CF3S(O)n-Containing olefins in cyclopropanation reactions

Article abstract of DOI:10.1016/j.jfluchem.2021.109802

Cyclopropanation of trifluoromethyl(sulfinyl, sulfonyl) ethylenes was achieved by utilization of α-bromo- or α,α-dibromo 1,3-dicarbonyl compounds in the presence of bases. DBU was found to be the best choice to get satisfactory yields of cyclopropanes with CF₃S(O)_n (n = 1, 2) groups if α-bromo-1,3-dicarbonyl compounds were used. A series of new cyclopropanes bearing trifluoromethylsulfinyl group were synthesized.

Full text of DOI:10.1016/j.jfluchem.2021.109802

Journal of Fluorine Chemistry xxx (xxxx) xxx
Contents lists available at ScienceDirect
Journal of Fluorine Chemistry
journal homepage: www.elsevier.com/locate/fluor
CF S(O) -Containing olefins in cyclopropanation reactions
3
n
*
Liubov V. Sokolenko , Eduard B. Rusanov, Yurii L. Yagupolskii
Institute of Organic Chemistry, NAS of Ukraine, Murmans’ka Str., 5, Kyiv-94, 02660, Ukraine
A R T I C L E I N F O
A B S T R A C T
Keywords:
Cyclopropanation of trifluoromethyl(sulfinyl, sulfonyl) ethylenes was achieved by utilization of -bromo- or
α
Trifluoromethylsulfinyl ethylenes
Trifluoromethylsulfonyl ethylenes
Trifluoromethylsulfoxides
Trifluoromethylsulfones
Cyclopropanation
α
,
α
-dibromo 1,3-dicarbonyl compounds in the presence of bases. DBU was found to be the best choice to get
satisfactory yields of cyclopropanes with CF S(O) -bromo-1,3-dicarbonyl compounds were
3
n
(n = 1, 2) groups if α
used. A series of new cyclopropanes bearing trifluoromethylsulfinyl group were synthesized.
1
. Introduction
trifluoromethylsulfides. In mentioned patent azoles derivatives bearing
trifluoromethylsulfinyl- and (trifluoromethylsulfonyl)cyclopropyl frag-
Trifluoromethyl vinyl sulfoxide and trifluoromethyl vinyl sulfone are
molecules under interest due to the strongly polarized (e.g.,
CF (CF SO
ments were shown to possess antifungal activity.
σ
p
It is noteworthy to mention that direct cyclopropanation reactions
(
3
SO) = 0.69,
σ
p
3
2
) = 0.96) [1] double bonds, which makes
starting
from
trifluoromethylsulfonyl
ethylene
and
tri-
these compounds attractive and promising precursors for the prepara-
tion of more complex molecules via modification of unsaturated part.
Although both compounds were synthesized in our laboratory in 1967
fluoromethylsulfinyl ethylene stayed unknown.
Herein we report our results in the field of cyclopropanation re-
actions of trifluoromethylsulfinyl and trifluoromethylsulfonyl ethylenes.
[
2], the properties of trifluoromethyl vinyl sulfoxide were not well
investigated till 2010 [3,4], when we found the more suitable and effi-
cient method for its preparation [3]. At the same time, trifluoromethyl
vinyl sulfone was earlier studied in the addition reactions with N-, O-, S-,
and C-nucleophiles [2,5,6] as well as in Diels-Alder reaction [7].
The cyclopropane ring is an important structural motif in diverse
bioactive compounds [8–10] due to its uncommon bonding and as a
result increasing drugs microsomal stability, brain permeability,
bioavailability, metabolic stability, etc [9].
2. Results and discussion
Various methods for carbene generating were well summarized in
the reviews [20,21]. Nevertheless, the most common and easy route to
functionalized carbenes/carbenoids for cyclopropanations remains
decomposition of diazocompounds under the action of metal catalysts
[22], for example, palladium diacetate [20,23,24] or dirhodium tet-
raacetate [25]. As a rule, reactions proceed in mild conditions with high
yields.
Cyclopropanes with trifluoromethylsulfonyl (triflyl) group were ob-
tained using different synthetic methodologies: intramolecular base-
mediated cyclization of γ-iodo-, γ-hydroxy-, or γ-triflyl alkyl triflones
Unfortunately, our attempts to introduce trifluoromethylsulfinyl
ethylene 1 or trifluoromethylsulfonyl ethylene 2 into cyclopropanation
[
11–13], the reaction of methyltrifluoromethylsulfone with 1,2-dibro-
moethane [14], cyclization of cyclic unsaturated triflones under fluo-
ride activation [7]. -Bis-triflylcyclopropanes were synthesized via
reaction with ethyl diazoacetate in the presence of Pd(OAc)
Rh (OAc) failed. If the reaction of olefin 1 bearing SOCF group with
ethyl diazoacetate was carried out in the presence of Pd(OAc) at an
ambient temperature product formation was not observed. Ethylene 2
with SO CF group in the same conditions reacted with ethyl diazo-
2
or
2
4
3
α
,α
2
reaction of arylhalonium bis(triflyl)methides with olefins [15–17] and
interaction of dibromo(bis)trifluoromethylsulfonyl methane with eth-
ylenes in the presence of tributylstibine [18].
