Synthesis of Trifluoromethylthiolated Alkenes and Ketones by Decarboxylative Functionalization of Cinnamic Acids

Article abstract of DOI:10.1002/asia.201601098

A tunable decarboxylative trifluoromethylthiolation of cinnamic acids with AgSCF₃ was developed to afford trifluoromethylthiolated alkenes or ketones by using transition metal-mediated conditions.

Full text of DOI:10.1002/asia.201601098

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Accepted Article
Title: Synthesis of trifluoromethylthiolated alkenes and ketones via decarboxylative
functionalization of cinnamic acids
Authors: Yangen Huang; Shen Pan; Feng-Ling Qing
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Synthesis of trifluoromethylthiolated alkenes and ketones via
decarboxylative functionalization of cinnamic acids
Shen Pan,[a] Yangen Huang*,[a] and Feng-Ling Qing[a,b]
Abstract:
A
tunable decarboxylative trifluoromethylthiolation of
generated at oxidative conditions. Then, the addition of SCF3
radical to cinnamic acid will generate radical intermediate A,
which further undergoes decarboxylation and oxidation may
generate SCF3-substituted alkenes or ketones depending on
conditions such as oxidants and additional nucleophiles (e.g.
water) (Scheme 1). Various efficient methods for synthesis of α-
SCF3-substituted ketones which act as important building blocks
have been reported including the trifluoromethylthiolation of α-
haloketones,24 β-ketoesters,25 silyl enol ethers26 and simple
ketones27 with different SCF3 sources. The decarboxylative
trifluoromethylthiolation of α,β-unsaturated carboxylic acids
would be another efficient method for synthesis of the α-SCF3
substituted ketones. As part of our continuing studies on
developing methodologies for introduction of SCF3 into organic
cinnamic acids with AgSCF3 was developed to afford
trifluoromethylthiolated alkenes or ketones, respectively, via
transition metal-mediated conditions.
The decarboxylative cross-coupling reaction of carboxylic
acids is a fundamentally important transformation in organic
chemistry, as carboxylic acids are abundant and inexpensive
stock chemicals.1 This reaction provides a powerful strategy for
the formation of carbon–carbon1c and carbon–heteroatom bonds
(e.g., C–F(Cl),2 C–N,3 C–P4 and C–S5) through transition-metal
catalysis and/or free radical mechanism.6 More specifically, its
application on the syntheses of fluorine-containing molecules
have attracted much attentions during the past decades.2c For
example, the decarboxylative trifluoromethylation has nicely
achieved by Hu,7 Liu,8 Maiti,9 Zhu,10 Duan,11 Cai12 and Altman13
using various trifluoromethylation reagents.14 However,
compared to large number reports on decarboxylative
molecules, herein we present
a
tunable and efficient
decarboxylative trifluoromethylthiolation of α,β-unsaturated
carboxylic acids to afford vinyl trifluoromethyl thioethers and α-
SCF3 substituted ketones, respectively.
trifluoromethylation,
trifluoromethylthiolation are very rare. Shen and co-workers
reported silver-catalyzed decarboxylative
the
reports
on
decarboxylative
a
trifluoromethylthiolation of aliphatic carboxylic acids in aqueous
emulsion to afford alkyl trifluoromethyl thioethers in high yields.15
Glorius and co-workers achieved the same conversion by visible
light promoted decarboxylation.16 Among common fluorine-
containing groups, SCF3 has the highest lipophilicity value
(x=1.44), which is much higher than those of SF5 (x=1.23),
OCF3 (x =1.04), CF3 (x =0.88), CH3 (x =0.52).17 So SCF3-
containing compounds are increasingly attractive for their
potential applications in agrochemicals and pharmaceuticals as
well as in materials science. Therefore, efficient methodologies
for syntheses of SCF3-containing molecules bearing Csp2−SCF3
and Csp3−SCF3 as well as Csp−SCF3 bonds have been
developed.18 However, facile construction of Cvinyl−SCF3 bonds
are limited, and prefunctionalized starting materials, such as
enamines,19 vinyl halides,20 vinylboronic acids21 or terminal
alkynes22 are usually used (Scheme 1).
Scheme 1. Methods for the syntheses of SCF3-substituted alkenes and α-
SCF3 substituted ketones.
