (t, J =6.8 Hz, 2 H), 2.68 (td, J = 6.8, 2.7 Hz, 2 H), 2.03 (t, J =2.6 Hz,
1 H). Analytical data were identical to those previously reported [22].
Diamond):
ν
(cmꢀ 1) = 3084, 2947, 1720, 1508, 1263, 1236, 852, 766.
4.2.4. Allyl 2-naphthoate
Following the procedure described by Mereddy and coworkers [21],
Na2CO3 (369 mg, 3.48 mmol, 3 equiv.) was added to a solution of
2-naphthoic acid (200 mg, 1.16 mmol, 1 equiv.) in DMSO (2.9 mL,
0.4 M). The reaction mixture was stirred at room temperature for 15 min
before allyl bromide (0.10 mL, 1.16 mmol, 1 equiv.) was added. The
reaction was stirred for 2 h at room temperature. Water was then added,
and the mixture was extracted with Et2O (3x) and washed with a satu-
rated solution of NaHCO3. The organic layers were combined, dried over
MgSO4, filtered and concentrated under reduced pressure. The crude
mixture was next purified by flash chromatography on silica gel using
hexane/EtOAc (95:5) as the eluent to afford the title compound as a
colorless oil (226 mg, 1.06 mmol, 91 %). 1H NMR (500 MHz, CDCl3): δ
(ppm) = 8.66 – 8.59 (m, 1 H), 8.09 (dd, J = 8.6, 1.7 Hz, 1 H), 7.99 – 7.93
(m, 1 H), 7.91 – 7.85 (m, 2 H), 7.62 – 7.57 (m, 1 H), 7.56 – 7.52 (m, 1 H),
6.10 (ddt, J = 17.2, 10.5, 5.7 Hz, 1 H), 5.46 (dq, J = 17.2, 1.6 Hz, 1 H),
5.33 (dq, J = 10.4, 1.3 Hz, 1 H), 4.90 (dt, J = 5.6, 1.4 Hz, 2 H). Analytical
data were identical to those previously reported [24].
4.2.9. But-3-yn-1-yl 4-methoxybenzoate
Following the procedure described by Gilmour and coworkers [27],
but-3-yl-1-ol (0.38 mL, 5.0 mmol, 1 equiv.) and 4-methoxy benzoyl
chloride (1.0 mL, 7.5 mmol, 1.5 equiv.) were dissolved in Et2O (15 mL,
0.3 M). Et3N (1.0 mL, 7.5 mmol, 1.5 equiv.) was added slowly, and the
reaction mixture was stirred for 24 h. The reaction mixture was diluted
with EtOAc and H2O, and the aqueous layer was extracted with EtOAc.
The combined organic layers were washed with H2O and brine, dried
over MgSO4 and filtered. The solvent was removed in vacuo and the
crude mixture was purified by flash chromatography on silica gel using
hexane/EtOAc (20:1) as the eluent to afford the title compound as a
white solid (0.67 g, 3.1 mmol, 61 %). 1H NMR (400 MHz, CDCl3): δ
(ppm) = 8.08 – 8.03 (m, 2 H), 6.94 – 6.91 (m, 2 H), 4.40 (t, J =6.3 Hz,
2 H), 3.87 (s, 3 H), 2.66 (td, J = 7.1, 2.7 Hz, 2 H), 2.03 – 2.02 (m, 1 H).
Analytical data were identical to those previously reported [22].
4.2.5. Dec-9-en-1-yl acetate
The title compound was prepared as previously reported [11].
4.2.6. ((But-3-yn-1-yloxy)methyl)benzene
4.2.10. But-3-yn-1-yl adamantane-1-carboxylate
Following the procedure described by Yamada and coworkers [25],
sodium hydride (79,3 mg, 60 % in mineral oil, 1.98 mmol, 1 equiv.),
tetrabutylammonium iodide (60.9 mg, 0.165 mmol, 8 mol%), and
benzyl bromide (0.283 mL, 2.38 mmol, 1.2 equiv.) were added to a so-
lution of 3-butyn-1-ol (0.150 mL, 1.98 mmol 1 equiv.) in THF (1.6 mL,
1.2 M) at 0 ℃. The resulting solution was stirred at 25 ◦C for 18 h,
quenched with sat. NH4Cl aq., and extracted with Et2O (3×). A com-
bined organic layer was washed with H2O and brine, dried over MgSO4,
filtered, and concentrated in vacuo. The residue was purified by flash
chromatography on silica gel using hexane/EtOAc (5:1) as the eluent to
give the title compound as a pale yellow oil in quantitative yield (32 mg,
1.98 mmol). 1H NMR (500 MHz, CDCl3): δ (ppm) = 7.35 ‒ 7.28 (m, 5 H),
Following the procedure described by Potkin and coworkers [30],
anhydrous pyridine (0,28 mL, 3.5 mmol, 1.2 equiv.) was added to a
solution of 1-adamantoyl chloride (0.60 mg, 3.0 mmol, 1 equiv.) and
but-3-yn-1-ol (0,23 mL, 3.0 mmol, 1 equiv.) in 70 mL of dry diethyl
ether. The mixture was allowed to stir at room temperature for 24 h. The
precipitate of pyridine hydrochloride was filtered off and washed with
30 mL of diethyl ether; the combined filtrates were washed with H2O
and saturated aqueous solution of sodium hydrogen carbonate. The
ethereal solution was dried over MgSO4, filtered and concentrated. The
crude product was purified by column chromatography using 100 %
hexane as the eluent to afford 73 % (0,50 g, 2.19 mmol) of the expected
product as a colorless oil. 1H NMR (400 MHz, CDCl3): δ (ppm) = 4.16 (t,
6

