Metal-Free Visible-Light-Promoted Trifluoromethylation of Vinylcyclopropanes Using Pyrylium Salt as a Photoredox Catalyst

Article abstract of DOI:10.1021/acs.joc.9b01033

Visible-light-induced metal-free trifluoromethylation of activated, carbocyclic, and unactivated vinylcyclopropanes via a ring-opening reaction using the Langlois reagent (CF₃SO₂Na) is reported to synthesize allylic trifluoromethylated derivatives. Allylic trifluoromethylation was achieved by a photo-oxidative single electron transfer (SET) process at an ambient temperature and under metal-free conditions and visible-light irradiation using pyrylium salt as a photoredox catalyst. The reported methodology has an operational simplicity, broad substrate scope, high functional group tolerance, and scalability.

Full text of DOI:10.1021/acs.joc.9b01033

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Note
Metal-free Visible Light Promoted Trifluoromethylation of
Vinylcyclopropanes Using Pyrylium Salt as Photoredox Catalyst
Palasetty Chandu, Krishna Gopal Ghosh, and Devarajulu Sureshkumar
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.9b01033 • Publication Date (Web): 03 Jun 2019
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Metal-Free Visible Light Promoted Trifluoromethylation of Vinylcyclopropanes Using
Pyrylium Salt as Photoredox Catalyst
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Palasetty Chandu, Krishna Gopal Ghosh and Devarajulu Sureshkumar*
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Department of chemical sciences, Indian Institute of Science Education and Research Kolkata Mohanpur-
741246, West Bengal, India
Abstract: Visible light induced metal-free trifluoromethylation of activated, carbocyclic and
unactivated vinylcyclopropanes via ring opening reaction using Langlois reagent (CF3SO2Na) is
reported to synthesize allylic trifluoromethylated derivatives. Allylic trifluoromethylation was
achieved by photo-oxidative single electron transfer (SET) process at ambient temperature and
metal-free condition under visible-light irradiation using pyrylium salt as photoredox catalyst.
The reported methodology has operational simplicity, broad substrate scope, high functional
group tolerance and scalability.
Trifluoromethyl group is a valuable moiety in pharmaceutical and agrochemical fields.1
Introduction of a trifluoromethyl moiety into biologically important molecule will affect
different properties like bioactivity, electrostatic interactions with targets, metabolic stability,
lipophilicity, and increase oxidative metabolism.2 Hence, the incorporation of fluorine moieties
into organic compounds is one of the essential topics in the field of organic synthesis. Csp2–CF3
formation is well studied,3 but Csp3–CF3 formation especially terminal allylic
trifluoromethylation is limited due to challenges associated with regio and stereoselective
installation of CF3 group.4 Allylic trifluoromethylated compounds are the essential building
blocks to synthesize many pharmaceutical drugs.5 Buchwald6a and Liu et al.6b showed allylic
trifluoromethylation of terminal alkenes using electrophilic fluorinating reagents, Togni and
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Umemoto respectively, by copper catalysis (Scheme 1a). Recently, Feng Liu group reported Fe-
catalyzed trifluoromethylation of activated vinylcyclopropanes using Togni reagent6c to synthesis
dihydronapthalene derivatives (Scheme 1a). Here, we report cheaper and atom economical
approach to synthesize allylic trifluoromethylated compounds using photoredox catalysis.
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Polypyridyl complexes of ruthenium and iridium metals are widely used as photocatalysts
due to their unique photophysical properties like longer excited state lifetime, different oxidative
and reductive potentials that can engage with organic molecules making them reactive
intermediate species.7 For instance, [Ir(dF-CF3-ppy)2(dtbpy)](PF6) is used in water splitting for
a) Previous work:
CF3
I
O
S
OTf
CF3
O
R
R
CF3
R
CF3
54-80%
CuTc (20 mol%)
40 °C
[(MeCN)4Cu]PF6 (15 mol%)
0 °C to rt
32-78%
Lei-liu work
Buchwald work
Feng Liu work:
F3C
F3C
I
O
R2
R3O2C CO2R3
FeCl2
R1
DCM
R1
+
O
R2
CO2R3
R3O2C
17-96%
Nicewicz et al
Acridium salt
Ar
Wei Li et al
CF3
b) This work:
R2
CF3SO2Na
CF3
"Ir" catalyst
Ar
O
Ar
BF4
pyrylium salt
R1
R1
CF3
Organo photocatalyst
R2
CF3
R1, R2 = EWG, alkyl
yields upto 95%
Scheme 1. a) Known allylic trifluoromethylation of alkenes. b) Generation of CF3 radicals by
photocatalytic pathway and trifluoromethylation of VCPs.
the production of hydrogen,8a-b OLED application8c-d and also in photoredox catalysis.8e-f The
major drawbacks of using Ru (0.0001 ppm) and Ir (0.01 ppm) are toxic and their low abundance
making them expensive.9 Organo-based photocatalysts are one of the best alternatives that are
sustainable and cost effective. Recently, Nicewicz et al.10 have developed the acridinium based
organo photocatalysts. Acridinium10 and pyrylium11 photocatalysts have high oxidative potentials
that can promote a new chemical reaction under visible light irradiation. However, the
preparation of acridinium salts requires tedious multistep processes.12 In contrast, pyrylium
photocatalysts can be prepared in a single step from corresponding aromatic aldehyde and
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acetophenone derivatives, which is very cost-effective.13 Pyrylium salts absorb in the visible
region and act as powerful oxidizing agents in their excited states.11,13,14 They can enhance the
formation of free radicals because of no net charge separation in electron transfer step.14
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Among the many trifluoromethylating reagents (Togni, Umemoto, TMSCF3, CF3SO2Na,
CF3I, CF3SO2Cl, etc.), Langlois (CF3SO2Na) reagent has received special attention due to its
easy handling, stability and cost-effectiveness. However, this reagent has high oxidation
potential (Eoxd = +1.05 V vs SCE)15 making the generation of the CF3 radical difficult. Few
methods are known for trifluoromethylation from CF3SO2Na using transition metal catalysts at
high temperatures16a-c and excess of explosive peroxides as strong oxidant.16d-f In the case of
17a
photocatalysis, generation of CF3 radical directly from CF3SO2Na using Mes.Acr.ClO4 and
[Ir(dF-CF3-ppy)2(dtbpy)](PF6)17b is known (Scheme 1b). However, till date, no other
photocatalysts have been explored. Here, we report for the first time, pyrylium organic salt as a
photocatalyst for the generation of CF3 radical using visible light and subsequent
trifluoromethylation of vinylcyclopropanes (VCPs) using Langlois’ reagent (Scheme 1b).
Though vinylcyclopropanes (VCP) are well known for radical clock experiments,4c,18 there
is no detailed study of ring opening of VCPs using photoredox catalysis. Here, we are reporting
trifluoromethylation of VCPs using Langlois reagent by organic photoredox catalysis. We
hypothesized generation of CF3 radical that could react with the vinyl moiety of VCPs and
undergo ring opening to form long alkyl chained allylic trifluoromethylated products. First, we
tried trifluoromethylation on activated VCP 1a as a model substrate using Macmillan19a and
Stephenson et al.19b conditions (Entry 1 and 2). However, these conditions failed to yield the
expected product. Next, we screened different photocatalysts as shown in Table 1.
Initially, we screened different Ru and Ir-metal photocatalysts for the trifluoromethylation
red
of VCP. Catalysts like Ru(bpy)3Cl2·6H2O (bpy = bipyridyl) {E1/2 = [*RuII/RuI] = +0.77 V vs
SCE in MeCN},20a Ir(ppy)2(dtbbpy)PF6 (dtbbpy
=
4,4′-di-tert-butyl-2,2′-dipyridyl)
{E1/2red[*IrIII/IrII] = +0.66 V vs SCE in MeCN}20b and fac-Ir(ppy)3(ppy = 2-phenylpyridine)
red
{E1/2red[*IrIII/IrII] = +0.31 V vs SCE in MeCN}20c and Eosin Y {E1/2 = [3EY*/EY•–] = +0.83 V
vs SCE in MeCN}20d have insufficient potentials to generate the CF3 radical, hence the reaction
failed to provide expected product (Entry 3-5 and 7).
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Table 1. Optimization of the Allylic Trifluoromethylationa
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Entry
1b
Photocatalyst
2 mol% Ru(Phen)3Cl2
2 mol% Ru(bpy)3Cl2·6H2O
2 mol% Ru(bpy)3Cl2·6H2O
2 mol% [Ir(ppy)2(dtbbpy)]PF6
2 mol% fac-Ir(ppy)3
2 mol% Ir[(dFCF3ppy)2(dtbbpy)]PF6 DCE
5 mol% Eosin Y
5 mol% Mes.Acr.ClO4
5 mol% Rhodamine B
10 mol% TPPT
10 mol% T(p-F)PPT
10 mol% T(p-Cl)PPT
10 mol% T(p-CH3)PPT
10 mol% T(p-CH3)PPT
10 mol% T(p-CH3)PPT
10 mol% T(p-CH3)PPT
10 mol% T(p-CH3)PPT
10 mol% T(p-CH3)PPT
10 mol% T(p-CH3)PPT
10 mol% T(p-CH3)PPT
10 mol% T(p-CH3)PPT
-
Solvent
CH3CN K2HPO4
CH3CN
MeOH
MeOH
MeOH
Additive
Yield (E:Z)g
13 (6:1)
6 (7:1)
NR
NR
NR
2c
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
3
4
5
6
7
8
9
10
11
12
13
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18
19
20
21d
21e
22f
39 (10:1)
NR
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DMSO
CH3CN
Toluene
DCE
DCE
DCE
DCE
DCE
DCE
DCE
42 (9:1)
10 (7:1)
52 (12:1)
40 (11:1)
38 (9:1)
69 (13:1)
29 (10:1)
49 (8:1)
38 (9:1)
trace
Open air
10 eq. HCO2H 63 (12:1)
10 eq. H2O 79 (13:1)
10 eq. AcOH 95 (13:1)
10 eq. AcOH
10eq. AcOH
10 eq. AcOH
81 (12:1)
NR
trace
10 mol% T(p-CH3)PPT
a
All reactions were performed in 0.15 mmol scale, 2 eq. of CF3SO2Na,
2 mL solvent, irradiated with 27 W Blue LEDs under Ar atm.
bCF3SO2Cl as CF3 source, cPyridine N-Oxide and TFAA as CF3 source
(details in ESI). 27 W household CFL as light source for 18 h, eNo
d
photocatalyst, no light, gyields measured using C6H5CF3 as internal
f
standard. E:Z ratio based on 19F NMR
.
Rhodamine-B {E1/2red = [RhB*/RhB•–] = +1.62 V vs SCE}20e furnished yield of 10% (entry
9). Ir[dF(CF3)ppy]2(dtbbpy)PF6 (dF(CF3)ppy = 3, 5-difluoro-2-[5-(trifluoromethyl)-2-pyridinyl]
phenyl) {E1/2 [*IrIII/II] = +1.21 V and E1/2 [IrIII/II] = −1.37 V vs SCE in MeCN}20f and
Acridinium catalyst {E1/2 [*Acr/Acr•–] = +2.06 V and E1/2red [Acr/Acr–] = –0.57 V vs SCE in
red
red
red
MeCN}17a are well known catalysts for trifluoromethylation17a,b but they resulted in poor yields
39% and 42% respectively in this case (entry 6 and 8). Pyrylium salts have higher oxidation
potentials (1.8 V to 2.3 V vs SCE in MeCN)11 and large absorption in the visible region. When
the reaction was carried out using 2,4,6-triphenylpyrylium tetrafluoroborate (TPPT) as a
photocatalyst, interestingly, the expected product was obtained with 52% yield (Entry
10).Further, we examined different substituted TPPT. Pyrylium salts with electron withdrawing
groups (p-F, p-Cl) decreased the catalytic activity of the reaction (Entry 11 and 12), while
electron donating group (Me) showed high catalytic reactivity with a yield of 69% (Entry 13) in
DCE as the solvent. Different proton sources were screened to improve catalyst efficiency. We
tried AcOH as proton source additive and the best yield of 95% was observed using 10 eq. of
AcOH (Entry 20). Addition of AcOH after the reaction did not improve the yield of the reaction.