We used trifluoromethylthiolation of cinnamic acid 1a as the
model system. The initiator, oxidant, and solvent critically affect
the efficiency of this reaction (for the optimization of the reaction
conditions, see ESI, Table S1). Initially, the reaction solvent was
examined with CuI and Ag2CO3 as initiator and K2S2O8 as
oxidant at 50 oC. The results disclosed that no reaction occurred
in neat solvent such as THF, DCE, CH3CN, DMSO and DMF,
however, the desired product 2a was detected in 40 % yield
when mixed solvents CH3CN/HOAc (4:1) were used. Next, the
copper salts including CuTC, CuOAc, CuCN, CuCl, CuBr,
(CH3CN)4CuPF6 CuCl2, CuSO4 and silver salts including Ag2CO3,
AgBF4, AgOAc, AgNO3, AgOTf, Ag2SO4 as initiator was explored.
The combination of CuI and Ag2CO3 was found to be the best
initiator. The investigation of oxidants disclosed that
peroxydisulfuric acid salts such as K2S2O8, Na2S2O8 and
(NH4)2S2O8 were better than PhI(OAc)2 and tert-butyl
hydroperoxide (TBHP). The yield of the decarboxylative
trifluoromethylthiolated alkene could be increased from 24% to
52% or 71% with the increase of reaction temperature from 50
Since 2012, we have been working on installations of SCF3
group onto organic molecules.23 We propose that
decarboxylative trifluoromethylthiolation might be suitable
strategy for the synthesis of vinyl trifluoromethylthioethers via a
radical pathway (Scheme 1, bottom). First, SCF3 radical can be
[a]
[b]
Mr. Shen Pan, Dr. Yangen Huang and Dr. Feng-Ling Qing
College of Chemistry, Chemical Engineering and Biotechnology
Donghua University
2999 North Renmin Road, Shanghai 201620, China
E-mail: hyg@dhu.edu.cn
Dr. Feng-Ling Qing
Key Laboratory of Organofluorine Chemistry
Shanghai Institute of Organic Chemistry, Chinese Academy of
Science
345 Lingling Road, Shanghai 200032, China
Supporting information for this article is given via a link at the end of
the document.((Please delete this text if not appropriate))
o
o
oC to 70 C or 90 C, respectively. Further optimization of the
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reaction conditions revealed that using AgSCF3 (2.0 equiv), CuI
(1.0 equiv) and Ag2CO3 (2.0 equiv), K2S2O8 (2.0 equiv) in
CH3CN/HOAc(2:1) at 90 C for 1 h could give the desired vinyl
trifluoromethyl thioether 2a in 84% yield with excellent E/Z
selectivity (94:6).
our interest to the synthesis of α-SCF3 substituted ketones via
the similar transformation. With cinnamic acid 1a as the model
substrate and AgSCF3 as SCF3 source, the reaction conditions
for the synthesis of α-SCF3 substituted ketone 3a were
optimized (for the optimization of the reaction conditions, see
ESI, Table S2). First, the reaction was performed with CuI as a
catalyst and K2S2O8 as an oxidant in CH3CN/H2O (2:1) at 50oC
for 12 h under O2 atmosphere, however, no desired product was
detected. Then, we investigated the effect of iron salts as
catalyst instead of Cu salts. Among the tested iron salts, the
best activity was observed with Fe(OAc)2 affording 3a in 13%
yield. The presence of silver salt was crucial to the
transformation, and Ag2SO4 was proved to be the most effective
and led to an increase in the yield to 62%. Similar to the
synthetic condition for vinyl trifluoromethyl thioether,
peroxydisulfuric acid salts such as K2S2O8, Na2S2O8 and
(NH4)2S2O8 were better than PhI(OAc)2 and tert-butyl
hydroperoxide (TBHP). Further screening of reaction conditions
revealed that the solvent mixture of CH3CN/H2O (2:1) was
superior to others, and prolonged reaction time from 12 h to 18 h
resulted higher yield (62 % to 70 %). It is noteworthy that the
transformation become sluggish under Argon atmosphere which
indicated that oxygen as a second oxidant was essential.