A. Gilbert et al.
Journal of Fluorine Chemistry 243 (2021) 109734
J =6.8 Hz, 2 H), 2.54 ‒ 2.50 (m, 2 H), 2.02 ‒ 1.98 (m, 4 H), 1.90 (d, J
=3.0 Hz, 6 H), 1.73 ‒ 1.70 (m, 6 H). Analytical data were identical to
those previously reported [30].
(1.18 M in hexane, 0.58 mL, 0.68 mmol) and dichloromethane (4.5 mL)
were engaged in general procedure to afford the title compound as a
colorless oil (124.7 mg, 0.35 mmol, 78 %) after purification by flash
chromatography using hexane/EtOAc (95:5) as the eluent. 1H NMR
(500 MHz, CDCl3): δ (ppm) = 8.02 – 7.97 (m, 2 H), 6.97 – 6.93 (m, 2 H),
4.73 – 4.64 (m, 1 H), 4.58 (dd, J = 11.9, 5.1 Hz, 1 H), 4.52 (dd, J = 11.9,
4.3. General procedure for the SF5Cl addition on alkenes
5.7 Hz, 1 H), 4.22 – 4.12 (m, 1 H), 4.08 – 3.97 (m, 1 H), 3.88 (s, 3 H); 13
C
To a sealable microwave vial containing the alkene (1 equiv.) under
argon was added a solution of 2,2-diphenylacetaldehyde (0.1 equiv.) in
dry dichloromethane (0.1 M). Pyrrolidine (0.1 equiv.) was then added,
and the reaction vial was sealed before SF5Cl (1.5 equiv.) was added to
the reaction mixture. The reaction was stirred at room temperature for
16 h under 23 W CFL lamp irradiation. The reaction was then quenched
with a saturated solution of NaHCO3. The phases were separated, and
the organic phase was dried over MgSO4, filtered and concentrated
under reduced pressure. The crude mixture was purified by flash chro-
matography on silica gel.
NMR (126 MHz, CDCl3): δ (ppm) = 165.4, 163.9, 131.9, 121.3, 113.9,
73.4 (p, J =14.9 Hz), 65.7, 55.5, 52.3 (p, J =4.4 Hz); 19F NMR (470 MHz,
CDCl3): δ (ppm) = 86.9 – 72.9 (m, 1 F), 66.8 (dt, J = 146.8, 7.9 Hz, 4 F);
HRMS-ESI (+) m/z calcd for C11H13ClF5O3S [M+H]+ 355.0189 found
355.0209; IR (ATR, Diamond):
1254, 1167, 816, 766.