Probably AcOH is involved in protonation of anionic species (7) during reaction and increases
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catalytic efficiency. We also tried H2O as additive its giving 79% of product. Blue LEDs gives
better yields and less time compared to house hold light (entry 21). Further, we also performed
background reactions in the absence of photocatalyst and light (Entry 22 and 23) that showed a
trace amount of the product. The yield of the reaction was profoundly affected by atmospheric
conditions, for example, when the reaction was carried out in the open air, only trace amounts of
the product was observed (Entry 17).
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Table 2. Substrate Scope for Allylic Trifluoromethylationa
aAll reactions were performed with 0.15 mmol scale, 2 eq. CF3SO2Na,
10 mol% T(p-CH3)PPT, 10 eq. AcOH, irradiated with 27 W blue LEDs
b
under Ar atm., parenthesis E:Z ratio based on 19F NMR, reaction scale
0.3 mmol
.
With optimized conditions, we envisage the substrate scope and limitation of this
trifluoromethylation reaction. This protocol was suitable for a broad range of VCPs (Table 2).
Synthetically interesting functional groups such as esters, cyano, keto, spiro, and sulphonates are
tolerable in this protocol. In all the cases allylic trifluoromethylated products were obtained 2a-
2d in good yields and selectivity. The substrates with di-esters 2e-2i showed yields in the range
of 79% to 95% with E:Z ratio up to 24:1. This protocol is highly chemoselective, for instance,
selective installation of trifluoromethyl group at vinyl center in the presence of C=O and C≡N,
trifluoromethyl group is selectively incorporated at vinyl center. Substrates like di-cyano 2n and
di-keto 2k VCPs show good yields with moderate selectivity. We examined the two different
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substituted VCPs, which also gave good yields and regio-selectivity (2j, 2l, 2m, 2o and 2p).
Next, we tried spiro-VCPs as substrates. Interestingly, these spiro-VCPs showed high selectivity
up to 99:1 (2q and 2r) than the normal VCPs.
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Table 3. Allylic Trifluoromethylation of Carbocyclic Vinylcyclopropanesa
aAll reaction were performed with 0.3 mmol scale, 10 mol%
photocatalyst, 5 eq. CF3SO2Na, 4 mL DCE, 10 eq. AcOH, irradiated
with 27 W blue LEDs, under Ar atm. Yields are based on 19F NMR
using PhCF3 as an internal standard.
Next, we tested our protocol with few carbocyclic VCPs. Carbocyclic motifs are essential
skeleton found in many natural products.21 This methodology was successfully tested with 5, 6,
and 8 membered carbocyclic VCPs (Table 3). In these cases, 4-(trifluoromethyl)cyclo-2-ene
derivatives (2s, 2u and 2v) were obtained in good yields22 as a single trans isomer.
Trifluoromethylation of unactivated VCPs is challenging compared to activated VCPs due
to their low reactivity. Here, we synthesized unactivated VCPs 1v-1y by reduction followed by
protection of 1f using benzoyl, acetyl, benzyl and tert-butyl groups. Trifluoromethylation of
unactivated VCPs was achieved by enhancing the reaction time, trifluoromethylated products 3a-
3d were obtained with good yields and selectivity (Table 4).
Table 4. Allylic Trifluoromethylation of Unactivated Cyclopropanesa
T(p-CH3)PPT (10 mol%)
CF3SO2Na (2 eq. )
RO
RO
RO
OR
DCE, AcOH (10 eq.), rt
CF3
1v-1y
27 W Blue LEDs, 18 - 24 h
3a-3d
OCOtBu
OBz
OAc
OBn
CF3
CF3
CF3
CF3
OCOtBu
OBz
OAc
OBn
Bn = (p-CF3)Bn
3a
72% (7:1)
3b
76% (8:1)
3c
3d
69% (6:1)
83% (37:1)b
aAll reaction were performed with 0.3 mmol scale, 10 mol%
photocatalyst, 2 eq. CF3SO2Na, 4 mL DCE, 10 eq. AcOH, irradiated
with 27 W blue LEDs under Ar atm. b5 eq. CF3SO2Na, E:Z ratios based
on 19F NMR.
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To demonstrate the scalability of this methodology with readily available organic pyrylium
(T(p-CH3)PPT) photocatalyst and starting materials, we performed a gram-scale reaction of 1e
with Langlois reagent to get product 2e in 71% yield. The solid-state structure confirmed the
trans-geometry across the double bond in the trifluoromethylated product 2a.
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To demonstrate the synthetic utility of the allylic trifluoromethylated product, we
performed different synthetic transformations (Scheme 2). Allylic trifluoromethylated product 2a
was converted into trifluoromethylated epoxide 4a, trifluoromethylated alkane 4b, 1,4-addition
product 4c, bromo, and chlorinated derivatives 4d, 4e respectively in good chemical yields and
selectivity.23a-d
Scheme 2. Transformation of product 2a into different functional groups
To gain mechanistic insights, we performed a control experiment in the presence of a
radical quencher (Scheme 3). In the presence of TEMPO 5a (1.5 eq.), formation of TEMPO-CF3
adduct 5b was observed by 19F NMR (376 MHz, CDCl3) as singlet (s, 3F) at δ –55.86 ppm. This
experiment suggests that the reaction follows a radical pathway.
Scheme 3. Control experiment with TEMPO
In line with this, we propose a mechanism for allylic trifluoromethylation photoredox cycle
as shown in Scheme 4. Irradiation of photocatalyst PC with visible light generates the excited-
state photocatalyst PC* species, which acts as a strong oxidant to generate the CF3 radical from
the Langlois reagent {CF3SO2Na/CF3 , E1/2oxi = +1.05 V vs SCE}.17a This CF3 radical reacts with
•
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the terminal alkene of 1a and further undergoes cyclopropane ring opening due to ring strain and
generates stable tertiary radical 6. Finally, the photocatalytic cycle could be accomplished by
reduction of tertiary radical 6 to give stable carbanion 7 and regeneration of photocatalyst PC.17b
Further, protonation of 7 forms the long alkyl chain product 2a.
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PhO2S
SO2Ph
SO2
CF3
1a
CH3
CF3
O
S
PhO2S
SO2Ph
NaO
CF3
SET
2
CF3
O
CH3
SET
NaBF4
PC
CH3
H3C
SO2Ph
PhO2S
CF3
Organo photocatlytic
cycle
O
6
CH3
BF4
PC*
H3C
SO2Ph
CH3
PhO2S
Na
CF3
7
AcOH _NaOAc
SO2Ph
O
CH3
BF4
PC
H3C
PhO2S
CF3
Blue LEDs
2a
Scheme 4. Proposed mechanism for allylic trifluoromethylation of VCPs
In summary, we have developed a new methodology for the synthesis of allylic
trifluoromethylated derivatives from activated, carbocyclic and unactivated VCPs that is scalable
to gram scale. To our knowledge, this is the first report to use the cheap pyrylium photocatalyst
for trifluoromethylation of VCPs. The reported protocol is an excellent alternative for expensive
and harsh metal catalyst conditions. Trifluoromethylation demonstrated here has good functional
group tolerance and the final product can be further functionalized into useful synthetic
intermediates.
EXPERIMENTAL SECTION:
General Information:
All solvents were dried and commercial reagents were purified following guidelines of L. L Chai
and Armarego purification of laboratory chemicals. Langlois reagent (CF3SO2Na) was purchased
from Tokyo Chemical Industries Chemicals (TCI) and all metal catalysts were either prepared as
per literature procedures or purchased (Sigma-Aldrich) and used without purification, unless
specified. Other reagents were obtained from commercial suppliers (Alfa Aesar and
Spectrochem). All reactions were conducted in dried glassware with magnetic stirring under
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Argon atmosphere, unless otherwise stated. Ethanolic solution of potassium permanganate or p-
anisaldehyde was used as TLC staining agent. Flash column chromatography was performed
using silica gel (230-400 μm, Merck) using the eluent system described for each experiment.
Organic solutions were concentrated under reduced pressure on a Büchi rotary evaporator. Blue
LEDs (9 x 3 = 27 W) were used as a visible light source. The light source was placed at a
distance of ~5 cm from the reaction tube with cooling fan. The yields were calculated based on
isolation after column purification, and the purity was determined by 19F NMR spectra. All NMR
spectra were recorded on 400 MHz Jeol and 500 MHz Bruker spectrometers. 1H, 13C and 19F
NMR spectral data are reported as chemical shifts (δ) in parts per million (ppm) and coupling
constants (J) are measured in Hertz (Hz). The following abbreviations are used to describe
multiplicities s=singlet, d=doublet, t=triplet, q=quartet, pent=pentet, br=broad, m=multiplet.
NMR spectra were processed in Mestrenova keeping CDCl3 residual peak at 7.26 ppm. High resolution
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mass spectra (HRMS, m/z) were recorded on
a
Bruker Micro-TOF spectrometry. IR
spectra were recorded on Perkin Elmer Frontier FT-IR spectrometer. Melting points of solids
were measured on a Griffin apparatus and are uncorrected. IUPAC names were obtained using
the ChemDraw software.
General procedure for the synthesis of the pyrylium salts:
.
Pyrylium salts were prepared according to the literature procedure.24 BF3 OEt2 was slowly added to a
mixture of the carbonyl compounds (if starting materials are solids, they were dissolved in a small amount
of toluene). After heating for 2 h at 100 ºC or until no fumes observed then cooled to the room
temperature, add THF slowly and stirred for 5 min. Solid was filtered and washed several times with ether
and purification was performed by multiple time recrystallization from acetone.
Reactivity of vinylcyclopropane under MacMillan’s reaction conditions25a
In a glovebox, substrate 1a (17.4 mg, 0.05 mmol, 1 eq.), Ru(phen)3Cl2 (0.36 mg, 0.0005 mmol, 0.01 eq.),
and K2HPO4 (26.1 mg, 0.15 mmol, 3 eq.) were weighed into a 10 mL reaction tube. The vial was fitted
with rubber septum and removed from the glove box, and the vial was sealed with parafilm. The
CF3SO2Cl (10.64 µL, 2 eq.) in MeCN (2 mL) was added by syringe and reaction tube placed in the above-
mentioned photo reactor setup with cooling fan. The reaction mixture was allowed to stir for 24 h. The
reaction was quenched with water (5 mL) and extracted with CH2Cl2 (2 x 5 mL). The combined organic
layers were dried over Na2SO4 and evaporated under reduced pressure. Trifluoromethyltoulene (0.1
1
mmol, 2 eq.) was added as internal standard, and the reaction was analyzed by H and 19F NMR
spectroscopy. The starting material 1a was recovered in 80% yield, and trifluoromethylated product 2a
was formed in less than 13% yield.
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Reactivity of vinylcyclopropane under Stephenson’s reaction conditions25b
To a 5 mL reaction tube equipped with a stir bar was added pyridine N-oxide (38 mg, 0.40 mmol, 1.0 eq.),
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Ru(bpy)3Cl2 6H2O (3.0 mg, 1.0 mol%) and substrate 1a (139.2 mg, 0.40 mmol). The combined materials
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were then dissolved in MeCN (2.0 mL) and stirred to form a homogeneous solution. Trifluoroacetic
anhydride (60 µL, 90 mg, 0.44 mmol, 1.1 eq.) was then added to the resulting solution. The reaction tube
was equipped with a rubber septum, and syringe needle was placed through the septum for the duration of
the reaction. 9 x 3 W Blue LED lights (positioned 5 cm away) were turned on and the reaction was
allowed to run for 12–15 h before the light source was removed. Workup was done by diluting the
reaction with CH2Cl2 and washing with 1 N HCl, followed by saturated NaHCO3 and then brine. The
organic layer was dried over Na2SO4 and concentrate under reduced pressure. Trifluoromethyltoulene (0.4
1
mmol, 1 eq.) was added as internal standard, and the reaction was analyzed by H and 19F NMR
spectroscopy, and trifluoromethylated product 2a was formed in less than 6% yield.