2
3
acetate mainly via 1,3-dipolar cycloaddition mechanism yielding, with
high probability, the corresponding pyrazoline (according to LC-MS)
contaminated by numerous side products that prevent its isolation in
individual form. The reaction of compound 2 with ethyl diazoacetate in
To the best of our knowledge, cyclopropanes bearing tri-
fluoromethylsulfinyl group were described to date in only one patent
[
19]
by
oxidation
of
corresponding
cyclopropane
*
Corresponding author.
E-mail address: sokolenko.liubov@gmail.com (L.V. Sokolenko).
https://doi.org/10.1016/j.jfluchem.2021.109802
Received 19 March 2021; Received in revised form 29 April 2021; Accepted 29 April 2021
Available online 8 May 2021
0
022-1139/© 2021 Elsevier B.V. All rights reserved.
Please cite this article as: Liubov V. Sokolenko, Journal of Fluorine Chemistry, https://doi.org/10.1016/j.jfluchem.2021.109802

L.V. Sokolenko et al.
Journal of Fluorine Chemistry xxx (xxxx) xxx
ionic compound, which was added to the double bond of ethylene 2 to
give intermediate A. In examples described in the literature [26,28] such
intermediates underwent intramolecular nucleophilic substitution of
bromine atom yielding corresponding cyclopropanes. The strong
3 2
electron-withdrawing nature of CF SO -group may be the reason for
anion stabilization and low rate of cyclization that allowed intermediate
A to lose a second bromine atom with following addition to another
molecule of ethylene 2. As a result, after work-up compound 5 was
obtained.
As far as absolutely different results were obtained for olefins under
investigation, as well as cyclopropane 4 was isolated in low yield, other
conditions for cyclopropanation reaction via ionic mechanism were
tested. Thus, triphenylphosphine instead of tributylstibine was used, but
no reaction occurred in this case.
Scheme 1. The reaction of ethylenes
1
and
2
with diethyl
α
,α-dibromomalonate and tributylstibine.
the presence of PdCl
Both olefins reacted with ethyl diazoacetate in the presence of
Rh (OAc) with the formation of complex mixtures of unidentified
products.
2 2
(dppf) led to the same result (according to LC-MS).
Cyclopropanation reactions with diethyl bromomalonate in the
presence of a base (NaH or DBU) is widely used in fullerene chemistry
and known as Bingel reaction [31,32]. Similar reactions with
electron-deficient olefins and diethyl bromomalonate were also
described [30]. We applied this methodology with some modifications
to cyclopropanation reactions of ethylenes 1, 2.
2
4
The alternative route to functionalized cyclopropanes was shown to
be cyclopropanation of electrophilic alkenes via ionic mechanism –
Michael-Initiated Ring Closure (MIRC) reactions [26]. In particular
cases, reactions of alkenes with diethyl dibromomalonate in the pres-
ence of stibines [27–29] and diethyl bromomalonate in the presence of
bases could be mentioned [30,31].
Experiments on compounds 1 and 2 interaction with diethyl bro-
momalonate and DBU were carried out in THF as a solvent. In com-
parison with described examples [30,31], reactions of ethylenes 1, 2
with diethyl bromomalonate/DBU proceeded with significant
exothermic effect; the optimal temperature for interaction was found to
Taking into account our previous results in cyclopropane synthesis
starting from dibromo(bis)trifluoromethylsulfonyl methane and
electron-deficient olefins under tributylstibine activation [18], we
◦
be -30 C. Both olefins in these conditions gave cyclopropanes in mod-
decided to apply such methodology to the CF
propanes preparation starting from ethylenes 1 and 2. As model dibro-
mide, we chose symmetrical diethyl -dibromomalonate 3 (Scheme 1).
It was found that compound reacted with diethyl
-dibromomalonate and tributylstibine yielding two diastereomeric
cyclopropanes in 26% total isolated yield. Surprisingly, the reaction of
ethylene 2 with diethyl -dibromomalonate and tributylstibine in the
3 n
S(O) -containing cyclo-
erate yields (Scheme 3).
If pyridine was used as the base in the reaction of olefin 1 with
diethyl bromomalonate, no reaction occurred; with DABCO the reaction
proceeded slowly with the low conversion of starting compounds. All the
abovementioned results are summarized in Table 1.