ν
(cmꢀ 1) = 2972, 2843, 1717, 1605,
4.3.5. 2-Chloro-3-(pentafluoro-λ6-sulfanyl)propyl 4-fluorobenzoate (2e)
Allyl 4-fluorobenzoate (50 mg, 0.28 mmol), 2,2-diphenylacetalde-
hyde (5 μL, 0.028 mmol), pyrrolidine (2 μL, 0.028 mmol), SF5Cl
4.3.1. (2-Chloro-4-phenylbutyl)pentafluoro-λ6-sulfane (2a)
(1.18 M in hexane, 0.35 mL, 0.42 mmol) and dichloromethane (2.8 mL)
were engaged in general procedure to afford the title compound as a
colorless oil (65.2 mg, 0.19 mmol, 69 %) after purification by flash
chromatography using hexane/EtOAc (95:5) as the eluent. 1H NMR
(500 MHz, CDCl3): δ (ppm) = 8.10 – 8.03 (m, 2 H), 7.18 – 7.13 (m, 2 H),
4.75 – 4.66 (m, 1 H), 4.58 (dd, J = 5.3, 2.1 Hz, 2 H), 4.21 – 4.10 (m, 1 H),
4.09 – 3.99 (m, 1 H); 13C NMR (126 MHz, CDCl3): δ (ppm) = 166.0 (d, J
=315.8 Hz), 165.2, 132.4 (d, J =9.5 Hz), 125.3 (d, J =3.0 Hz), 115.9 (d,
J =22.0 Hz), 73.3 (p, J =15.0 Hz), 66.1, 52.2 (p, J =4.4 Hz); 19F NMR
(470 MHz, CDCl3): δ (ppm) = 83.1 – 80.3 (m, 1 F), 66.8 (dt, J = 146.7,
7.9 Hz, 4 F), -104.1 – -104.3 (m, 1 F); GC–MS (CI) [19]: m/z calcd for
4-phenyl-1-butene (50 mg, 0.38 mmol), 2,2-diphenylacetaldehyde
(7 μL, 0.038 mmol), pyrrolidine (3 μL, 0.038 mmol), SF5Cl (1.38 M in
hexane, 0.41 mL, 0.57 mmol) and dichloromethane (3.8 mL) were
engaged in general procedure to afford the title compound as a colorless
oil (87.5 mg, 0.30 mmol, 78 %) after purification by flash chromatog-
raphy using hexane/EtOAc (98:2) as the eluent. 1H NMR (500 MHz,
CDCl3): δ (ppm) = 7.33 – 7.29 (m, 2 H), 7.26 – 7.17 (m, 3 H), 4.30 (dtd,
J = 9.6, 6.3, 3.3 Hz, 1 H), 4.09 – 3.97 (m, 1 H), 3.96 – 3.83 (m, 1 H), 2.98
– 2.89 (m, 1 H), 2.79 (ddd, J = 13.8, 8.9, 7.4 Hz, 1 H), 2.32 – 2.20 (m,
1 H), 2.04 (dtd, J = 14.3, 9.3, 4.9 Hz, 1 H); 19F NMR (470 MHz, CDCl3): δ
(ppm) = 84.8 – 79.9 (m, 1 F), 66.4 (dt, J = 146.5, 8.1 Hz, 4 F). Analytical
data were identical to those previously reported [31].
C
10H10ClF6O2S [M+H]+ 343.00 found 343.07; IR (ATR, Diamond):
ν
(cmꢀ 1) = 1726, 1603, 1508, 1261, 1119, 1090, 818, 638.
4.3.6. 2-Chloro-3-(pentafluoro-λ6-sulfanyl)propyl 2-naphthoate (2f)
4.3.2. 1-Chloro-2-(pentafluoro-λ6-sulfanyl)ethyl benzoate (2b)
Allyl 2-naphthoate (100 mg, 0.47 mmol), 2,2-diphenylacetaldehyde
Vinyl benzoate (50 mg, 0.34 mmol), 2,2-diphenylacetaldehyde (6 μL,
(8 μL, 0.047 mmol), pyrrolidine (4 μL, 0.047 mmol), SF5Cl (1.18 M in
0.034 mmol), pyrrolidine (3 μL, 0.034 mmol), SF5Cl (1.48 M in hexane,
hexane, 0.60 mL, 0.71 mmol) and dichloromethane (4.7 mL) were
engaged in general procedure to afford the title compound as a colorless
oil (85.3 mg, 0.23 mmol, 48 %) after purification by flash chromatog-
raphy using hexane/EtOAc (95:5) as the eluent. 1H NMR (500 MHz,
CDCl3): δ (ppm) = 8.68 – 8.53 (m, 1 H), 8.05 (dd, J = 8.6, 1.7 Hz, 1 H),
8.01 – 7.96 (m, 1 H), 7.93 – 7.88 (m, 2 H), 7.63 (ddd, J = 8.2, 6.8, 1.3 Hz,
1 H), 7.58 (ddd, J = 8.1, 7.0, 1.3 Hz, 1 H), 4.80 – 4.72 (m, 1 H), 4.70 –
4.55 (m, 2 H), 4.28 – 4.16 (m, 1 H), 4.16 – 4.01 (m, 1 H); 13C NMR
(126 MHz, CDCl3): δ (ppm) = 165.8, 135.8, 132.4, 131.6, 129.5, 128.7,
128.5, 127.9, 126.9, 126.2, 125.0, 73.4 (p, J =14.8 Hz), 66.1, 52.2 (p, J
=4.3 Hz); 19F NMR (470 MHz, CDCl3): δ (ppm) = 83.9 – 79.9 (m, 1 F),
66.8 (dt, J = 146.7, 7.9 Hz, 4 F); HRMS-ESI (+) m/z calcd for
C14H13ClF5O2S [M+H]+ 375.0239 found 375.0259; IR (ATR, Diamond):
0.34 mL, 0.51 mmol) and dichloromethane (3.4 mL) were engaged in
general procedure to afford the tittle compound as a colorless oil
(68.8 mg, 0.22 mmol, 66 %) after purification by flash chromatography
using hexane/EtOAc (95:5) as the eluent. 1H NMR (500 MHz, CDCl3): δ
(ppm) = 8.09 – 8.05 (m, 2 H), 7.67 – 7.62 (m, 1 H), 7.52 – 7.47 (m, 2 H),
7.14 (dd, J = 9.8, 2.1 Hz, 1 H), 4.48 – 4.38 (m, 1 H), 4.25 – 4.17 (m, 1 H);
19F NMR (470 MHz, CDCl3): δ (ppm) = 81.4 – 80.1 (m, 1 F), 66.7 (dt,
J = 147.2, 8.1 Hz, 4 F). Analytical data were identical to those previ-
ously reported [11].