General Procedure for synthesis of vinylcyclopropanes:
Vinylcyclopropanes (1a, 1e-1i, 1k, 1l, 1n, 1q and 1r) were prepared from the reported literature
procedure26 and other vinylcyclopropanes (1b-1d, 1j, 1m, 1o and 1p) were synthesized by following
protocol. The corresponding active methylene compound (2 mmol, 1 eq.) and 1,4-dibromobut-2-ene (1
eq.) were added to a round bottom flask with a stir bar under nitrogen atmosphere. To this was added
tetrahydrofuran (0.2 M) and Cesium carbonate (2.5 eq.). After fitting the condenser, reaction mixture was
stirred for overnight at 60 °C. After cooling down to room temperature, the reaction mixture was filtered
over Celite and washed with diethyl ether. The organic phase was washed with saturated aqueous
NaHCO3, followed by water and brine. After filtration over Na2SO4, the solvent was removed under
reduced pressure. The crude product was purified by silica gel column chromatography using hexane and
ethyl acetate as the eluent. Corresponding vinylcyclopropanes obtained as solid/liquid with good yields.
Spectral data of activated vinylcyclopropanes:
4,4'-(2-Vinylcyclopropanedisulfonyl)bis(chlorobenzene) (1b): White solid (mp: 152-156 °C), (650
1
mg, Yield 79%); H NMR (400 MHz, CDCl3): δ 7.97 (d, J = 8.7 Hz, 2H), 7.90 (d, J = 8.5 Hz, 2H), 7.53
(dd, J = 17.2, 8.7 Hz, 4H), 6.11 – 5.86 (m, 1H), 5.43 (d, J = 17.1 Hz, 1H), 5.34 (d, J = 10.3 Hz, 1H), 3.24
(dd, J = 18.6, 9.2 Hz, 1H), 2.33 (dd, J = 8.5, 6.6 Hz, 1H), 2.05 (dd, J = 10.1, 6.3 Hz, 1H). 13C{1H} NMR
(101 MHz, CDCl3): δ 141.3, 141.2, 137.6, 136.9, 131.1, 131.0, 130.5, 129.3, 128.9, 122.7, 64.0, 32.8,
20.4. FT-IR data (KBr, in cm-1): 3092, 2906, 1578, 1477, 1429, 1396, 1336, 1319, 1296, 1280, 1262,
1248, 1214, 1197, 1177, 1151, 1139, 1088, 1059, 1011, 970, 942. HRMS (ESI-TOF) m/z: [M + H]+ calcd
for C17H15Cl2O4S2 416.9783; Found: 416.9781.
4,4'-(2-Vinylcyclopropanedisulfonyl)bis(methylbenzene) (1c): White solid (mp: 110-114 °C), (544
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mg, yield 72%); H NMR (400 MHz, CDCl3): δ 7.89 (d, J = 8.3 Hz, 2H), 7.82 (d, J = 8.2 Hz, 2H), 7.32
(dd, J = 11.2, 8.4 Hz, 4H), 6.06 (dt, J = 17.4, 9.7 Hz, 1H), 5.40 (d, J = 17.1 Hz, 1H), 5.31 (d, J = 10.2 Hz,
1H), 3.21 (dd, J = 18.4, 9.2 Hz, 1H), 2.44 (s, 3H), 2.43 (s, 3H), 2.30 (dd, J = 8.3, 6.3 Hz, 1H), 2.09 (dd, J
= 10.0, 6.2 Hz, 1H).13C{1H} NMR (101 MHz, CDCl3): δ 145.2, 145.1, 136.3, 135.6, 131.1, 129.5, 129.4,
129.3, 129.0, 121.7, 64.0, 32.6, 21.6, 20.0. FT-IR data (KBr, in cm-1): 3056, 3034, 3001, 2981, 2956,
2923, 1923, 1869, 1801, 1631, 1596, 1405, 1382, 1330, 1198, 1164, 1136. HRMS (ES-TOF) m/z: [M +
H]+ calcd for C19H21O4S2 377.0876; Found: 377.0872.
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4,4'-(2-Vinylcyclopropanedisulfonyl)bis(methoxybenzene) (1d): White solid (mp: 48-51 °C), (550
1
mg, yield 68%); H NMR (400 MHz, CDCl3): δ 7.93 (d, J = 9.0 Hz, 2H), 7.86 (d, J = 9.0 Hz, 2H), 6.97
(dd, J = 12.2, 9.0 Hz, 4H), 6.05 (dt, J = 17.0, 9.7 Hz, 1H), 5.39 (d, J = 17.1 Hz, 1H), 5.30 (d, J = 10.2 Hz,
1H), 3.87 (s, 4H), 3.86 (s, 2H), 3.19 (dd, J = 18.4, 9.1 Hz, 1H), 2.26 (dd, J = 8.3, 6.2 Hz, 1H), 2.03 (dd, J
= 10.0, 6.1 Hz, 1H).13C{1H} NMR (101 MHz, CDCl3): δ 164.0, 164.0, 131.8, 131.2, 130.7, 130.0, 121.6,
113.9, 113.6, 64.3, 55.6, 32.6, 20.1. FT-IR data (KBr, in cm-1): 3901, 3866, 3852, 3817, 3671, 3648,
3628, 3116, 3090, 3016, 2954, 2843, 1594, 1499, 1441, 1416, 1322, 1299, 1269, 1156, 1116, 1080, 1020.
HRMS (ESI-TOF) m/z: [M + H]+ calcd for C19H21O6S2 409.0774; Found: 409.0769.
Methyl-1-(phenylsulfonyl)-2-vinylcyclopropanecarboxylate (1j): White solid, (mp: 66-69 °C), (400
1
mg, yield 74%, single isomer); H NMR (400 MHz, CDCl3): δ 7.93 (d, J = 8.4 Hz, 2H), 7.63 (t, J = 7.6
Hz, 1H), 7.54 (t, J = 7.7 Hz, 2H), 5.60 – 5.47 (m, 1H), 5.36 (d, J = 16.9 Hz, 1H), 5.18 (d, J = 10.2 Hz,
1H), 3.61 (s, 3H), 2.89 (dd, J = 18.0, 8.5 Hz, 1H), 2.25 (dd, J = 9.9, 5.5 Hz, 1H), 1.97 (dd, J = 8.3, 5.5 Hz,
1H). 13C{1H} NMR (101 MHz, CDCl3): δ 165.0, 139.8, 133.6, 130.9, 128.8, 120.5, 52.7, 51.0, 32.0, 19.7.
FT-IR data (KBr, in cm-1): 3447, 3097, 3064, 3037, 3015, 3005, 2959, 1978, 1873, 1834, 1733, 1635,
1442, 1309, 1207, 1164, 1143, 1085, 1062, 1032. HRMS (ESI-TOF) m/z: [M + H]+ calcd for C13H15O4S
267.0686; Found: 267.0683.
1-Benzoyl-2-vinylcyclopropanecarbonitrile (1m): Colorless oil, (183 mg, yield 46%, single Isomer);
1H NMR (400 MHz, CDCl3): δ 7.96 (dd, J = 8.4, 1.3 Hz, 2H), 7.63 – 7.58 (m, 1H), 7.50 (t, J = 7.6 Hz,
2H), 5.84 – 5.73 (m, 1H), 5.50 (d, J = 16.2 Hz, 1H), 5.45 (d, J = 10.3 Hz, 1H), 2.57 (dd, J = 16.6, 8.6 Hz,
1H), 2.33 (dd, J = 8.8, 4.9 Hz, 1H), 1.74 (dd, J = 7.8, 4.9 Hz, 1H).13C{1H} NMR (101 MHz, CDCl3): δ
191.4, 135.5, 133.6, 132.5, 128.6, 128.6, 121.2, 118.9, 99.9, 35.9, 26.3, 23.9. FT-IR data (KBr, in cm-1):
2264, 1728, 1437, 1269, 1166. HRMS (ESI-TOF) m/z: [M + H]+ calcd for C13H11NO 198.0913; Found:
198.0910.
Ethyl-1-cyano-2-vinylcyclopropanecarboxylate (1o): Colorless oil, (mixture of diastereomers 1:1)
(285 mg, yield 86%); 1H NMR (400 MHz, CDCl3): δ 5.70 – 5.51 (m, 1H), 5.39 (dd, J = 17.2, 1.5 Hz, 1H),
5.32 (d, J = 10.3 Hz, 0.6H), 5.22 (d, J = 10.1 Hz, 0.4H), 4.26 – 4.14 (m, 2H), 2.52 (dt, J = 16.8, 8.6 Hz,
1H), 1.95 – 1.81 (m, 1.5H), 1.60 (dd, J = 7.9, 5.1 Hz, 0.5H), 1.28 (q, J = 7.0 Hz, 3H).13C{1H} NMR (101
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MHz, CDCl3): δ 166.9, 164.9, 132.0, 130.4, 121.1, 120.5, 118.4, 116.5, 62.7, 62.5, 35.4, 33.4, 23.6, 22.3,
20.9, 20.1, 13.9, 13.8. FT-IR data (KBr, in cm-1): 2985, 2959, 2934, 2850, 1736, 1438, 1370, 1343, 1252,
1138, 1053, 973, 913, 858, 646. HRMS (ESI-TOF) m/z: [M + H]+ calcd for C9H12NO2 166.0863; Found:
166.0862.
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tert-Butyl-1-tosyl-2-vinylcyclopropanecarboxylate (1p): White solid (mp: 60-64 °C) (457 mg, yield
1
71%, single isomer); H NMR (400 MHz, CDCl3): δ 7.80 (d, J = 8.3 Hz, 2H), 7.33 (d, J = 8.2 Hz, 2H),
5.55 (ddd, J = 17.4, 10.1, 8.3 Hz, 1H), 5.37 (d, J = 16.8 Hz, 1H), 5.19 (d, J = 10.6 Hz, 1H), 2.82 (dd, J =
18.0, 8.3 Hz, 1H), 2.44 (s, 3H), 2.17 (dd, J = 9.9, 5.4 Hz, 1H), 1.89 (dd, J = 7.8, 5.4 Hz, 1H), 1.29 (s, 9H).
13C{1H} NMR (101 MHz, CDCl3): δ 163.3, 144.3, 137.3, 131.2, 129.4, 128.5, 120.0, 83.7, 51.4, 31.2,
27.8, 21.6, 18.9. FT-IR data (KBr, in cm-1): 3100, 2982, 2932, 1722, 1645, 1598, 1497, 1480, 1461, 1432,
1398, 1369, 1321, 1256, 1213, 1157, 1136, 1083. HRMS (ESI-TOF) m/z: [M + Na]+ for calcd for
C17H22O4SNa 345.1131; Found: 345.1128.
Synthesis of the carbocyclic vinylcyclopropanes:
Dimethyl-bicyclo[3.1.0]hex-2-ene-6,6-dicarboxylate (1s):27a In an oven-dried 50 mL Schlenk tube
equipped with a magnetic stir bar and cooled under argon, was added Rh2(OAc)4 (13 mg, 0.03 mmol) and
freshly cracked cyclopentadiene (2.8 mL, 32.5 mmol). Dimethyl 2-diazomalonate (0.86 mL, 6.5 mmol)
was added neat over 10 h by means of a gas-tight syringe (using syringe pump) at room temperature. The
solution was run through a pipette plug of silica and eluted with hexane. The collected organic layer was
concentrated and purified by medium pressure liquid chromatography using 5% EtOAc and hexane as
eluent to obtain the compound 1s in 61% yield (779 mg) as a colorless oil. 1H NMR (400 MHz, CDCl3):
δ 5.76 (dd, J = 3.8, 1.2 Hz, 1H), 5.58 (d, J = 5.3 Hz, 1H), 3.68 (s, 3H), 3.60 (s, 3H), 2.82 – 2.59 (m, 3H),
2.40 (t, J = 6.1 Hz, 1H).13C{1H} NMR (101 MHz, CDCl3): δ 170.3, 166.5, 132.1, 129.4, 52.6, 52.2, 39.3,
38.6, 34.3, 31.6.