o
With the optimized conditions in hand, the scope of the Cu-
mediated
decarboxylative
trifluoromethylthiolation
for
preparation of vinyl trifluoromethyl thioether was examined. A
variety of aryl substituted α,β-unsaturated carboxylic acids can
be transformed into the desired vinyl trifluoromethyl thioether in
moderate to good yields (Table 1). Cinnamic acid with an alkyl
substitution at ortho-, meta- or para-position gave comparative
yield and E/Z selectivity (2b-2d, 2g and 2h). Halogen on the
aromatic ring was well tolerated (2i-2l), providing a synthetic
handle for further functionalization. Naphthyl and heteroaryl α,β-
unsaturated carboxylic acids also gave corresponding vinyl
trifluoromethyl thioether in moderate yields (2m-2q). In most
cases, the E/Z selectivity was good with a ratio range of 78:22-
94:6, however, the reversion of the E/Z selectivity was observed
for pyridyl α,β-unsaturated carboxylic acid (2p, E/Z 0:100).
Unfortunately, aliphatic substituted α,β-unsaturated carboxylic
acids and cinnamic acids with a strong electron-withdrawing
group such as nitro, cyano, formyl and trifluoromethyl groups
were not suitable substrates.
The scope of substrates for the synthesis of α-SCF3
substituted ketones under the optimized condition [Fe(OAc)2 (1.0
equiv), AgSCF3 (1.0 equiv), Ag2SO4 (2.0 equiv), Na2S2O8 (2.0
equiv) in CH3CN/H2O (2:1) and O2 at 50oC for 18 h] was then
investigated. A variety of α,β-unsaturated carboxylic acids could
be efficiently converted to the desired α-SCF3 substituted
ketones in moderate to good yields (Table 2). Electron-donating
and electron-withdrawing substituents at the ortho-, meta- or
para -positions on the aromatic ring of cinnamic acids have little
influence on the reaction performance. The oxidative
decarboxylative trifluoromethylthiolation of para- and meta-
methoxyphenyl acrylic acid and para- and meta-tolyl acrylic acid
proceeded smoothly to give 3b-3e in good yields (45-63%).The
α-SCF3 substituted ketones with isopropyl (3f) and phenyl (3g)
substituents were also obtained in yield of 55% and 65%,
respectively. Halogen on the aromatic ring was well tolerated in
the reaction. The yields of para-, meta- and ortho- chlorophenyl
(3h-3j) and bromophenyl (3k-3m) α-SCF3-substituted ketones
were varied in the range of 35% to 75%. Unlike the synthesis of
vinyl trifluoromethyl thioethers, cinnamic acids with strong
electron-withdrawing substituents were also suitable substrates
to afford the corresponding para-, meta-trifluoromethyl (3n-3o),
para-, meta-cyanophenyl (3q-3r), para-fluorophenyl (3p), 3,4-
dichlorophenyl (3s) and para-formyl (3t) α-SCF3-substituted
ketones in moderate to good yields (53-75%). The α,β-
unsaturated carboxylic acid with an extra methyl group on the α
position also gave 1-phenyl-2-((trifluoromethyl)thio)propan-1-one
(3x) in 66% yield. However, the yields of acetamidophenyl (3u,
31%) and heterocycle aromatic (3w, 20%) substituted α-SCF3
substituted ketones were poor. Surprisingly, when p-nitro-
cinnamic acid was applied to the iron-mediated reaction system,
the vinyl trifluoromethyl thioether (2y, 63%) was obtained as a
major product along with α-SCF3 substituted ketone (3y, 21%).
Table 1. Copper-mediated decarboxylative trifluoromethylthiolation to form
trifluoromethyl thioethers.[a,b].
[a] Reaction conditions: 1 (1.0 equiv), AgSCF3 (2.0 equiv), CuI (1.0 equiv)
and Ag2CO3 (2.0 equiv), K2S2O8 (2.0 equiv) in CH3CN/HOAc (2:1) at 90 o
C
for 1 h under atmosphere. [b] Isolated yields, the E/Z ratio were determined
by 19F NMR spectroscopy.
Table 2. Iron-mediated decarboxylative trifluoromethylthiolation to form α-
Based on the successful preparation of vinyl trifluoromethyl
thioethers by decarboxylative trifluoromethylthiolation, we turned
SCF3 substituted ketones.[a,b].
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Scheme 2. Isotope-labeling experiments under the standard conditions.