α,α
1
α,α
It is evident from Table 1 that diethyl bromomalonate 6 combined
with DBU is the most suitable reagent for cyclopropanation reactions
starting from olefins 1 and 2.
α,α
same conditions led to product 5 formation in 42% yield. NMR data of
compound 5 is in accordance with the literature [6] and additionally, we
confirmed its structure by X-ray analysis (Fig. 1).
Cyclopropanation reactions of trifluoromethylsulfinyl ethylene 1
(Table 2) and trifluoromethylsulfonyl ethylene 2 (Table 3) using a va-
We propose the following scheme for compound 5 formation
riety of
α
-bromo dicarbonyl compounds as well as -bromo malonodi-
α
(
Scheme 2). Initially, dibromide 3 reacted with tributylstibine to form an
nitrile were performed following these optimization studies.
Fig. 1. Molecular structure of compound 5. Ellipsoids are drawn at a 50% probability level.
2

L.V. Sokolenko et al.
Journal of Fluorine Chemistry xxx (xxxx) xxx
Scheme 2. A possible scheme for compound 5 formation.
Scheme 3. The reaction of ethylenes 1 and 2 with diethyl -bromomalonate and DBU.
α
It is noteworthy to mention that ethyl bromoacetate bearing only one
electron-withdrawing group is inefficient in the reaction with ethylene 1
and DBU as the conversion of ethylene 1 was low and only tar formation
formation and product 16 was isolated from the reaction mixture with
low yield.
The structure of synthesized compounds was proved by 2D NMR and
APT spectra using product 14 as an example (see Supporting
Information).
was observed. The reaction of olefin 1 with -bromo malonodinitrile was
α
accompanied by significant tar formation as well, thus product 11 was
isolated with only 70% purity and low yield after two column chroma-
tography processes. In the case of 2-bromo-1-phenylbutane-1,3-dione
traces of product 13 were detected in the crude reaction mixture by
3. Conclusions
1
H NMR, but due to large quantities of tar, we were not able to isolate it
In conclusion, cyclopropanation reactions starting from tri-
from the reaction mixture. Compounds 4 and 9 were formed as two
diastereomers, which were separated by column chromatography to
give single diastereomers with 85% de. Diastereomers of cyclopropanes
fluoromethylsulfinyl ethylene 1 and trifluoromethylsulfonyl ethylene 2
were studied. It was shown that olefins 1 and 2 reacted with -bromo
α
dicarbonyl compounds with DBU as a base to give cyclopropanes
bearing functional groups in moderate yields. A series of new cyclo-
propanes with trifluoromethylsulfinyl group were synthesized.
1
0 were not separated by column chromatography; the only series of
fractions with different diastereomers ratios were obtained. Two out of
the three diastereomers of product 12 were isolated in pure form after
column chromatography; the third one was obtained as the mixture with
another diastereomer.
4. Experimental
Interestingly, compound 15 was formed as one diastereomer ac-
cording to 1H NMR of the crude reaction mixture. Diastereomers of
compounds 17 and 18 were separated by column chromatography to
4.1. General information
Reactions were carried out under dry argon using flame-dried
glassware. THF was distilled over sodium immediately before use.
Tributylstibine [33], diethyl dibromomalonate [34], dibenzyl
give pure ones with >99% de. Similar to the reaction of
α-bromo
malonodinitrile with olefin 1, its reaction with ethylene 2 led to tar
3

L.V. Sokolenko et al.
Journal of Fluorine Chemistry xxx (xxxx) xxx
Table 1
Optimization of the cyclopropanation reactions of ethylenes 1 and 2.
a
◦
Reactions were carried out at -30 C to RT without solvent.
b
◦
Reactions were carried out in THF at -30 C to RT.
malonate [35], dibenzyl bromomalonate [36], diethyl bromomalonate
30], -bromomalonodinitrile [37], ethyl -bromoacetoacetate [38]
4.2. Preparation of -bromo-pivaloylacetonitrile
α
[
α
α
were prepared according to the literature procedures.
To the solution of pivaloylacetonitrile (1 g, 8 mmol) in dioxane (20
mL) bromine (1.28 g, 8 mmol) in dioxane (40 mL) was added dropwise
over 2 h at room temperature. The reaction mixture was stirred at room
temperature until complete discolouration occurred, then diluted by
Purification of products by column chromatography (CC) was per-
formed on Silica gel, 70-230 mesh 60A (Aldrich), or neutral activated
1
(
Brockmann activity I) aluminium oxide 60A (Aldrich). H NMR spectra
were recorded at 500 MHz with Bruker AVANCE DRX 500 instrument, or
methyl-tert-butyl ether (MTBE) (60 mL), washed with 10% NaHCO
. Sol-
3
3
4
00 MHz with Bruker AC-300, or 400 MHz with Varian UNITY – Plus
00 spectrometer, or 600 MHz with Agilent ProPulse 600 instrument.