4.3.3. 9-Chloro-10-(pentafluoro-λ6-sulfanyl)decyl benzoate (2c)
Dec-9-en-1-yl benzoate (100 mg, 0.38 mmol), 2,2-diphenylacetalde-
hyde (7 μL, 0.038 mmol), pyrrolidine (3 μL, 0.038 mmol), SF5Cl
ν
(cmꢀ 1) = 3063, 2974, 1720, 1277, 1194, 1130, 818, 638.
(1.18 M in hexane, 0.49 mL, 0.58 mmol) and dichloromethane (3.8 mL)
were engaged in general procedure to afford the title compound as a
colorless oil (132.6 mg, 0.31 mmol, 81 %) after purification by flash
chromatography using hexane/CH2Cl2 (70:30) as the eluent. 1H NMR
(500 MHz, CDCl3): δ (ppm) = 8.08 – 7.98 (m, 2 H), 7.59 – 7.51 (m, 1 H),
7.47 – 7.40 (m, 2 H), 4.41 – 4.22 (m, 3 H), 4.04 – 3.95 (m, 1 H), 3.95 –
3.82 (m, 1 H), 1.98 – 1.82 (m, 1 H), 1.84 – 1.66 (m, 3 H), 1.62 – 1.51 (m,
1 H), 1.50 – 1.41 (m, 3 H), 1.40 – 1.29 (m, 6 H); 13C NMR (126 MHz,
CDCl3): δ (ppm) = 166.7, 132.8, 130.5, 129.5, 128.3, 77.0 (p, J
=13.1 Hz), 65.0, 55.8 (p, J =4.3 Hz), 37.5, 29.2, 29.1, 28.69, 28.68,
26.0, 25.9; 19F NMR (470 MHz, CDCl3): δ (ppm) = 84.9 – 80.5 (m, 1 F),
66.2 (dt, J = 146.4, 8.1 Hz, 4 F); HRMS-ESI (+) m/z calcd for
4.3.7. Ethyl 4-chloro-2-methyl-5-(pentafluoro-λ6-sulfanyl)pentanoate (2 g)
Ethyl 2-methylpent-4-enoate (50 mg, 0.35 mmol), 2,2-diphenylace-
taldehyde (6 μL, 0.035 mmol), pyrrolidine (3 μL, 0.035 mmol), SF5Cl
(1.48 M in hexane, 0.36 mL, 0.53 mmol) and dichloromethane (3.5 mL)
were engaged in general procedure to afford the title compound as a
colorless oil (33.3 mg, 0.11 mmol, 31 %) in a 51:49 diastereoisomeric
mixture after purification by flash chromatography using hexane/EtOAc
(95:5) as the eluent. 1H NMR (500 MHz, CDCl3): δ (ppm) = 4.51 – 4.43
(m, 1H, dia a), 4.42 – 4.34 (m, 0.95H, dia b), 4.17 (app. p, J =7.1 Hz,
3.90H, dia a + b), 4.08 – 3.97 (m, 2H, dia a), 3.97 – 3.84 (m, 1.90H, dia
b), 2.91 – 2.81 (m, 1H, dia a), 2.80 – 2.72 (m, 0.95H, dia b), 2.35 (ddd,
J = 13.8, 10.7, 2.7 Hz, 0.95H, dia a), 2.23 – 2.12 (m, 1H, dia a), 2.05 –
1.94 (m, 0.95H, dia b), 1.68 (ddd, J = 14.3, 11.0, 3.2 Hz, 1H, dia a), 1.27
(td, J = 7.1, 1.5 Hz, 5.85H, dia a + b), 1.24 (d, J =7.2 Hz, 3H, dia a), 1.22
(d, J =7.0 Hz, 2.85H, dia b); 19F NMR (470 MHz, CDCl3): δ (ppm) = 83.7
– 82.0 (m, 1.95 F, dia a + b), 66.6 (dt, J = 147.1, 8.2 Hz, 4 F, dia a), 66.5
(dt, J = 146.5, 8.2 Hz, 3.8 F, dia b). Analytical data were identical to
C
17H25ClF5O2S [M+H]+ 423.1202 found 423.1178; IR (ATR, Diamond):
(cmꢀ 1) = 2932, 2858, 1717, 1273, 1111, 1070, 839, 710.