Dimethyl-bicyclo[4.1.0]hept-2-ene-7,7-dicarboxylate (1t):27b In an oven-dried 10 mL Sealed tube
equipped with a magnetic stir bar under argon, was added Rh2(OAc)4 (13 mg, 0.03 mmol). Dimethyl 2-
diazomalonate (0.86 mL, 6.5 mmol) was added and excess of cyclohexadiene (5-10 eq.) added. The
reaction mixture was heated to 120 °C for 1 h, until no dimethyl 2-diazomalonate remains. Reaction
mixture was concentrated and purified by silica column using 5% EtOAc and hexane. The compound 1t
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was isolated as gummy solid in 93% yield (1.3 g) which became solid at 20 °C; H NMR (400 MHz,
CDCl3): δ 5.92 – 5.76 (m, 1H), 5.72 – 5.57 (m, 1H), 3.72 (s, 3H), 3.71 (s, 3H), 2.17 – 1.56 (m, 6H).
13C{1H} NMR (101 MHz, CDCl3): δ 170.0, 167.6, 127.8, 121.7, 52.6, 52.4, 40.7, 26.6, 24.4, 20.4, 15.9.
Dimethyl-bicyclo[6.1.0]non-2-ene-9,9-dicarboxylate (1u):27c In an oven-dried 10 mL Sealed tube
equipped with a magnetic stir bar under argon, was added Rh2(OAc)4 (13 mg, 0.03 mmol). Dimethyl 2-
diazomalonate (0.86 mL, 6.5 mmol) was added and excess of cyclooctadiene (2-5 eq.) added. Reaction
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concentrated and purified by silica column using 5% EtOAc and hexane. The compound 1u was isolated
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as colorless oily liquid in 68% yield (1.05 g). H NMR (400 MHz, CDCl3): δ 5.77 (tdd,
J = 7.2, 4.4, 2.4
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Hz, 1H), 5.54 (d, J = 11.3 Hz, 1H), 3.72 (s, 3H), 3.71 (s, 3H), 2.45 – 2.31 (m, 2H), 2.07 – 1.68 (m, 6H),
1.51 – 1.36 (m, 1H), 1.11 (ddd, J = 15.2, 12.5, 3.1 Hz, 1H). 13C{1H} NMR (101 MHz, CDCl3): δ 171.1,
167.0, 136.2, 120.5, 52.6, 52.0, 36.0, 32.8, 30.1, 29.6, 29.5, 24.7, 23.9.
Synthesis of the unactivated vinylcyclopropanes:
(
2-Vinylcyclopropane-1,1-diyl)dimethanol (S1): To a solution of diester 1f (14 mmol) in THF (50
o
mL) was cooled to 0 C and LiAlH4 (4 eq.) was added in several portions
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After heating for 2 h, the
mixture was cooled to rt, add 2 mL H2O followed by 1 M solution of Rochelle’s salt (10 mL) were
cautiously added, the layers are separate out. The solid part filtered off. The filtrate was concentrated and
extract with 3 x 50 mL DCM. Combine the organic layers and dried over Na2SO4. After evaporation of
solvent, di-alcohol S1 appeared as colorless liquid, which was used further without purification (1.7 g,
crude yield 95%); 1H NMR (400 MHz, CDCl3 δ 5.67 (ddd, J = 17.02, 10.14, 8.09 Hz, 1H), 5.15 (dd, J =
17.02, 0.85 Hz, 1H), 5.04 (dd, J = 10.14, 0.85 Hz, 1H), 3.83 (dd, J = 11.71, 6.52 Hz, 1H), 3.63- 3.57 (m,
3H), 3.30 (br s, 2H), 1.63-1.51 (m, 1H), 0.83 (dd, J = 8.09, 5.43 Hz, 1H), 0.65 (t, J = 5.43 Hz, 1H).
13C{1H} NMR (101 MHz, CDCl3): δ 136.2, 115.9, 69.1, 64.4, 30.5, 25.2, 15.5.
(2-Vinylcyclopropane-1,1-diyl)bis(methylene)dibenzoate (1v): It was prepared from the following
literature report.28a A solution of 200 mg (1.6 mmol) of (2-vinylcyclopropane-1,1-diyl)dimethanol S1 in 5
mL of pyridine stirred at 0 °C under protection from moisture was treated with 15.2 mL (680 mg, 4.8
mmol) of benzoyl chloride (added dropwise over 15 min.). The reaction mixture was stirred at room
temperature for 2 h, then treated with 2 mL of H2O, and stirred overnight. The mixture was concentrated
under reduced pressure. The residual oil was dissolved in 50 mL of EtOAc and washed successively with
Sat. CuSO4 solution and bicarbonate. The organic phase was dried (MgSO4), filtered, concentrated and
purified by column chromatography using 5-10% EtOAc and hexane to obtain compound 1v as colorless
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oil in 77% yield (410 mg); H NMR (400 MHz, CDCl3): δ 8.03 (dd, J = 7.0, 1.4 Hz, 4H), 7.55 (dd, J =
14.8, 7.2 Hz, 2H), 7.40 (t, J = 7.7 Hz, 4H), 5.83 – 5.68 (m, 1H), 5.24 (d, J = 16.9 Hz, 1H), 5.12 (d, J =
10.4 Hz, 1H), 4.64 (d, J = 12.0 Hz, 1H), 4.36 (dt, J = 17.5, 11.8 Hz, 3H), 1.87 (dd, J = 14.5, 7.5 Hz, 1H),
1.16 (dd, J = 8.4, 5.5 Hz, 1H), 0.97 (t, J = 5.8 Hz, 1H). 13C{1H} NMR (101 MHz, CDCl3): δ 166.5, 134.9,
133.0, 132.9, 130.1, 130.0, 129.6, 128.3, 128.3, 116.9, 69.1, 65.3, 25.8, 25.7, 15.9.
(2-Vinylcyclopropane-1,1-diyl)bis(methylene)diacetate (1w): It was prepared from the following the
literature reports.28b A 25 mL of two neck round bottom flask was dried by heat gun under nitrogen
atmosphere. After nitrogen was filled, to the solution of (2-vinylcyclopropane-1,1-diyl)dimethanol S1
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(150 mg, 1.2 mmol) in pyridine (0.6 mL) was added anhydrous acetic anhydride (1.5 mL) dropwise
slowly. The resulting mixture was stirred at rt for 24 hours. After cooling to 0 °C, 4 mL of H2O was added
slowly. The reaction mixture was filtered and extracted with DCM (4 x 10 mL). The combined organic
layer was washed successively with sat. aq. CuSO4 (10 mL), 5% HCl (10 mL), sat. aq. NaHCO3 (10 mL),
and brine (10 mL). The organic layer was dried over MgSO4 and concentrated under reduced pressure.
The residue was purified by column chromatography using 5-10% EtOAc and hexane to obtain
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compound 1w in 53% yield (135 mg); H NMR (400 MHz, CDCl3): δ 5.63 (ddd, J = 10.6, 8.9, 5.7 Hz,
1H), 5.15 (d, J = 16.8 Hz, 1H), 5.07 (d, J = 10.6 Hz, 1H), 4.20 (d, J = 12.0 Hz, 1H), 4.07 (d, J = 12.0 Hz,
1H), 3.99 (d, J = 12.0 Hz, 1H), 3.93 (d, J = 12.0 Hz, 1H), 2.07 (s, 1H), 2.05 (s, 1H), 1.70 – 1.62 (m, 1H),
0.96 (dd, J = 8.5, 5.5 Hz, 1H), 0.78 (t, J = 5.5 Hz, 1H). 13C{1H} NMR (101 MHz, CDCl3): δ 171.1, 134.9,
116.8, 68.2, 64.2, 25.5, 25.4, 20.9, 20.8, 15.6.
4,4'-(Vinylcyclopropane1,1diyl)bis(methylene)bis(oxy))bis(methylene)bis((trifluoro-
methyl)benzene) (1x): A 25 mL of two neck round bottom flask was dried using heat gun under Argon
atmosphere. Added 3 equivalents of NaH (55% washed with pentane) and argon back filed for 3 times.
Reaction mixture was cooled to 0 °C then 200 mg (1.56 mmol) of (2-vinylcyclopropane-1,1-
diyl)dimethanol S1 in DMF (5 mL) added slowly, stirred for 15 min. Then add 1-(bromomethyl)-4-
(trifluoromethyl)benzene 1.1 g (4.5 mmol) in DMF added dropwise over 15 min. Stirred at rt for
overnight. Reaction quenched by addition of water, extracted with 2 x 10 mL ethyl acetate, the organic
layer washed with H2O (4 x 10 mL) and brine respectively. Combined organic layer was dried over
Na2SO4, evaporated the solvent and purified by column chromatography using 5% EtOAc and hexane as
eluent to obtained product 1x in 78% yield (520 mg); 1H NMR (400 MHz, CDCl3): δ 7.57 (d, J = 7.9 Hz,
4H), 7.42 (d, J = 7.9 Hz, 4H), 5.74 – 5.55 (m, 1H) 5.15 (d, J = 16.5 Hz, 1H), 5.05 (d, J = 10.0 Hz, 1H),
4.56 (s, 2H), 4.54 (d, J = 2.9 Hz, 2H), 3.68 (d, J = 10.1 Hz, 1H), 3.62 (d, J = 9.8 Hz, 1H), 3.42 (d, J =
10.1 Hz, 1H), 3.34 (d, J = 9.8 Hz, 1H), 1.59 (dd, J = 15.0, 8.4 Hz, 1H), 0.93 (dd, J = 8.4, 5.2 Hz, 1H),
0.71 (t, J = 5.2 Hz, 1H). 13C{1H} NMR (101 MHz, CDCl3): δ 142.6, 136.1, 127.5, 127.4, 126.9 (q, 272
Hz), 125.3, 125.2, 125.2, 115.7, 74.5, 72.1, 72.0, 70.1, 27.3, 25.0, 15.3. 19F NMR (471 MHz, CDCl3): δ -
62.54 (s, 6F). IR data (KBr, in cm-1): 1399, 1330, 1190, 1123. HRMS (ESI-TOF) m/z: [M + H]+ calcd for
C23H23F6O2 445.1597; Found: 445.1597.
(2-Vinylcyclopropane-1,1-diyl)bis(methylene)bis(2,2-dimethylpropanoate) (1y): A 25 mL of round
bottom two neck flask was dried by heat gun under Argon atm. Added 20 mol% of DMAP and argon
back filed for 3 times. Then 1.0 mL of pyridine was added and cooled to 0 °C followed by 200 mg (1.56
mmol) of (2-vinylcyclopropane-1,1-diyl)dimethanol in DCM (5 mL) was added slowly and stirred for 15
min. Next tert-butyl acetyl chloride (40.7 mmol) in DCM was added drop wise over 15 min. Reaction
mixture was stirred overnight at room temperature, Reaction mixture was diluted with DCM, washed with
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CuSO4, brine solution and dried over Na2SO4. Solvent was evaporated under reduced pressure and
purified by flash column chromatography using 5% EtOAc and hexane as eluent. Compound 1y was
obtained as a colorless liquid in 89% yield (410 mg). 1H NMR (400 MHz, CDCl3): δ 5.67 – 5.54 (m, 1H),
5.14 (d, J = 16.8 Hz, 1H), 5.04 (dd, J = 9.2, 8.1 Hz, 1H), 4.20 (d, J = 12 Hz, 1H), 4.11 (d, J = 11.5 Hz,
1H), 3.91 (dd, J = 11.7, 7.3 Hz, 2H), 1.65 (dd, J = 14.3, 7.5 Hz, 1H),1.25 (s, 9H), 1.20 (s, 9H), 1.01 – 0.93
(m, 1H), 0.77 (t, J = 5.7 Hz, 1H). 13C{1H} NMR (101 MHz, CDCl3): δ 178.4, 174.0, 135.1, 116.5, 67.5,
64.1, 40.2, 38.9, 38.8, 27.1, 26.5, 25.8, 25.1, 15.6. IR data (KBr, in cm-1): 1813, 1729, 1483, 1403, 1281,
1141, 1001, 604. HRMS (ESI-TOF) m/z: [M + H]+ calcd for C17H29O4 297.2060; Found: 297.2059.