F NMR spectra were recorded on Varian UNITY – Plus 400 spec-
solution (3 × 15 mL), water (3 × 15 mL), and dried over MgSO
4
vents were removed on the rotor evaporator to yield 2.13 g (85%) of
desired product, which was used for further reactions without
purification.
1
9
trometer at 376.5 MHz or 470 MHz with Bruker AVANCE DRX 500 in-
strument or 188 MHz with Bruker AC-200. Chemical shifts are given in
Spectroscopic data were in agreement with the literature [39].
4 3
ppm relative to Me Si and CCl F, respectively, as internal or external
standards. 13C NMR-spectra (proton decoupled) were recorded on a
Bruker AVANCE DRX 500 instrument at 125.7 MHz, or on Varian UNITY
4.3. Preparation of 2-bromo-1-phenyl-1,3-butanedione
–
Plus 400 spectrometer at 100.6 MHz, or 150.8 MHz with Agilent
N-Bromosuccinimide (1.65 g, 9.3 mmol) was added to the solution of
1-phenyl-1,3-butanedione (1.5 g, 9.3 mmol) in dichloromethane (20
mL). The reaction mixture was stirred at room temperature for 48 h. The
solution was washed with 10% HCl solution (3 × 10 mL), water (3 × 10
ProPulse 600 instrument. Melting points were determined in open
capillaries using the SMP3 instrument (Stuart Scientific Bibby Sterlin
Ltd, Stone, Staffordshire, UK). Elemental analysis was performed in the
Analytical Laboratory of the Institute of Organic Chemistry, NAS of
Ukraine, Kyiv.
mL), and dried over MgSO . The solvent was removed on the rotor
4
evaporator to yield 2.1 g (94%) of desired product, which was used for
4

L.V. Sokolenko et al.
Journal of Fluorine Chemistry xxx (xxxx) xxx
Table 2
Cyclopropanation reactions of trifluoromethylsulfinyl ethylene 1.
a
Entry
X
Y
Product (diastereomers ratio)
Total yield (%)
b
1
2
3
4
5
6
7
H
COOEt
COOEt
COOBn
8
0
d
COOEt
COOBn
CN
4 (1:7)
60
55
30
15
30
d
9 (1:15)
t
d
COBu
10 (1.3:2:1)
e
CN
CN
11 (one diastereomer)
d
COCH
COCH
3
3
COOCH
COPh
3
12 (1:1:1)
c
13
0
a
Isolated yield.
b
c
Only tar formation was observed as well as a large quantity of starting olefin 1 was detected in the reaction mixture.
Only tar formation was observed, the product was not isolated from the reaction mixture by column chromatography.
d
e
1
Diastereomers ratio obtained in the crude reaction mixture according to H NMR integration ratio.
Only one diastereomer with 70% purity was isolated from the reaction mixture by two column chromatography processes.
Table 3
Cyclopropanation reactions of trifluoromethylsulfonyl ethylene 2.
a
Entry
X
Y
Product (diastereomers ratio)
Total yield (%)
1
2
3
4
5
6
COOEt
COOBn
CN
COOEt
COOBn
7
40
47
60
10
27
30
14
t
b
COBu
15 (one diastereomer)
c
CN
CN
16
d
COCH
COCH
3
3
COOCH
COPh
3
17 (3:1)
d
18 (1:1)
a
Isolated yield.
b
c
1
Only one diastereomer was formed according to H NMR of the crude reaction mixture.
Significant tar formation was observed, the product was isolated from the reaction mixture by column chromatography with ~90% purity.
d
1
Diastereomers ratio obtained in the crude reaction mixture according to H NMR integration ratio.
further reactions without purification.
All fractions were combined, the solvent was removed in vacuo.
In the case of ethylene 1 column chromatography of the residue on
silica (eluent pentane – MTBE, 100:5) led to corresponding diastereo-
meric cyclopropanes 4 as colourless oils. Yield of first diastereomer 0.20
g (10%), second one 0.30 g (16%); total yield 0.5 g (26%).
In the case of ethylene 2 addition of pentane led to the formation of
the product 5 precipitate. The precipitate was filtered off, washed with
pentane, and dried on air to give pure compound 5 as a white solid. Yield
0.7 g (47%).
Spectroscopic data were in agreement with the literature [40].