ν
4.3.4. 2-Chloro-3-(pentafluoro-λ6-sulfanyl)propyl 4-methoxybenzoate
(2d)
Allyl 4-methoxybenzoate (87.1 mg, 0.45 mmol), 2,2-diphenylacetal-
dehyde (8 μL, 0.045 mmol), pyrrolidine (4 μL, 0.045 mmol), SF5Cl
7

A. Gilbert et al.
Journal of Fluorine Chemistry 243 (2021) 109734
those previously reported [32].
using hexane/Et2O (96:4) as the eluent. 1H NMR (500 MHz, CDCl3): δ
(ppm) = 4.64 – 4.59 (m, 1 H), 4.12 – 4.05 (m, 1 H), 3.96 – 3.88 (m, 1 H),
3.61 – 3.59 (m, 2 H), 2.45–2.51 (m,1 H), 2.27 – 2.17 (m, 1 H); 13C NMR
(126 MHz, CDCl3): δ (ppm) = 39.7, 30.3, 29.7, 28.6; 19F NMR (470 MHz,
CDCl3): δ (ppm) = 83.2 – 82.0 (m, 1 F), 66.8 (dt, J = 146.7, 8.2 Hz, 4 F);
GC–MS (EI) [19]: m/z calcd for C4H7BrClF5S [M]+ 295.91 found 296.20;
4.3.8. (3-(Benzyloxy)-2-chloropropyl)pentafluoro-λ6-sulfane (2 h)
((allyloxy)methyl)benzene (50 mg, 0.34 mmol), 2,2-diphenylacetal-
dehyde (6 μL, 0.034 mmol), pyrrolidine (3 μL, 0.034 mmol), SF5Cl
(1.48 M in hexane, 0.34 mL, 0.51 mmol) and dichloromethane (3.4 mL)
were engaged in general procedure to afford the title compound as a
colorless oil (58.5 mg, 0.19 mmol, 56 %) after purification by flash
chromatography using hexane/CH2Cl2 (80:20) as the eluent. 1H NMR
(500 MHz, CDCl3): δ (ppm) = 7.41 – 7.34 (m, 2 H), 7.36 – 7.29 (m, 3 H),
4.59 (s, 2 H), 4.47 (ddt, J = 7.8, 6.7, 4.4 Hz, 1 H), 4.31 – 4.23 (m, 1 H),
3.92 – 3.81 (m, 1 H), 3.76 (dd, J = 10.5, 4.6 Hz, 1 H), 3.60 (dd, J = 10.4,
6.7 Hz, 1 H); 19F NMR (470 MHz, CDCl3): δ (ppm) = 84.1 – 81.6 (m, 1 F),
66.6 (dt, J = 146.8, 8.1 Hz, 4 F). Analytical data were identical to those
previously reported [33].
IR (ATR, Diamond):
652.
ν
(cmꢀ 1) = 2932, 1493, 1448, 1084, 837, 754, 696,
4.4. General procedure for the SF5Cl addition on alkynes
To a sealable microwave vial containing the alkyne (1 equiv.) under
argon was added a solution of 2,2-diphenylacetaldehyde (0.1 equiv.) in
dry diethyl ether (0.1 M). Pyrrolidine (0.1 equiv.) was then added, and
the reaction vial was sealed before SF5Cl (3.0 equiv.) was added to the
reaction mixture. The reaction was stirred at room temperature for 16 h
under 23 W CFL lamp irradiation. The reaction was then quenched with
a saturated solution of NaHCO3. The phases were separated, and the
organic phase was dried over MgSO4, filtered and concentrated under
reduced pressure. The crude mixture was purified by flash chromatog-
raphy on silica gel.