General procedure for the allylic trifluoromethylation of vinylcyclopropanes: To an oven dried
borosilicate test tube equipped with a magnetic stir bar was added VCP (0.15 mmol, 1 eq.), CF3SO2Na
(0.3 mmol, 2 eq.) and 10 mol% photocatalyst T(p-CH3)PPT (6.6 mg, 0.1 eq.). The reaction tube was
vacuumed and backfilled with argon (3 times) and put a septum over the reaction tube. Next, 90 µL
AcOH (10 eq.) and 2 mL of DCE was added through the septum by a syringe, and placed approximately 5
cm from light setup. After 6 h of the reaction, 10 mL of water was added and extracted with DCM (3 x 20
mL). The combined organic layer was dried over Na2SO4 and solvent was removed under reduced
pressure. The crude product was then purified by flash column chromatography on silica gel (mesh 230-
400) using hexane and EtOAc as an eluent to afford the corresponding allylic trifluoromethylated product.
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Spectral data of allylic trifluoromethyl derivatives:
(E)-(6,6,6-Trifluorohex-3-ene-1,1-diyldisulfonyl)dibenzene (2a): White solid, (mp: 98-102 °C), dr
1
(13 : 1); (57.2 mg, yield 91%); H NMR (400 MHz, CDCl3): δ 7.95 – 7.91 (m, 4H), 7.68 (t, J = 7.6 Hz,
2H), 7.55 (t, J = 7.9 Hz, 4H), 5.80 – 5.66 (m, 1H), 5.46 – 5.30 (m, 1H), 4.50 (t, J = 6.0 Hz, 1H), 2.93 (t, J
13
= 6.3 Hz, 2H), 2.77 – 2.65 (m, 2H). C{1H} NMR (101 MHz, CDCl3): δ 137.6, 134.7, 131.4, 129.5,
129.4, 129.2, 129.1, 125.5 (q, J = 276.8 Hz), 122.4 (d, J = 3.2 Hz), 83.0, 36.9 (q, J = 29.9 Hz), 28.6. 19F
NMR (376 MHz, CDCl3): δ –66.04 (t, J = 10.7 Hz). FT-IR (KBr, in cm-1): 3171, 2935, 2853, 1816, 1585,
1480, 1379, 1328, 1311, 1293, 1270, 1254, 1203, 1112, 1081, 997, 970, 940, 895, 841, 740, 688, 646.
HRMS (ESI-TOF) m/z: [M + H]+ calcd for C18H18F3O4S2 419.0593; Found: 419.0590.
(E)-4,4'-(6,6,6-Trifluorohex-3-ene-1,1-diyldisulfonyl)bis(chlorobenzene) (2b): White solid, (mp:
1
90-92 °C), dr (12 : 1); (57.3 mg; yield 79%); H NMR (400 MHz, CDCl3): δ 7.89 (d, J = 8.7 Hz, 4H),
7.56 (d, J = 8.5 Hz, 4H), 5.83 – 5.71 (m, 1H), 5.51 – 5.35 (m, 1H), 4.45 (t, J = 6.1 Hz, 1H), 2.91 (t, J =
6.5 Hz, 2H), 2.84 – 2.68 (m, 2H). 13C{1H} NMR (101 MHz, CDCl3): δ 141.9, 135.8, 131.1, 131.1, 129.6,
129.5, 125.5 (q, J = 276.8 Hz), 122.9 (d, J = 3.1 Hz), 83.4, 37.0 (q, J = 30.0 Hz), 28.6. 19F NMR (376
MHz, CDCl3): δ –66.08 (t, J = 10.6 Hz). FT-IR (KBr, in cm-1): 3093, 2904, 1577, 1475, 1429, 1397, 1334,
1321, 1296, 1261, 1247, 1215, 1198, 1176, 1089, 1057, 1012, 762, 711, 655. HRMS (ESI-TOF) m/z: [M -
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H]+ calcd for C18H14Cl2F3O4S2 484.9688; Found: 484.9677.
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(E)-4,4'-(6,6,6-Trifluorohex-3-ene-1,1-diyldisulfonyl)bis(methylbenzene) (2c): Semi solid, dr (11 :
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1); (54.3 mg, yield 81%); H NMR (400 MHz, CDCl3): δ 7.82 (d, J = 8.3 Hz, 4H), 7.36 (d, J = 8.1 Hz,
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4H), 5.85 – 5.63 (m, 1H), 5.42 – 5.29 (m, 1H), 4.40 (t, J = 5.8 Hz, 1H), 2.90 (t, J = 6.5 Hz, 2H), 2.81 –
2.64 (m, 2H), 2.46 (s, 6H). 13C{1H} NMR (101 MHz, CDCl3): δ 146.1, 146.0, 134.7, 131.8, 129.8, 129.7,
129.7, 129.6, 125.6 (q, J = 276.7 Hz), 122.3 (d, J = 3.2 Hz), 83.3, 37.0 (q, J = 29.9 Hz), 28.8, 21.7. 19F
NMR (376 MHz, CDCl3): δ –66.16 (t, J = 10.6 Hz). FT-IR (KBr, in cm-1): 3103, 3072, 3011, 2944, 2843,
1597, 1579, 1497, 1464, 1443, 1416, 1332, 1301, 1266, 1151, 1080, 1050, 1022, 971, 863, 805, 764, 724,
703, 674, 625. HRMS (ESI-TOF) m/z: [M + H]+ calcd for C20H22F3O4S2 447.0906; Found: 447.0901.
(E)-4,4'-(6,6,6-Trifluorohex-3-ene-1,1-diyldisulfonyl)bis(methoxybenzene (2d): White solid, (mp:
1
97-98 °C), dr (13 : 1); (55.3 mg, yield 77%); H NMR (400 MHz, CDCl3): δ 7.87 (d, J = 9.0 Hz, 4H),
7.01 (d, J = 9.0 Hz, 4H), 5.95 – 5.62 (m, 1H), 5.52 – 5.24 (m, 1H), 4.37 (t, J = 5.9 Hz, 1H), 3.90 (s, 6H),
2.89 (t, J = 6.3 Hz, 2H), 2.81 – 2.68 (m, 2H). 13C{1H} NMR (101 MHz, CDCl3): δ 164.5, 132.0, 132.0,
128.9, 125.6 (q, J = 276.6 Hz), 122.1 (d, J = 3.1 Hz), 114.4, 114.3, 83.5, 55.7, 37.0 (q, J = 29.9 Hz), 29.0.
19F NMR (376 MHz, CDCl3): δ –66.13 (t, J = 10.7 Hz). FT-IR (KBr, in cm-1): 3103, 3072, 3011, 2944,
2843, 1597, 1579, 1497, 1464, 1443, 1416, 1332, 1301, 1266, 1151, 1080, 1050, 1022, 971, 863, 805,
764, 724, 703, 674, 625. HRMS (ESI-TOF) m/z: [M + H]+ calcd for C20H22F3O6S2 479.0804; Found:
479.0799.
(E)-Dimethyl-2-(5,5,5-trifluoropent-2-en-1-yl)malonate (2e): Colorless liquid, dr (27 : 1); (61.2 mg,
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yield 80%); H NMR (400 MHz, CDCl3): δ 5.73 – 5.60 (m, 1H), 5.49 (dt, J = 15.2, 7.0 Hz, 1H), 3.72 (s,
6H), 3.44 (t, J = 7.5 Hz, 1H), 2.75 (qd, J = 10.7, 7.4 Hz, 2H), 2.64 (t, J = 7.1 Hz, 2H). 13C{1H} NMR (101
MHz, CDCl3): δ 169.0, 133.2, 125.7 (q, J = 276.6 Hz), 121.3 (d, J = 3.5 Hz), 52.5, 51.2, 37.2 (q, J = 29.8
Hz), 31.7. 19F NMR (376 MHz, CDCl3): δ –66.56 (t, J = 10.7 Hz). FT-IR (KBr, in cm-1): 1737, 1436,
1402, 1261, 1146, 605. HRMS (ESI-TOF) m/z: [M + H]+ calcd for C10H14F3O4 255.0839; Found:
255.0839.
(E)-Diethyl-2-(5,5,5-trifluoropent-2-en-1-yl)malonate (2f): Colorless oil, dr (22 : 1); (67.1 mg, yield
79%); 1H NMR (400 MHz, CDCl3): δ 5.75 – 5.57 (m, 1H), 5.59 – 5.31 (m, 1H), 4.18 (qd, J = 7.2, 2.3 Hz,
4H), 3.39 (t, J = 7.5 Hz, 1H), 2.75 (qd, J = 10.6, 7.3 Hz, 2H), 2.64 (t, J = 7.2 Hz, 2H), 1.25 (t, J = 7.2 Hz,
6H). 13C{1H} NMR (101 MHz, CDCl3): δ 168.7, 133.4, 125.7 (q, J = 276.4 Hz), 121.0 (d, J = 3.5 Hz),
61.5, 51.5, 37.2 (q, J = 29.8 Hz), 31.6, 14.0. 19F NMR (376 MHz, CDCl3): δ –66.54 (t, J = 10.7 Hz). FT-
IR (KBr, in cm-1): 3099, 3034, 2983, 2932, 2874, 1722, 1643, 1597, 1496, 1479, 1459, 1437, 1397, 1370,
1325, 1082, 1015, 878, 668. HRMS (ESI-TOF) m/z: [M + H]+ calcd for C12H18F3O4 283.1152; Found:
283.1148.
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(E)-Diisopropyl-2-(5,5,5-trifluoropent-2-en-1-yl)malonate (2g): Colorless oil, dr (22 : 1); (78.1 mg,
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yield 84%); H NMR (400 MHz, CDCl3): δ 5.76 – 5.63 (m, 1H), 5.48 (dt, J = 15.3, 3.9 Hz, 1H), 5.10 –
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4.98 (m, 2H), 3.33 (t, J = 7.6 Hz, 1H), 2.83 – 2.67 (m, 2H), 2.62 (t, J = 7.2 Hz, 2H), 1.23 (d, J = 6.4 Hz,
12H). 13C{1H} NMR (101 MHz, CDCl3): δ 168.2, 133.6, 125.8 (q, J = 276.5 Hz), 120.8 (d, J = 3.4 Hz),
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69.0, 51.9, 31.4, 37.2 (q, J = 29.8 Hz), 21.6, 21.5. 19F NMR (376 MHz, CDCl3): δ –66.49 (t, J = 10.6 Hz).
FT-IR (KBr, in cm-1): 2985, 2936, 2881, 1747, 1731, 1471, 1432, 1374, 1340, 1272, 1253, 1178, 1139,
1105, 1057, 972, 911, 844, 824, 647. HRMS (ESI-TOF) m/z: [M + Na]+ calcd for C14H21F3O4Na
333.1284; Found: 333.1280.