4
.4. General procedure for cyclopropanation reactions using diethyl
dibromomalonate and tributylstibine (Method A)
Diethyl dibromomalonate (6.3 mmol) was placed into the flask and
◦
tributylstibine (6.9 mmol) was added dropwise at -30 C followed by the
addition of ethylene 1 or 2 (6.9 mmol) at the same temperature. The
reaction mixture was gently warmed to room temperature and then
stirred for 24 h. To separate products from Sb-containing compounds
Diethyl 2,2-bis(2-(trifluoromethylsulfonyl)ethyl)malonate (5). mp 65-
66◦C (Lit. 67-68◦C) [6]. H NMR (CDCl , 400 MHz) δ 1.26-1.29 (m, 6H,
1
3
2CH ), 2.35-2.39 (m, 4H, 2CH ), 3.39-3.44 (m, 4H, 2CH ), 4.23-4.28 (m,
3
2
2
2 3
column chromatography on Al O using MTBE as eluent was performed.
5

L.V. Sokolenko et al.
Journal of Fluorine Chemistry xxx (xxxx) xxx
4
1
2
H, 2CH
2
). 19F NMR (CDCl
3
, 376.5 MHz) δ -78.25 (s). 13C NMR (CDCl
3
,
S, 12.00. Found: C, 44.95; H, 44.51; S, 12.01.
First diastereomer:
1
25.7 MHz) δ 168.0, 118.9 (q, JC-F = 328.1 Hz, CF
3
), 62.5, 54.5, 45.4,
1
5.5, 13.4. Anal. Calcd for C13
H
18
F
6
O
6
S
2
: C, 34.82; H, 4.05; S, 14.30.
H NMR (CDCl
Hz, 6.0 Hz, CH), 2.36 (t, 1H, J = 6.0 Hz, CH), 3.32 (t, 1H, J = 8.5 Hz,
3
, 500 MHz) δ 1.39 (s, 9H, t-Bu), 2.05 (dd, 1H, J = 8.5
Found: C, 34.84; H, 4.04; S, 14.29.
CH). 19F NMR (CDCl
MHz) δ 201.4, 125.4 (q, JC-F = 335.6 Hz, CF
= 3.8 Hz, C-SOCF ), 25.9, 21.6, 19.8.
Second diastereomer:
, 188 MHz) δ -72.85 (s). C NMR (CDCl
13
3
3
, 125.7
1
3
4
.5. General procedure for cyclopropanation reactions using
α
-bromo
3
), 118.0, 46.0, 41.3 (q, JC-
dicarbonyl compounds or -bromo malonodinitrile and DBU (Method B)
α
F
3
1
To the solution of ethylene 1 or 2 (7 mmol) in THF (10 mL) solution
H NMR (CDCl
3
, 300 MHz) δ 1.41 (s, 9H, t-Bu), 1.93 (t, 1H, J = 6.0
of
α
-bromo dicarbonyl compound or
α
-bromo malonodinitrile (7 mmol)
Hz, CH), 2.20 (dd, 1H, J = 8.0 Hz, 6.0 Hz, CH), 3.27 (t, 1H, J = 8 Hz,
◦
1
9
1
3
in THF (10mL) was added at -30 C. To the resulting mixture solution of
DBU (7 mmol) in THF (10 mL) was added dropwise with such a rate to
CH). F NMR (CDCl
3
, 188 MHz) δ -71.31 (s). C NMR (CDCl
3
, 125.7
1
3
MHz) δ 201.3, 125.1 (q, JC-F = 335.6 Hz, CF
3
), 116.3, 46.1, 43.8 (q, JC-
◦
keep the temperature in the range -30÷-25 C. After the addition of DBU
F
= 3.8 Hz, C-SOCF
3
), 25.9, 21.2, 20.9.
reaction mixture was gently warmed to room temperature and then
stirred for 24 h. Ether (30 mL) was added to the reaction mixture, the
precipitate was filtered off, and organic solvents were removed in vacuo.
Column chromatography of residue led to desired cyclopropanes
isolation.
Third diastereomer:
1
H NMR (CDCl
3
, 300 MHz) δ 1.43 (s, 9H, t-Bu), 2.17 (dd, 1H, J = 9.0
Hz, 6.5 Hz, CH), 2.27 (t, 1H, J = 6.5 Hz, CH), 3.51 (t, 1H, J = 9.0 Hz,
CH). 19F NMR (CDCl
MHz) δ 202.6, 124.7 (q, JC-F = 335.6 Hz, CF
= 3.8 Hz, C-SOCF ), 25.9, 21.5, 19.9.
2-(Trifluoromethylsulfinyl)cyclopropane-1,1-dicarbonitrile (11). First
, 188 MHz) δ -72.77(s). C NMR (CDCl
13
3
3
, 125.7
1
3
3
), 115.9, 46.1, 45.8 (q, JC-
Diethyl 2-(trifluoromethylsulfinyl)cyclopropane-1,1-dicarboxylate (4).