4.3.9. (2-Chloro-2-phenylethyl)pentafluoro-λ6-sulfane (2i)
Styrene (51 mg, 0.49 mmol), 2,2-diphenylacetaldehyde (8 μL,
0.049 mmol), pyrrolidine (4 μL, 0.049 mmol), SF5Cl (1.48 M in hexane,
0.50 mL, 0.73 mmol) and dichloromethane (4.9 mL) were engaged in
general procedure to afford the title compound as a colorless oil (68 mg,
0.25 mmol, 52 %) after purification by flash chromatography using 100
% hexane as the eluent. 1H NMR (500 MHz, CDCl3): δ (ppm) = 7.41 –
7.37 (m, 5 H), 5.36 (t, J =6.8 Hz, 1 H), 4.36 – 4.24 (m, 2 H); 13C NMR
4.4.1. (Z)-(4-(benzyloxy)-2-chlorobut-1-en-1-yl)pentafluoro-λ6-sulfane
(4a)
(126 MHz, CDCl3): δ (ppm) = 138.5, 129.4, 129.1, 126.9, 56.4, 56.3; 19
F
((but-3-yn-1-yloxy)methyl)benzene (23 mg, 0.14 mmol), 2,2-diphe-
NMR (470 MHz, CDCl3): δ (ppm) = 84.3 – 79.5 (m, 1 F), 66.4 (dt,
nylacetaldehyde (2 μL, 0.014 mmol), pyrrolidine (1 μL, 0.014 mmol),
J = 147.4, 8.1 Hz, 4 F). GC–MS (EI) [19]: m/z calcd for C8H8ClF5S [M]+
SF5Cl (1.38 M in hexane, 0.30 mL, 0.42 mmol) and diethyl ether
(1.4 mL) were engaged in general procedure to afford the title com-
pound as a colorless oil (30 mg, 0.09 mmol, 66 %) after purification by
flash chromatography using hexane/Et2O (97:3) as the eluent. 1H NMR
(500 MHz, CDCl3): δ (ppm) = 7.37 – 7.29 (m, 5 H), 6.69 (d, J =7.2 Hz,
1 H), 4.53 (s, 2 H), 3.87 (s, 3 H), 3.73 (t, J = 6.7, 2 H), 3.04 – 3.02 (m,
2 H); 13C NMR (126 MHz, CDCl3): δ (ppm) = 144.1 (q, J = 6.3), 138.5 (q,
J = 21.4), 137.8, 128.4, 127.7, 127.5, 73.0, 66.5, 36.1; 19F NMR
(470 MHz, CDCl3): δ (ppm) = 83.0 – 81.7 (m, 1 F), 67.8 (dd, J = 151.5,
8.3 Hz, 4 F). HRMS-ESI (+) m/z calcd for C11H13ClF5OS [M+H]+
266.00 found 266.13; IR (ATR, Diamond):
949, 876, 849, 816, 694.
ν
(cmꢀ 1) = 2930, 1458, 1184,
4.3.10. (2-(4-(tert-butyl)phenyl)-2-chloroethyl)pentafluoro-λ6-sulfane
(2 j)
1-(tert-butyl)-4-vinylbenzene (50 mg, 0.31 mmol), 2,2-diphenylace-
taldehyde (6 μL, 0.031 mmol), pyrrolidine (3 μL, 0.031 mmol), SF5Cl
(1.18 M in hexane, 0.40 mL, 0.47 mmol) and dichloromethane (3.1 mL)
were engaged in general procedure to afford the title compound as a
yellow oil (46 mg, 0.14 mmol, 46 %) after purification by flash chro-
matography using 100 % hexane as the eluent. 1H NMR (500 MHz,
CDCl3): δ (ppm) = 7.42 – 7.40 (m, 2 H), 7.32 – 7.30 (m, 2 H), 5.37 – 5.34
(m, 1 H), 4.33 – 4.23 (m, 2 H), 1.31 (s, 9 H); 13C NMR (126 MHz, CDCl3):
322.0281 found 322.0278; IR (ATR, Diamond):
1443, 1246, 1057, 831, 754, 689.
ν
(cmꢀ 1) = 2957, 2897,
4.4.2. (Z)-(2-chloro-3-phenylprop-1-en-1-yl)pentafluoro-λ6-sulfane (4b)
δ (ppm) = 152.6, 135.4, 126.5, 126.0, 56.4, 56.3, 56.2, 34.7, 31.2; 19
F
4-phenyl-1-butyne (18 mg, 0.14 mmol), 2,2-diphenylacetaldehyde
NMR (470 MHz, CDCl3): δ (ppm) = 82.3 – 82.0 (m, 1 F), 66.3 (dt,
(2 μL, 0.014 mmol), pyrrolidine (1 μL, 0.014 mmol), SF5Cl (1.48 M in
J = 147.2, 7.8 Hz, 4 F). GC–MS (EI) [19]: m/z calcd for C8H8ClF5S [M]+
hexane, 0.28 mL, 0.41 mmol) and diethyl ether (1.4 mL) were engaged
in general procedure to afford the title compound as a colorless oil
(33 mg, 0.11 mmol, 80 %) after purification by flash chromatography
using 100 % hexane as the eluent.
322.06 found 322.27; IR (ATR, Diamond):
1109, 879, 816, 783, 679.
ν
(cmꢀ 1) = 2966, 1396, 1202,
4.3.11. 9-Chloro-10-(pentafluoro-λ6-sulfanyl)decyl acetate (2l)
1H NMR (500 MHz, CDCl3): δ (ppm) = 7.33 – 7.30 (m, 2 H), 7.25 –
7.20 (m, 3 H), 6.64 (p, J =8.2 Hz, 1 H), 2.98 – 2.91 (m, 4 H); 19F NMR
(470 MHz, CDCl3): δ (ppm) = 85.2 – 82.7 (m, 1 F), 67.3 (dd, J = 151.5,
8.2 Hz, 4 F). Analytical data were identical to those previously reported
[11].