(E)-Di-tert-butyl-2-(5,5,5-trifluoropent-2-en-1-yl)malonate (2h): Colorless oil, dr (17 : 1); (48.2 mg,
yield 95%); 1H NMR (400 MHz, CDCl3): δ 5.75 – 5.58 (m, 1H), 5.55 – 5.39 (m, 1H), 3.19 (t, J = 7.6 Hz,
1H), 2.81 – 2.67 (m, 2H), 2.54 (t, J = 7.2 Hz, 2H), 1.43 (s, 18H). 13C{1H} NMR (101 MHz, CDCl3): δ
168.1, 133.9, 125.8 (q, J = 276.3 Hz), 120.4 (d, J = 3.3 Hz), 81.6, 53.3, 37.2 (q, J = 29.8 Hz), 31.5, 27.8.
19F NMR (376 MHz, CDCl3): δ –66.46 (t, J = 10.7 Hz). FT-IR (KBr, in cm-1): 2982, 2935, 1728, 1481,
1460, 1433, 1395, 1371, 1344, 1255, 1140, 1058, 971, 848, 745, 646. HRMS (ESI-TOF) m/z: [M + Na]+
calcd for C16H25F3O4Na 361.1597; Found: 361.1591.
(E)-Dibenzyl-2-(5,5,5-trifluoropent-2-en-1-yl)malonate (2i): Colourless oil, dr (18 : 1); (48.2 mg,
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yield 79%); H NMR (400 MHz, CDCl3): δ 7.39 – 7.27 (m, 10H), 5.71 – 5.58 (m, 1H), 5.52 – 5.39 (m,
1H), 5.16 (d, J = 2.1 Hz, 4H), 3.55 (t, J = 7.4 Hz, 1H), 2.76 – 2.62 (m, 4H). 13C{1H} NMR (101 MHz,
CDCl3): δ 168.3, 135.2, 133.0, 128.5, 128.4, 128.2, 125.7 (q, J = 276.7 Hz), 121.3 (d, J = 3.5 Hz), 67.2,
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51.5, 37.1 (q, J = 29.7 Hz), 31.6. F NMR (376 MHz, CDCl3): δ -66.39 (t, J = 10.6 Hz). FT-IR (KBr, in
cm-1): 3089, 3066, 2915, 1728, 1671, 1638, 1596, 1446, 1320, 1289, 1208, 1159, 1144, 1084, 755, 724,
688, 665. HRMS (ESI-TOF) m/z: [M + H]+ calcd for C22H22F3O4 407.1470; Found: 407.1468.
(E)-Methyl-7,7,7-trifluoro-2-(phenylsulfonyl)hept-4-enoate (2j): Colorless oil, dr (10 : 1); (37.3 mg,
yield 74%); 1H NMR (400 MHz, CDCl3): δ 7.87 (d, J = 7.4 Hz, 2H), 7.70 (t, J = 7.7 Hz, 1H), 7.58 (t, J =
7.8 Hz, 2H), 5.63 – 5.44 (m, 2H), 4.00 (dd, J = 11.4, 3.9 Hz, 1H), 3.63 (s, 3H), 2.88 – 2.50 (m, 4H).
13C{1H} NMR (101 MHz, CDCl3): δ 165.6, 136.8, 134.5, 130.9, 129.3, 129.2, 129.1, 125.5 (q, J = 276.4
Hz), 122.8 (d, J = 3.4 Hz), 69.9, 52.9, 37.1 (q, J = 29.9 Hz), 29.8. 19F NMR (376 MHz, CDCl3): δ –66.45
(t, J = 10.6 Hz). FT-IR (KBr, in cm-1): 2987, 1741, 1641, 1447, 1372, 1326, 1270, 1204, 1139, 1084,
1057, 1036, 974, 916, 861, 841, 761, 741, 723, 689, 649. HRMS (ESI-TOF) m/z: [M + H]+ calcd for
C14H16F3O4S 337.0716; Found: 337.0710.
(E)-1,3-Diphenyl-2-(5,5,5-trifluoropent-2-en-1-yl)propane-1,3-dione (2k): White solid, mp: 49-51
°C, dr (8 : 1); (39.5 mg, yield 76%); 1H NMR (400 MHz, CDCl3): δ 7.95 (dd, J = 9.1, 2.0 Hz, 4H), 7.57
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(dt, J = 8.4, 1.3 Hz, 2H), 7.45 (t, J = 7.7 Hz, 4H), 5.78 (dt, J = 14.5, 7.1 Hz, 1H), 5.53 – 5.42 (m, 1H),
5.30 (t, J = 6.7 Hz, 1H), 2.88 (t, J = 7.0 Hz, 2H), 2.71 (qd, J = 10.7, 7.9 Hz, 2H). 13C{1H} NMR (101
MHz, CDCl3): δ 195.4, 135.8, 134.4, 133.6, 128.9, 128.5, 125.7 (q, J = 276.5 Hz), 120.7 (d, J = 3.3 Hz),
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56.5, 37.1 (q, J = 29.8 Hz), 32.3. 19F NMR (376 MHz, CDCl3): δ –66.35 (t, J = 10.7 Hz). FT-IR (KBr, in
cm-1): 2956, 1743, 1688, 1597, 1581, 1451, 1435, 1344, 1269, 1253, 1137, 1058, 975, 847, 782, 739, 691,
646. HRMS (ESI-TOF) m/z: [M + H]+ calcd for C20H18F3O2 347.1253; Found: 347.1248.
(E)-Methyl-2-benzoyl-7,7,7-trifluorohept-4-enoate (2l): Colorless oil, dr (9 : 1); (39.7 mg, yield
88%); 1H NMR (400 MHz, CDCl3): δ 7.96 (dd, J = 8.3, 1.3 Hz, 2H), 7.57 (dd, J = 9.1, 5.3 Hz, 1H), 7.46
(t, J = 7.7 Hz, 2H), 5.78 – 5.62 (m, 1H), 5.61 – 5.38 (m, 1H), 4.41 (t, J = 7.2 Hz, 1H), 3.65 (s, 3H), 2.81 –
2.62 (m, 4H). 13C{1H} NMR (101 MHz, CDCl3): δ 194.1, 169.6, 135.9, 133.7, 133.6, 128.7, 128.5, 125.7
(d, J = 276.5 Hz), 120.9 (d, J = 3.5 Hz), 53.4, 52.4, 37.0 (q, J = 29.8 Hz), 31.8. 19F NMR (376 MHz,
CDCl3): δ –66.51 (t, J = 10.7 Hz). FT-IR (KBr, in cm-1): 3034, 2981, 2933, 1720, 1644, 1599, 1497, 1434,
1397, 1369, 1325, 1288, 1211, 1132, 1081, 1016, 988, 949, 904, 877, 841, 818, 731, 706, 668. HRMS
(ESI-TOF) m/z: [M + H]+ calcd for C15H16F3O3 301.1046; Found: 301.1043.
(
E)-2-Benzoyl-7,7,7-trifluorohept-4-enenitrile (2m): Colorless oil, dr (8 : 1); (56.8 mg, yield 71%);
1H NMR (400 MHz, CDCl3): δ 7.96 (d, J = 1.6 Hz, 2H), 7.67 (t, J = 7.9 Hz, 1H), 7.53 (t, J = 7.7 Hz, 2H),
5.84 – 5.72 (m, 1H), 5.70 – 5.56 (m, 1H), 4.38 (dd, J = 7.9, 6.1 Hz, 1H), 2.93 – 2.69 (m, 4H). 13C{1H}
NMR (101 MHz, CDCl3): δ 189.8, 134.9, 134.9, 134.0, 131.3, 129.3, 128.9, 125.7 (q, J = 276.5 Hz),
123.5 (d, J = 3.4 Hz), 116.7, 39.5, 37.3 (q, J = 30.0 Hz), 32.4. 19F NMR (376 MHz, CDCl3): δ –66.27 (t, J
= 10.6 Hz). FT-IR (KBr, in cm-1): 3433, 3094, 3023, 2933, 2864, 1743, 1720, 1589, 1432, 1372, 1334,
1269, 1242, 1126, 1056, 971, 915, 842, 801, 743, 687, 651. HRMS (ESI-TOF) m/z: [M - H ]+ calcd for
C14H11F3NO 266.0798; Found: 266.0802.
(E)-2-(5,5,5-Trifluoropent-2-en-1-yl)malononitrile (2n): Colorless liquid, dr (8 : 1); (47.2 mg, yield
84%); 1H NMR (400 MHz, CDCl3): δ 5.87 – 5.74 (m, 2H), 3.79 (t, J = 6.6 Hz, 1H), 2.99 – 2.84 (m, 2H),
2.78 (t, J = 6.1 Hz, 2H). 13C{1H} NMR (101 MHz, CDCl3): δ 128.2, 126.4 (d, J = 3.3 Hz), 125.3 (q, J =
276.6 Hz), 111.8, 37.1 (q, J = 30.3 Hz), 33.6, 22.9. 19F NMR (376 MHz, CDCl3): δ –66.14 (t, J = 10.5
Hz). FT-IR (KBr, in cm-1): 2921, 2258, 1721, 1431, 1373, 1343, 1325, 1254, 1212, 1186, 1143, 1059, 976,
911, 845, 649. HRMS (ESI-TOF) m/z: [M - H]+ calcd for C8H6F3N2 187.0489; Found: 187.0481.
(E)-Ethyl-2-cyano-7,7,7-trifluorohept-4-enoate (2o): Colorless oil, dr (10 : 1); (57.2 mg, yield 81%);
1H NMR (400 MHz, CDCl3): δ 5.76 – 5.66 (m, 1H), 5.66 – 5.54 (m, 1H), 4.22 (q, J = 7.3 Hz, 2H), 3.55 (t,
J = 6.6 Hz, 1H), 2.86 – 2.73 (m, 2H), 2.66 (t, J = 6.8 Hz, 2H), 1.27 (t, J = 7.2 Hz, 3H). 13C{1H} NMR
(101 MHz, CDCl3): δ 165.2, 130.6, 125.5 (q, J = 276.6 Hz), 123.4 (d, J = 3.1 Hz), 115.8, 62.8, 37.2, 36.9
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(q, J = 30.1 Hz), 32.4, 13.7. 19F NMR (376 MHz, CDCl3): δ –66.46 (t, J = 10.6 Hz). FT-IR (KBr, in cm-1):
2988, 2940, 2252, 1746, 1620, 1432, 1371, 1340, 1253, 1211, 1140, 1057, 975, 911, 854, 648. HRMS
(ESI-TOF) m/z: [M + H]+ calcd for C10H13F3NO2 236.0893; Found: 236.0890.
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(E)-tert-Butyl-7,7,7-trifluoro-2-tosylhept-4-enoate (2p): Colorless oil, dr (39 : 1); (42.3 mg, yield-
72%); 1H NMR (400 MHz, CDCl3): δ 7.75 (d, J = 8.3 Hz, 2H), 7.36 (d, J = 8.1 Hz, 2H), 5.65 – 5.54 (m,
1H), 5.54 – 5.44 (m, 1H), 3.87 (dd, J = 11.4, 3.8 Hz, 1H), 2.81 – 2.57 (m, 4H), 2.46 (s, 3H), 1.34 (s, 9H).
13C{1H} NMR (101 MHz, CDCl3): δ 164.1, 145.4, 134.1, 131.3, 129.6, 129.4, 125.6 (q, J = 276.6 Hz),
122.3 (d, J = 3.4 Hz), 37.2 (q, J = 29.9 Hz). 83.5, 70.4, 37.2 (q, J = 29.9 Hz), 29.8, 27.6, 21.7. 19F NMR
(376 MHz, CDCl3): δ –66.31 (t, J = 10.6 Hz). FT-IR (KBr, in cm-1): 2975, 2932, 1727, 1599, 1573, 1493,
1456, 1395, 1369, 1319, 1260, 1140, 1111, 1083, 1015, 843, 813, 709, 665, 583. HRMS (ESI-TOF) m/z:
[M - H]+ calcd for C18H22F3O4S 391.1196; Found: 391.1204.