F
3
(
Method B) Eluent pentane – MTBE, 100:5. After column chromatog-
raphy yield of first diastereomer 0.30 g (15%), second one 0.93 g (45%);
total yield 1.23 g (60%). Colourless oils.
chromatography process: pentane – MTBE, from 100:0 to 0:100; second
chromatography process: pentane – MTBE, 100:10. Yield 0.22 g (15%)
1
First diastereomer:
with 70% purity. Colourless oil. H NMR (CDCl
3
, 400 MHz) δ 2.36 (dd,
1
H NMR (CDCl
3
, 400 MHz) δ 1.28 (t, 6H, J = 6.8 Hz, 2CH
3
), 1.87 (dd,
1H, J = 8.8 Hz, 7.2 Hz, CH), 2.66 (t, 1H, J = 7.2 Hz, CH), 3.39 (t, 1H,
19
1
H, J = 8.4 Hz, 6.8 Hz, CH), 2.26 (t, 1H, J = 6.8 Hz, CH), 3.03 (t, 1H,
J = 8.8 Hz, CH). F NMR (CDCl , 188 MHz) δ -72.06 (s).
3
1
9
J = 6.8 Hz, CH), 4.24 (q, 4H, J = 6.8 Hz, 2CH
2
). F NMR (CDCl
3
, 376.5
Methyl 1-acetyl-2-((trifluoromethylsulfinyl)cyclopropane-1-carboxylate
(12). Eluent pentane – MTBE, 100:10. After column chromatography
yield of first diastereomer 0.14 g (8%), second one 0.10 g (6%), and
mixture of second and third diastereomers in 2:1 ratio 0.30 g (16%);
total yield 0.54 g (30%). Colourless oils.
1
3
MHz) δ -73.42 (s). C NMR (CDCl
3
, 125.7 MHz) δ 167.4, 164.8, 125.2
),
S: C, 39.74; H, 4.34; S,
1
(
q, JC-F = 334.4 Hz, CF
3
), 62.9, 62.8, 37.9 (q, JC-F = 3.8 Hz, C-SOCF
3
3
1
3.1, 13.9, 13.8, 12.8. Anal. Calcd for C10
13 3 5
H F O
0.61. Found: C, 39.75; H, 4.34; S, 10.62.
Second diastereomer:
First diastereomer:
1
1
H NMR (CDCl
3
, 500 MHz) δ 1.29-1.36 (m, 6H, 2CH
3
), 1.87 (t, 1H,
H NMR (CDCl
3
, 400 MHz) δ 1.86 (t, 1H, J = 7.2 Hz, CH), 2.25 (t, 1H,
), 3.08 (t, 1H, J = 7.2 Hz, CH), 3.82 (s,
, 376.5 MHz) δ -73.50 (s). Anal. Calcd for
S: C, 37.21; H, 3.51; S, 12.42. Found: C, 37.22; H, 3.52; S,
J = 6.5 Hz, CH), 1.99 (dd 1H, J = 9 Hz, 6.5 Hz, CH), 3.36 (dd, 1H, J = 9
J = 6.4 Hz, CH), 2.40 (s, 3H, CH
3
1
9
19
Hz, 6.5 Hz, CH), 4.25-4.39 (m, 4H, 2CH
2
). F NMR (CDCl
3
, 376.5 MHz)
3 3
3H, CH ). F NMR (CDCl
1
3
1
δ -72.45 (s). C NMR (CDCl
3
, 125.7 MHz) δ 166.6, 165.5, 125.4 (q, JC-
C
8
9
H F
3
O
4
3
1
2.40.
Second diastereomer:
F
= 335.6 Hz, CF
6.6, 13.9, 13.8. Anal. Calcd for C10
0.61. Found: C, 39.75; H, 4.33; S, 10.60.
Diethyl 2-(trifluoromethylsulfonyl)cyclopropane-1,1-dicarboxylate (7).
Eluent pentane – MTBE, 100:5. Yield 0.90 g (40%) (Method B). Col-
3
), 63.0, 62.9, 40.27 (q, JC-F = 3.8 Hz, C-SOCF
3
), 34.4,
1
13 3 5
H F O
S: C, 39.74; H, 4.34; S,
1
1
H NMR (CDCl
3
, 400 MHz) δ 1.92-1.98 (m, 2H, 2CH), 2.55 (s, 3H,
19
CH
3
), 3.50 (t, 1H, J = 7.2 Hz, CH), 3.82 (s, 3H, CH
3
). F NMR (CDCl
3
,
1
3
376.5 MHz) δ -73.36 (s). C NMR (CDCl
3
, 125.7 MHz) δ 199.2, 167.8,
1
1
3
ourless oil. H NMR (CDCl
3
, 600 MHz) δ 1.28-1.32 (m, 6H, 2CH3), 1.96
125.4 (q, JC-F = 335.6 Hz, CF
3
), 53.5, 42.7 (q, JC-F = 3.8 Hz, C-SOCF
3
),
(
dd, 1H, J = 8.4 Hz, 6 Hz, CH), 2.21 (t, 1H, J = 6 Hz, CH), 3.36 (t, 1H,
39.6, 30.4, 29.7, 18.2. Anal. Calcd for C H F O
8 9 3 4
S: C, 37.21; H, 3.51; S,
1
9
J = 8.4 Hz, CH), 4.18-4.31 (m, 4H, 2CH
2
). F NMR (CDCl
3
, 376.5 MHz)