Dec-9-en-1-yl acetate (50 mg, 0.25 mmol), 2,2-diphenylacetalde-
hyde (4 μL, 0.025 mmol), pyrrolidine (2 μL, 0.025 mmol), SF5Cl
(1.48 M in hexane, 0.26 mL, 0.38 mmol) and dichloromethane (2.5 mL)
were engaged in general procedure to afford the title compound as a
colorless oil (48.7 mg, 0.13 mmol, 53 %) after purification by flash
chromatography using hexane/EtOAc (95:5) as the eluent. 1H NMR
(500 MHz, CDCl3): δ (ppm) = 4.38 – 4.32 (m, 1 H), 4.06 (t, J =6.8 Hz,
2 H), 4.03 – 3.96 (m, 1 H), 3.95 – 3.84 (m, 1 H), 2.05 (s, 3 H), 1.97 – 1.82
(m, 1 H), 1.79 – 1.68 (m, 1 H), 1.67 – 1.50 (m, 3 H), 1.49 – 1.44 (m, 1 H),
1.38 – 1.25 (m, 8 H); 19F NMR (470 MHz, CDCl3): δ (ppm) = 84.8 – 79.7
(m, 1 F), 66.2 (dt, J = 146.4, 8.1 Hz, 4 F). Analytical data were identical
to those previously reported [7b].
4.4.3. (Z),(E)-(2-chloro-5-phenylpent-1-en-1-yl)pentafluoro-λ6-sulfane
(4c)
4-phenyl-1-pentyne (29 mg, 0.20 mmol), 2,2-diphenylacetaldehyde
(4 μL, 0.020 mmol), pyrrolidine (2 μL, 0.020 mmol), SF5Cl (1.48 M in
hexane, 0.40 mL, 0.60 mmol) and diethyl ether (2.0 mL) were engaged
in general procedure to afford the title compound as a mixture of
inseparable (Z) and (E) products (75:25) as a yellow oil (51 mg,
0.17 mmol, 84 %) after purification by flash chromatography using 100
4.3.12. (4-Bromo-2-chlorobutyl)pentafluoro-λ6-sulfane (2 m)
% hexane as the eluent. 1H NMR (500 MHz, CDCl3) (Z):(E):
δ
4-Bromobut-1-ene (53 mg, 0.39 mmol), 2,2-diphenylacetaldehyde
(ppm) = 7.45–7.46 (m, 1 H), 7.30 – 7.28 (m, 2 H), 7.22 – 7.17 (m, 3 H),
6.77 (p, J =9.3 Hz, 1 H), 6.62 (p, J =8.3 Hz, 1 H), 2.90 (t, J =5.7 Hz,
2 H), 2.84 (t, J =6.3 Hz, 2 H), 2.72 (t, J =7.8 Hz, 2 H), 2.67 (t, J =7.7 Hz,
2 H), 2.00 – 1.95 (m, 2 H), 1.94 – 1.88 (m, 2 H); 13C NMR (126 MHz,
CDCl3): δ (ppm) = 140.9, 137.2, 137.1, 129.8, 129.4, 128.4, 128.3,
(7 μL, 0.039 mmol), pyrrolidine (3 μL, 0.039 mmol), SF5Cl (1.48 M in
hexane, 0.40 mL, 0.58 mmol) and dichloromethane (3.9 mL) were
engaged in general procedure to afford the title compound as a colorless
oil (59 mg, 0.20 mmol, 51 %) after purification by flash chromatography
8

A. Gilbert et al.
Journal of Fluorine Chemistry 243 (2021) 109734
126.5, 126.1, 125.0, 35.5, 35.0, 29.5, 28.8, 22.4; 19F NMR (470 MHz,
CDCl3): δ (ppm) = 88.0 – 85.1 (m, 1 F), 84.5 – 80.1 (m, 1 F), 67.4 (dd,
J = 151.4, 8.4 Hz, 4 F), 67.3 (dd, J = 150.1, 9.4 Hz, 4 F). GC–MS (EI)
[19]: m/z calcd for C11H12ClF5S [M]+ 306.03 found 305.93; IR (ATR,
139.1, 139.0, 59.9, 40.7, 38.6, 36.4, 34.8, 34.7, 27.8; 19F NMR
(470 MHz, CDCl3): δ (ppm) = 82.8 – 81.5 (m, 1 F), 67.6 (dd, J = 151.4,
8.2 Hz, 4 F). GC–MS (CI) [19]: m/z calcd for C15H21ClF5O2S [M+H]+
395.08 found 395.27; IR (ATR, Diamond):
1454, 1230, 1074, 825, 717.
ν
(cmꢀ 1) = 2907, 2854, 1726,
Diamond):
ν
(cmꢀ 1) = 2930, 1497, 1454, 1088, 887, 829, 716, 698.