(E)-2,2-Dimethyl-5-(5,5,5-trifluoropent-2-en-1-yl)-1,3-dioxane-4,6-dione (2q): White solid, (m.p:
102-104 °C) dr (99 : 1); (68.6 mg, yield 86%); 1H NMR (400 MHz, CDCl3): δ 5.83 – 5.69 (m, 1H), 5.67 –
5.57 (m, 1H), 3.59 (t, J = 5.1 Hz, 1H), 2.88 – 2.84 (m, 2H), 2.83 – 2.70 (m, 2H), 1.78 (s, 3H), 1.74 (s,
3H). 13C{1H} NMR (101 MHz, CDCl3): δ 164.7, 131.8, 125.7 (d, J = 276.4 Hz), 123.1 (d, J = 3.4 Hz),
105.1, 46.1, 37.2 (q, J = 29.8 Hz), 29.0, 28.3, 26.8. 19F NMR (376 MHz, CDCl3): δ –66.36 (t, J = 10.7
Hz). FT-IR (KBr, in cm-1): 3446, 3098, 3016, 3004, 2988, 1978, 1923, 1874, 1733, 1634, 1584, 1421,
1307, 1205, 1164, 1085, 1065, 1020, 989, 883, 826, 795, 689, 666. HRMS (ESI-TOF) m/z: [M - H]+ calcd
for C11H12F3O4 265.0693; Found: 265.0695.
(E)-2-(5,5,5-Trifluoropent-2-en-1-yl)-1H-indene-1,3(2H)-dione (2r): Colorless oil, dr (32 : 1); (31.6
mg, yield 79%); 1H NMR (400 MHz, CDCl3): δ 7.96 (dd, J = 5.7, 3.1 Hz, 2H), 7.84 (dd, J = 5.7, 3.1 Hz,
2H), 5.70 – 5.60 (m, 1H), 5.55 – 5.45 (m, 1H), 3.10 (t, J = 5.8 Hz, 1H), 2.74 (t, J = 6.5 Hz, 2H), 2.65 (qd,
J = 10.6, 7.2 Hz, 2H). 13C{1H} NMR (101 MHz, CDCl3): δ 199.9, 142.5, 135.7, 132.3, 125.6 (q, J = 276.5
Hz), 123.2, 121.9 (d, J = 3.3 Hz), 53.1, 37.1 (q, J = 29.8 Hz), 29.4. 19F NMR (376 MHz, CDCl3): δ –
66.60 (t, J = 10.7 Hz). FT-IR (KBr, in cm-1): 3101, 2978, 2930, 1723, 1646, 1460, 1433, 1396, 1369,
1323, 1260, 1210, 1016, 991, 948, 921, 669. HRMS (ESI-TOF) m/z: [M - H]+ calcd for C14H10F3O2
267.0638; Found: 267.0641.
(Z)-Dimethyl-2-(4-(trifluoromethyl)cyclopent-2-en-1-yl)malonate (2s): Colorless liquid, (yield
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61%); H NMR (400 MHz, CDCl3): δ 5.99 (d, J = 4.6 Hz, 1H), 5.75 – 5.70 (m, 1H), 3.75 (s, 3H), 3.74 (s,
3H), 3.60 – 3.51 (m, 1H), 3.47 – 3.38 (m, 1H), 3.34 (d, J = 8.5 Hz, 1H), 2.33 – 2.21 (m, 1H), 1.94 (ddd, J
= 14.5, 8.5, 5.5 Hz, 1H). 13C{1H} NMR (101 MHz, CDCl3): δ 168.6, 168.5, 137.7, 127.1 (d, J = 278.5
Hz), 127.0 (d, J = 2.4 Hz), 55.9, 52.6, 49.4 (d, J = 28.6 Hz), 44.9, 29.7, 28.0. 19F NMR (376 MHz,
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CDCl3): δ –72.82 (d, J = 8.7 Hz). FT-IR (KBr, in cm-1): 1733, 1400, 1119, 601. HRMS (ESI-TOF) m/z:
[M + H]+ calcd for C11H14F3O4 267.0839; Found: 267.0834.
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(Z)-Dimethyl-2-4-(trifluoromethyl)cyclohex-2-en-1-yl)malonate (2t): Colorless liquid, (yield 71%);
1H NMR (400 MHz, CDCl3): δ 5.83 (d, J = 10.3 Hz, 1H), 5.70 (d, J = 10.0 Hz, 1H), 3.74 (s, 3H), 3.74 (s,
3H), 3.30 (d, J = 8.2 Hz, 1H), 3.00 – 2.79 (m, 1H), 2.08 – 1.87 (m, 1H), 1.63 (dd, J = 10.7, 2.4 Hz, 2H),
1.40 (tdd, J = 13.1, 10.6, 2.6 Hz, 2H). 13C{1H} NMR (101 MHz, CDCl3): δ 168.4, 168.4, 132.5, 126.9 (q,
J = 279.0 Hz), 122.6 (d, J = 2.8 Hz), 40.4 (q, J = 27.3 Hz), 56.0, 52.5, 35.3, 24.9, 21.3. 19F NMR (376
MHz, CDCl3): δ –72.94 (d, J = 8.7 Hz). FT-IR (KBr, in cm-1): 1739, 1435, 1338, 1253, 1151, 605. HRMS
(ESI-TOF) m/z: [M + H]+ calcd for C12H16F3O4 281.0995; Found: 281.0997.
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(Z)-Dimethyl-2-(4-(trifluoromethyl)cyclooct-2-en-1-yl)malonate (2u): Colorless liquid, (yield
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67%); H NMR (400 MHz, CDCl3): δ 5.68 (dd, J = 12.1, 6.1 Hz, 1H), 5.50 (ddd, J = 12.2, 6.9, 1.2 Hz,
1H), 3.73 (s, 3H), 3.72 (s, 3H), 3.42 (d, J = 7.1 Hz, 1H), 3.39 – 3.18 (m, 2H), 1.93 – 1.60 (m, 8H).
13C{1H} NMR (101 MHz, CDCl3): δ 168.8, 168.6, 133.2, 127.4 (q, J = 279.3 Hz), 123.6 (d, J = 2.4 Hz),
57.2, 52.5, 43.0 (q, J = 25.8 Hz).39.5, 29.7, 29.5, 25.5, 25.5, 23.8. 19F NMR (376 MHz, CDCl3): δ –72.63
(d, J = 8.8 Hz). FT-IR (KBr, in cm-1): 1738, 1434, 1394, 1265, 1165, 606. HRMS (ESI-TOF) m/z: [M +
H]+ calcd for C14H20F3O4 309.1308; Found: 309.1300.
(E)-2-(5,5,5-Trifluoropent-2-en-1-yl)propane-1,3-diyl-dibenzoate (3a): Colorless liquid dr (7: 1);
(87.7 mg, yield 72%); 1H NMR (400 MHz, CDCl3): δ 8.03 (d, J = 7.6 Hz, 4H), 7.56 (t, J = 7.5 Hz, 2H),
7.43 (t, J = 7.7 Hz, 4H), 5.83 – 5.73 (m, 1H), 5.60 – 5.47 (m, 1H), 4.43 (ddd, J = 25.4, 11.3, 5.6 Hz, 4H),
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2.89 – 2.71 (m, 2H), 2.43 (ddd, J = 11.2, 7.8, 3.3 Hz, 1H), 2.37 (t, J = 7.0 Hz, 2H). C{1H} NMR (101
MHz, CDCl3): δ 166.4, 134.3, 133.1, 129.9, 129.6, 128.4, 125.8 (q, J = 276.7 Hz), 121.0 (d, J = 3.4 Hz),
64.4, 37.6, , 37.3 (q, J = 29.8 Hz), 31.7. 19F NMR (376 MHz, CDCl3): δ –66.43 (t, J = 10.7 Hz). FT-IR
(KBr, in cm-1): 3065, 3034, 2956, 2897, 2853, 1723, 1603, 1586, 1493, 1451, 1375, 1314, 1270, 1175,
1135, 1111, 1069, 1025, 971, 842, 802, 710, 688, 651. HRMS (ESI-TOF) m/z: [M + Na]+ calcd for
C22H21F3O4Na 429.1284; Found: 429.1279.
(E)-2-(5,5,5-Trifluoropent-2-en-1-yl)propane-1,3-diyl-diacetate (3b): Colorless liquid, dr (8 : 1);
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(64.5 mg, yield 76%); H NMR (400 MHz, CDCl3): δ 5.79 – 5.58 (m, 1H), 5.57 – 5.33 (m, 1H), 4.05 (qd,
J = 11.2, 5.6 Hz, 4H), 3.05 – 2.41 (m, 2H),2.20 – 2.08 (m, 3H), 2.06 (s, 6H). 13C{1H} NMR (101 MHz,
CDCl3): δ 170.9, 134.3, 125.8 (q, J = 276.7 Hz), 120.8 (d, J = 3.2 Hz), 63.7, 37.3 (q, J = 29.6 Hz), 37.1,
31.4, 20.8. 19F NMR (376 MHz, CDCl3): δ –66.61 (t, J = 10.7 Hz). FT-IR (KBr, in cm-1): 1736, 1403,
1134, 603. HRMS (ESI-TOF) m/z: [M + H]+ calcd for C12H18F3O4 283.1152; Found: 283.1149.
(E)-4,4'-(((2-(5,5,5-Trifluoropent-2-en-1-yl)propane-1,3-diyl)bis(oxy))bis(methylene))bis
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((trifluoromethyl)benzene) (3c): Colorless liquid, dr (37 : 1); (128.mg, yield 83%); 1H NMR (400
MHz, CDCl3): δ 7.59 (d, J = 8.1 Hz, 4H), 7.42 (d, J = 8.0 Hz, 4H), 5.77 – 5.60 (m, 1H), 5.50 – 5.32 (m,
1H), 4.54 (s, 4H), 3.56 – 3.46 (m, 4H), 2.82 – 2.67 (m, 2H), 2.23 (t, J = 7.0 Hz, 2H), 2.05 (dt, J = 12.5,
6.3 Hz, 1H). 13C{1H} NMR (101 MHz, CDCl3): δ 142.6, 135.7, 127.4, 126.0 (q, J = 277.7 Hz), 125.5 (q, J
= 276 Hz), 125.3(d, J = 3.6 Hz), 119.8 (d, J = 3.2 Hz), 72.3, 70.4, 39.3, 37.3 (d, J = 29.6 Hz), 31.7. 19F
NMR (471 MHz, CDCl3): δ –62.54 (6F, s), –66.65 (3F, t, J = 10.1 Hz). FT-IR (KBr, in cm-1): 1406, 1329,
1253, 1134, 601. HRMS (ESI-TOF) m/z: [M + H]+ calcd for C24H24F9O2 515.1627; Found: 515.1628.
(E)-2-(5,5,5-Trifluoropent-2-en-1-yl)propane-1,3-diyl bis(2,2-dimethylpropanoate)) (3d):
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Colorless liquid, dr (6 : 1); (75.9 mg, yield- 69%); H NMR (400 MHz, CDCl3): δ 5.73 – 5.63 (m, 1H),
5.49 – 5.40 (m, 1H), 4.03 (qd, J = 11.1, 5.4 Hz, 4H), 2.88 – 2.69 (m, 2H), 2.25 – 2.07 (m, 3H), 1.19 (s,
18H). 13C{1H} NMR (126 MHz, CDCl3): δ 178.3, 134.3, 126.1 (q, 280.78 Hz), 120.8 (d, J = 3.6 Hz).
63.3, 37.3, 38.8,37.3 (q, 24.24 Hz), 31.5, 27.1. 19F NMR (376 MHz, CDCl3): δ –66.62 (t, J = 10.7 Hz).
FT-IR (KBr, in cm-1): 1734, 1411, 1387, 1164, 1077, 600. HRMS (ESI-TOF) m/z: [M + H]+ calcd for
C18H30F3O4 367.2091; Found: 367.2082.