On the basis of these observations and previous
reports,8,9,28 a plausible mechanism is proposed (Scheme 3).
Initially, the oxidation of AgSCF3 by peroxydisulfuric acid salt
affords Ag(II)SCF3 species, which triggers the F3CS radical after
the following single electron transfer course. Reaction of the
cinnamic acid with Cu(I) or Fe(II) would produce a salt of B. The
addition of F3CS radical to B generates the corresponding alkyl
radical intermediate C. Single electron transfer of C with Ag(II) to
form the key intermediate D, which underwent elimination to
afford vinyl trifluoromethyl thioethers 2. The carbon cation
intermediate
intermediate E in the presence of water. E was then oxidized by
O2 to produce and byproduct aldehyde. Finally,
D
will quickly transformed into hydroxyl
F
decarboxylation of F leads to the desired α-SCF3 ketones.
Fe(OAc)2 and CuI are likely to assist the elimination of CO2.
[a] Reaction conditions: 1 (2.0 equiv), AgSCF3 (1.0 equiv), Fe(OAc)2 (1.0
equiv), Ag2SO4 (2.0 equiv), Na2S2O8 (2.0 equiv), O2 (balloon) in
CH3CN/H2O (2:1) at 50 oC for 18 h. [b] Isolated yields.
In order to understand the reaction mechanism, the radical
trapping and isotope-labeling experiments were carried out.
When 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) or 2,6-di-
tert-butyl-4-methylphenol (BHT) as radical scavenger was added
to the reaction systems, the iron/copper mediated
decarboxylative trifluoromethylthiolation between cinnamic acid
and AgSCF3 were both totally suppressed, suggesting that these
transformation might proceed via a radical process (see ESI).
Molecular oxygen is essential to the formation of α-SCF3
substituted ketones. When the reaction was carried out under an
argon atmosphere, the corresponding α-SCF3 substituted ketone
3a was not obtained, indicating that the formation of α-SCF3
substituted ketones required the presence of oxygen. In an
attempt to gain close insights into the origin of the oxygen in the
newly formed carbonyl group of α-SCF3-substituted ketones,
isotope labeling experiments were performed by using 18O-
labeled water as a co-solvent instead of normal water. The
content of 18O-labeled product 3a (18O-3a) was increased to
78%, showing that the oxygen atom of carbonyl group in 3a was
from water instead of molecular oxygen (Scheme 2).
Scheme 3. Proposed reaction mechanism.
In conclusion, the decarboxylative trifluoromethylthiolation
of α,β-unsaturated carboxylic acids was achieved. Vinyl
trifluoromethyl thioethers and α-SCF3 substituted ketones can be
selectively synthesized via adjusting the reaction systems with
AgSCF3 as SCF3 source. These reactions have good functional
group compatibilities, and provides novel pathway for the
construction of C-SCF3 bonds. Preliminary mechanism study
revealed that these reactions proceeded via
a
radical
mechanism, and oxygen atoms of carbonyl group of products 3
was found to be derived from water. Further investigation of
these procedures focusing on using alkyl-substituted acrylic
acids as substrates is currently underway in our laboratory.
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Acknowledgements
This work was supported by the National Natural Science
Foundation of China (21421002, 21332010, and 21272036),
National Basic Research Program of China (2012CB21600),
Shanghai Municipal Education Commission (No. 13ZZ047) and
Fundamental Research Funds for the Central Universities
(2232015D3-13). We also gratefully acknowledge the invaluable
discussion with Prof. Dr. Bo Xu.
Keywords: Trifluormethylthiolation • decarboxylation • ketone •
alkene • cinnamic acid
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Chemistry - An Asian Journal
10.1002/asia.201601098
COMMUNICATION
Entry for the Table of Contents
COMMUNICATION
Shen Pan, Yangen Huang,* Feng-Ling
Qing
Page No. – Page No.
Synthesis of trifluoromethylthiolated
alkenes and ketones via
decarboxylative functionalization of
cinnamic acids
The decarboxylative trifluoromethylthiolation of cinnamic acids was achieved. Vinyl
trifluoromethyl thioethers and -SCF3-substituted ketones can be selectively
synthesized via adjusting the reaction systems with AgSCF3 as SCF3 source.
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