4.4.4. (Z)-4-chloro-5-(pentafluoro-λ6-sulfanyl)pent-4-en-1-yl benzoate
(4d)
4.4.8. (Z)-(2-chloro-2-phenylvinyl)pentafluoro-λ6-sulfane (4 h)
Phenylacetylene (32 mg, 0.31 mmol), 2,2-diphenylacetaldehyde
Pent-4-yn-1-yl benzoate (20 mg, 0.10 mmol), 2,2-diphenylacetalde-
(6 μL, 0.031 mmol), pyrrolidine (2 μL, 0.031 mmol), SF5Cl (1.18 M in
hyde (2
μ
L, 0.010 mmol), pyrrolidine (1
μL, 0.010 mmol), SF5Cl
hexane, 0.53 mL, 0.93 mmol) and diethyl ether (3.1 mL) were engaged
in general procedure to afford the title compound as a colorless oil
(27 mg, 0.10 mmol, 33 %) after purification by flash chromatography
using 100 % hexane as the eluent. 1H NMR (500 MHz, CDCl3): δ
(ppm) = 7.43 – 7.39 (m, 3 H), 7.37 – 7.34 (m, 2 H), 6.93 (p, J =7.6 Hz,
1 H); 19F NMR (470 MHz, CDCl3): δ (ppm) = 81.9 – 80.6 (m, 1 F), 69.0
(dd, J = 152.9, 7.6 Hz, 4 F). Analytical data were identical to those
previously reported [11].
(1.48 M in hexane, 0.21 mL, 0.30 mmol) and diethyl ether (1.0 mL) were
engaged in general procedure to afford the title compound as a colorless
oil (28 mg, 0.08 mmol, 81 %) after purification by flash chromatography
using hexane/Et2O (95:5) as the eluent. 1H NMR (500 MHz, CDCl3): δ
(ppm) = 8.05 – 8.03 (m, 2 H), 7.59 – 7.56 (m, 1 H), 7.45 (td, J = 7.8,
1.5 Hz, 2 H), 6.66 (p, J =8.2 Hz, 1 H), 4.38 (td, J = 6.1, 1.5 Hz, 2 H), 2.90
(t, J =7.7 Hz, 2 H), 2.17 – 2.11 (m, 2 H); 13C NMR (126 MHz, CDCl3): δ
(ppm) = 166.4, 137.6, 137.5, 137.3, 133.0, 129.9, 129.5, 128.4, 63.5,
32.9, 26.5; 19F NMR (470 MHz, CDCl3): δ (ppm) = 83.2 – 81.9 (m, 1 F),
67.3 (dd, J = 151.1, 8.4 Hz, 4 F). HRMS-ESI (+) m/z calcd for
Declaration of Competing Interest
The authors report no declarations of interest.
Acknowledgments
C
12H13ClF5O2S [M+H]+ 351.0239 found 351.0247; IR (ATR, Diamond):
(cmꢀ 1) = 3078, 2964, 1718, 1452, 1269, 835, 708, 640.
ν
4.4.5. (Z)-3-chloro-4-(pentafluoro-λ6-sulfanyl)but-3-en-1-yl benzoate (4e)
But-3-yn-1-yl benzoate (19 mg, 0.11 mmol), 2,2-diphenylacetalde-
We acknowledge the financial support of the Natural Sciences and
Engineering Research Council of Canada (NSERC), OmegaChem and
hyde (2 μL, 0.011 mmol), pyrrolidine (1 μL, 0.011 mmol), SF5Cl
´
(1.48 M in hexane, 0.22 mL, 0.33 mmol) and diethyl ether (1.1 mL) were
engaged in general procedure to afford the title compound as a colorless
oil (27 mg, 0.08 mmol, 72 %) after purification by flash chromatography
using hexane/Et2O (98:02) as the eluent. 1H NMR (500 MHz, CDCl3): δ
(ppm) = 8.03 (dd, J =8.4 Hz, 1.3 Hz, 2 H), 7.63 – 7.51 (m, 1 H), 7.45 (m,
2 H), 6.77 (p, J =8.2 Hz, 1 H), 4.61 (t, J =6.2 Hz, 2 H), 3.19 (t, J =6.5 Hz,
2 H); 13C NMR (126 MHz, CDCl3): δ (ppm) = 166.2, 133.2, 129.6, 128.4,
60.8, 35.1, 30.3, 29.7; 19F NMR (470 MHz, CDCl3): δ (ppm) = 83.2 –
81.9 (m, 1 F), 67.3 (dd, J = 151.3, 8.2 Hz, 4 F). GC–MS (CI) [19]: m/z
calcd for C11H11ClF5O2S [M+H]+ 337.00 found 336.93; IR (ATR, Dia-
Universite Laval.
Appendix A. Supplementary data
Supplementary material related to this article can be found, in the
online version, at doi:https://doi.org/10.1016/j.jfluchem.2021.10
9734.
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