Procedure for the further functionalization of allylic trifluoromethylated product:
2-(2,2-bis(Phenylsulfonyl)ethyl)-3-(2,2,2-trifluoroethyl)oxirane (4a): To an oven dried two neck
round bottom flask, add 2a (0.2 mmol, 84 mg) in Argon atmosphere. Next 5 mL of CHCl3 added and
cooled in ice bath, then freshly recrystallized 75% m-CPBA (0.5 mmol, 86 mg) in CHCl3 was added over
15 min. then allowed to the room temperature for overnight. The reaction mixture was concentrated on
rotor vapor and purified by column chromatography. The the compound 4a was isolated as colorless
liquid in 64% yield (55.6 mg), dr (4 : 1); 1H NMR (400 MHz, CDCl3): δ 7.90 (dd, J = 14.3, 7.4 Hz, 4H),
7.70 (td, J = 7.6, 2.9 Hz, 2H), 7.60 – 7.51 (m, 4H), 4.61 (dd, J = 6.9, 4.8 Hz, 1H), 3.22 (td, J = 5.7, 1.8
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Hz, 1H), 2.92 (ddd, J = 6.6, 4.9, 1.7 Hz, 1H), 2.54 – 2.25 (m, 4H). C{1H} NMR (101 MHz, CDCl3): δ
137.6, 137.0, 134.8, 129.6, 129.4, 129.3, 129.3, 129.3, 125.5 (d, J = 274.2 Hz), 80.5, 54.3, 53.1 (d, J = 3.9
Hz), 36.8 (q, J = 29.1 Hz), 28.3. 19F NMR (376 MHz, CDCl3): δ –64.34 (t, J = 10.4 Hz). FT-IR data (KBr,
in cm-1): 3101, 2978, 2930, 1496, 1478, 1396, 1323, 1260, 1134, 1082, 903, 880, 841, 818, 730, 669.
HRMS (ESI-TOF) m/z: [M + H]+ calcd For C18H18F3O5S2 435.0542; Found: 435.0538.
(6,6,6-Trifluorohexane-1,1-diyldisulfonyl)dibenzene (4b): To an oven dried two neck round bottom
flask, added 2a (0.2 mmol, 84 mg) in Ar atm. followed by 5 mol% Pd-C, 8 eq. AcOH and 5 mL of
isopropanol. Finally added 8 eq. of NaBH4 in one portion and reaction was monitored by TLC. Reaction
was quenched using 2 N HCl, extract with EtOAc (2 x 10 mL), concentrated under vacuum and purified
by column chromatography using 5-10% EtOAc and hexane as eluent, the compound 4b isolated as
Colorless liquid in 95% yield(79.8 mg) which can become solid in low temperatures. White solid, mp: 34-
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35 °C, (yield 95%) ; H NMR (400 MHz, CDCl3): δ 7.94 (dd, J = 8.3, 1.3 Hz, 4H), 7.73 – 7.66 (m, 2H),
7.57 (t, J = 7.7 Hz, 4H), 4.38 (t, J = 5.6 Hz, 1H), 2.19 (dt, J = 7.9, 7.5 Hz, 2H), 2.08 – 1.95 (m, 2H), 1.67
(dt, J = 11.9, 7.7 Hz, 2H), 1.57-1.41 (m, 2H). 13C{1H} NMR (101 MHz, CDCl3): δ 137.7, 134.676, 129.5,
129.2, 126.8 (q, J = 276.3 Hz), 83.2, 33.1 (q, J = 28.7 Hz), 27.0, 25.3, 21.5 (d, J = 2.7 Hz). 19F NMR (376
MHz, CDCl3): δ –66.22 (t, J = 10.8 Hz). FT- IR data (KBr, in cm-1): 2923, 2259, 1720, 1432, 1372, 1340,
1323, 1253, 1210, 1187, 1142, 1059, 972, 910, 848, 648. HRMS (ESI-TOF) m/z: [M + H]+ calcd for
C18H20F3O4S2 421.075; Found: 421.0747.
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(E)-Ethyl-9,9,9-trifluoro-4,4-bis(phenylsulfonyl)non-6-enoate (4c): To an oven dried two neck
round bottom flask, added NaH (1.5 eq.) and cooled to 0 °C then 2a (0.2 mmol, 84 mg) in THF (5 mL)
was added under Ar atm. Then ethyl acrylate (3. eq.) in THF added drop wise over 10 min and allowed
the reaction to stir at rt for 48 h. The reaction was quenched by addition of the 5 mL water. Organic part
separated and washed with brine, dried over Na2SO4 and concentrated under vacuum. Product was
purified by column chromatography using 10-15% EtOAc and hexane as eluent. The compound 4c was
isolated as a colorless liquid in 76% yield (78.9 mg), dr (10 : 1). 1H NMR (400 MHz, CDCl3): δ 8.05 (d, J
= 7.7 Hz, 4H), 7.73 (t, J = 7.3 Hz, 2H), 7.60 (t, J = 7.8 Hz, 4H), 5.97 – 5.83 (m, 1H), 5.59 – 5.50 (m, 1H),
4.12 (q, J = 7.2 Hz, 2H), 2.99 (d, J = 6.6 Hz, 2H), 2.87 – 2.73 (m, 4H), 2.58 – 2.51 (m, 2H), 1.25 (t, J =
7.1 Hz, 3H). 13C{1H} NMR (101 MHz, CDCl3): δ 172.0, 136.6, 135.0, 134.9, 131.4, 129.5, 128.9, 125.7
(q, J = 276.3 Hz), 124.4 (d, J = 3.6 Hz), 89.5, 60.9, 37.4 (q, J = 30.0 Hz), 33.2, 28.8, 25.3, 25.2, 14.2. 19F
NMR (376 MHz, CDCl3): δ –66.11 (t, J = 10.6 Hz). FT-IR data (KBr, In cm-1): 3074, 2984, 2925, 2850,
1734, 1582, 1448, 1380, 1335, 1313, 1253. HRMS (ESI-TOF) m/z: [M + H]+ calcd for C23H26F3O6S2
519.1117; Found: 519.1102.
(E)-(1-Bromo-6,6,6-trifluorohex-3-ene-1,1-diyldisulfonyl)dibenzene (4d): To oven dried 20 mL
round bottom flask charged with magnetic stirred, added 2a (0.2 mmol) in 1:1 THF followed by water and
NBS (0.3 mmol, 1.5 eq.). The reaction stirred for overnight and workup with ethyl acetate (2 x 10 mL),
the combined organic layer was washed with NaHCO3, brine and dried over Na2SO4. Organic layer was
concentrated under reduced pressure and purified by column chromatography using 5-10% EtOAc and
hexane as eluent. The compound 4d was isolated as colorless oil in 58% yield (57.5 mg), dr (15 : 1). 1H
NMR (400 MHz, CDCl3): δ 8.09 (dd, J = 8.4, 1.3 Hz, 4H), 7.75 (dd, J = 10.8, 4.6 Hz, 2H), 7.60 (t, J = 7.9
Hz, 4H), 5.98 – 5.88 (m, 1H), 5.53 (m, 1H), 3.25 (d, J = 6.9 Hz, 2H), 2.92 – 2.78 (m, 2H). 13C{1H} NMR
(101 MHz, CDCl3): δ 135.3, 135.1, 132.1, 129.7, 128.7, 125.6 (d, J = 276.8 Hz), 124.1 (d, J = 3.2 Hz),
93.5, 38.1, 37.2 (q, J = 30.0 Hz). 19F NMR (376 MHz, CDCl3): δ –66.01 (t, J = 10.6 Hz). FT-IR data
(KBr, In cm-1): 1748, 1463, 1394, 1294, 1168, 611 HRMS (ESI-TOF) m/z: [M + H]+ calcd for
C18H17BrF3O4S2 496.9698; Found: 496.9694.
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(E)-(1-Chloro-6,6,6-trifluorohex-3-ene-1,1-diyldisulfonyl)dibenzene (4e): To an oven dried 20 mL
round bottom flask charged with magnetic stirred, added 2a (0.2 mmol), chloramine T (0.3 mmol, 1.5 eq.)
and PhMe3NBr (0.03 mmol, 0.15 eq.). Argon was back filled for 3 times over 10 min, 5 mL CH3CN
added and stirred for overnight. After finishing of the reaction, filter off the solid, the liquid part
concentrated and purified by column chromatography using 5-10% EtOAc and hexane as eluent. The
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desired compound 4e was isolated as colorless liquid in 98% yield (88.9 mg), dr (12 : 1). H NMR (400
MHz, CDCl3): δ 8.08 (dd, J = 8.6, 1.2 Hz, 4H), 7.77 – 7.71 (m, 2H), 7.59 (t, J = 7.0 Hz, 4H), 5.97 – 5.84
(m, 1H), 5.57 – 5.47 (m, 1H), 3.25 (dd, J = 6.7, 1.2 Hz, 2H), 2.84 (td, J = 17.8, 10.1 Hz, 2H). 13C{1H}
NMR (101 MHz, CDCl3): δ 135.3, 135.0, 132.1, 131.8, 129.6, 128.8, 128.6, 125.6 (q, J = 277.0 Hz),
124.0 (d, J = 3.6 Hz), 93.5, 38.1, 37.1 (q, J = 30.2 Hz). 19F NMR (376 MHz, CDCl3): δ –65.97 (t, J = 10.7
Hz). FT-IR data (KBr, In cm-1) 1739, 1434, 1403, 1254, 1160, 608. HRMS (ESI-TOF) m/z: [M + H]+
calcd for C18H17ClF3O4S2 453.0203; Found: 453.0206.
Typical procedure for the gram scale synthesis: To an oven dried 100 mL round bottom flask
equipped with a magnetic stir bar was added VCP 1e (1.10 g, 6 mmol), CF3SO2Na (1.87 g, 12 mmol) and
10 mol% photocatalyst T(p-CH3)PPT (262 mg, 0.6 mmol). The reaction tube was vacuumed and
backfilled with argon (3 times) and put a septum over the reaction tube. Then 1.8 mLAcOH and 80 mL of
DCE was added through the septum by a syringe, and placed approximately 5 cm from light setup. After 6
h of the reaction 50 mL of water was added and extracted with DCM (3 x 50 mL). The combined organic
layer was dried over Na2SO4 and solvent was removed under reduced pressure. The crude product was
then purified by flash column chromatography on silica gel mesh 230-400 using 10% DCM and hexane
as an eluent to afford the product 2e (1.07 g, 71%)
Typical procedure for Control experiment with TEMPO:
To an oven dried borosilicate test tube equipped with a magnetic stir bar was added VCP (0.15 mmol, 1
eq.), CF3SO2Na (0.3 mmol, 2 eq.) TEMPO (0.23 mmol, 1.5 eq.) and 10 mol% photocatalyst T(p-CH3)PPT
(6.6 mg, 0.1 eq.). The reaction tube was vacuumed and backfilled with argon (3 times) and put a septum
over the reaction tube. Next, 90 µL AcOH (10 eq.) and 2 mL of DCE was added through the septum by a
syringe, and after 30 min reaction quenched and added PhCF3 (0.15 mmol) to the reaction mixture and
taken 19F NMR. Formation of TEMPO-CF3 adduct 5b was observed by 19F NMR (376 MHz, CDCl3): as
singlet (s, 3F) at δ –55.86 ppm with 31% yield.
ASSOCIATED CONTENT
Supporting Information
The Supporting Information is available free of charge on the
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X-ray crystallographic data of 2a
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Copies of 1H, 13C{1H} and 19F NMR spectra of known and all new compounds
COSY and NOESY spectra of compound 2s
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AUTHOR INFORMATION
Corresponding Author
suresh@iiserkol.ac.in
pc16rs018@iiserkol.ac.in
kgg15rs014@iiserkol.ac.in
Notes
The authors declare no competing financial interests.
ACKNOWLEDGMENT
Dedicated to Professor Srinivasan Chandrasekaran on the occasion of his 73rd birthday. Financial support
from the IISER Kolkata for startup Grant, SERB for Early Carrier Research (ECR) Grant and DST-SERB
for Ramanujan Fellowship are acknowledged. PC and KGG thank UGC and DST for their PhD
fellowship.
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