12.42. Found: C, 37.20; H, 3.50; S, 12.41.
1
3
1
δ -77.89 (s). C NMR (CDCl
3
, 150.8 MHz) δ 164.2, 160.8, 117.0 (q, JC-
Third diastereomer:
3
1
3
H NMR (CDCl , 500 MHz) δ 1.86-1.94 (m, 2H, 2CH), 2.42 (s, 3H,
19
F
= 327.2 Hz, CF
5.9, 11.6, 11.4. Anal. Calcd for C10
0.07. Found: C, 39.75; H, 4.11; S, 10.08.
Dibenzyl 2-(trifluoromethylsulfinyl)cyclopropane-1,1-dicarboxylate (9).
3
), 61.3, 60.7, 35.0 (q, JC-F = 1.5 Hz, C-SO
2 3
CF ), 33.7,
1
H
13
F
3
O
6
S: C, 37.74; H, 4.12; S,
CH
(CDCl
167.4, 125.4 (q, JC-F = 335.6 Hz, CF
SOCF ), 39.4, 29.02, 29.0, 18.8.
Dibenzyl 2-(trifluoromethylsulfonyl)cyclopropane-1,1-dicarboxylate
(14). Eluent pentane – MTBE, 100:5. Yield 1.45 g (47%). White solid.
3
), 3.29 (dd, 1H, J = 8.8 Hz, 7.0 Hz, CH), 3.85 (s, 3H, CH
3
). F NMR
1
3
1
3
, 376.5 MHz) δ -73.73 (s). C NMR (CDCl
3
, 125.7 MHz) δ 198.3,
1
3
3
), 53.4, 42.0 (q, JC-F = 3.8 Hz, C-
Eluent pentane – MTBE, 100:30. Yield 1.64 g (55%). White solid. mp 55-
6 C.
Major diastereomer:
3
◦
5
1
◦
1
H NMR (CDCl
3
, 500 MHz) δ 1.93 (t, 1H, J = 6.5 Hz, CH), 2.03 (dd,
mp 45-46 C. H NMR (CDCl
3
, 500 MHz) δ 2.02 (dd, 1H, J = 8.5 Hz, 6.0
1
H, J = 8.5 Hz, 6.5 Hz, CH), 3.43 (t, 1H, J = 8.5 Hz, CH), 5.19 (s, 2H,
Hz, CH), 2.31 (t, 1H, J = 6.0 Hz, CH), 3.45 (t, 1H, J = 8.5 Hz, CH), 5.16-
19
19
CH
2
), 5.27 (s, 2H, CH
2
), 7.27-7.35 (m, 10H, ArH). F NMR (CDCl
3
,
5.29 (m, 4H, 2CH
2
), 7.25-7.37 (m, 10H, 10 ArH). F NMR (CDCl
3
, 376.5
1
3
13
3
76.5 MHz) δ -72.34 (s). C NMR (CDCl
34.4, 134.3, 128.69, 128.68, 128.66, 128.6, 128.5, 128.3, 125.4 (q,
3
, 125.7 MHz) δ 166.5, 165.4,
MHz) δ -77.70 (s). C NMR (CDCl
134.1, 128.8, 128.7, 128.6, 128.5, 128.2, 119.3 (q,
CF ), 69.0, 37.5, 35.9, 18.4. Anal. Calcd for C20
3.87; S, 7.25. Found: C, 54.29; H, 3.88; S, 7.25.
3
, 125.7 MHz) δ 166.2, 162.9, 134.4,
1
1
1
J
C-F = 326.8 Hz,
3
J
C-F = 335.6 Hz, CF
4.3, 17.1. Anal. Calcd for C20
Found: C, 56.35; H, 4.01; S, 7.51.
Minor diastereomer (as 7% impurity in the major one):
3
), 68.9, 68.6, 40.8 (q,
J
C-F = 3.8 Hz, C-SOCF
3
),
3
17 3 6
H F O S: C, 54.30; H,
3
17 3 5
H F O
S: C, 56.34; H, 4.02; S, 7.52.
1-Pivaloyl-2-(trifluoromethylsulfonyl)cyclopropane-1-carbonitrile (15).
Eluent pentane – MTBE, 100:5. Yield 1.2 g (60%). White solid. mp 55-
1
◦
1
H NMR (CDCl
3
, 500 MHz) δ 2.36 (t, 1H, CH), 3.09 (t, 1H, CH), 3.99
), 5.27 (s, 2H, CH ), 7.27-7.35 (m, 10H,
, 376.5 MHz) δ -72.78 (s).
-Pivaloyl-2-(trifluoromethylsulfinyl)cyclopropane-1-carbonitrile (10).
Eluent pentane – MTBE, 100:10. Yield of diasteremers mixture 0.56 g
30%). Colourless oil. Anal. Calcd for C10 NO S: C, 44.94; H, 4.53;
56 C. H NMR (CDCl , 500 MHz) δ 1.44 (s, 9H, t-Bu), 2.21 (dd, 1H,
3
(
t, 1H, CH), 5.19 (s, 2H, CH
2
2
J = 8.5 Hz, 6.5 Hz, CH), 2.38 (t, 1H, J = 6.5 Hz, CH), 3.33 (t, 1H, J = 8.5
19 13
1
9
ArH). F NMR (CDCl
3
Hz, CH). F NMR (CDCl
3
, 470 MHz) δ -76.95 (s). C NMR (CDCl
3
,
1
1
125.7 MHz) δ 200.4, 119.2 (q, JC-F = 326.8 Hz, CF
3
), 114.6, 46.2, 40.3,
25.9, 21.8, 21.6. Anal. Calcd for C10
12 3 3
H F NO S: C, 42.40; H, 4.27; S,
(
H
12
F
3
2
11.32. Found: C, 42.39; H, 4.28; S, 11.34.
6

L.V. Sokolenko et al.
Journal of Fluorine Chemistry xxx (xxxx) xxx
2
-(Trifluoromethylsulfonyl)cyclopropane-1,1-dicarbonitrile
(16).
Declaration of Competing Interest
Eluent pentane – MTBE, 100:15. Yield 0.16 g (10%) with 90% purity.
1
Colourless oil. H NMR (acetone-d6, 400 MHz) δ 2.92 (t, 1H, J = 7.6 Hz,
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
1
9
CH), 3.08 (t, 1H, J = 8.8 Hz, CH), 4.78 (t, 1H, J = 8.8 Hz, CH). F NMR
1
3
(
CDCl
19.7 (q, JC-F = 326.0 Hz, CF
Methyl 1-acetyl-2-((trifluoromethylsulfonyl)cyclopropane-1-carboxylate
3
, 376.5 MHz) δ -76.48 (s). C NMR (acetone-d6, 100.6 MHz) δ
1
1
3
), 112.3, 110.6, 39.2, 20.8, 7.2.
Liubov V. Sokolenko reports was provided by Institute of Organic
Chemistry, NAS of Ukraine.
(
17). Eluent pentane – MTBE, 100:10. Yield of first diastereomer 0.35 g
(
18%), second one 0.17 g (9%); total yield 0.52 g (27%). Colourless oils.
Supplementary materials
First diastereomer:
1
H NMR (CDCl
3
, 400 MHz) δ 1.82 (dd, 1H, J = 8.6 Hz, 6 Hz, CH),
), 3.37 (t, 1H, J = 8.6 Hz, CH),
Supplementary material associated with this article can be found, in
the online version, at doi:10.1016/j.jfluchem.2021.109802.
2
.19 (t, 1H, J = 6 Hz, CH), 2.38 (s, 3H, CH
3
1
9
13
3
.85 (s, 3H, CH
, 100.6 MHz) δ 197.5, 165.4, 119.3 (q, C-F = 327.0 Hz, CF
8 9 3 5
3.8, 41.6, 38.2, 28.2, 19.5. Anal. Calcd for C H F O S: C, 35.04; H,
3
). F NMR (CDCl
3
, 376.5 MHz) δ -77.75 (s). C NMR
1
(
CDCl
3
J
3
),
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3
[
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[
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(18).
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second one 0.34 g (15%); total yield 0.68 g (30%). White solids.
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R
f
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9
13
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, 376.5 MHz) δ -78.25 (s). C NMR (CDCl
3
, 125.7
[
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3
11 3 4
H F O
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◦
1
2358–2366, https://doi.org/10.1021/ja00269a037.
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f
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1
1
9
13
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, 376.5 MHz) δ -78.02 (s). C NMR (CDCl
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[
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F
6
O
S
8 2
, M = 480.39,monoclinic, space
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◦
3
ꢀ 3
ꢀ 1
(
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[
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8