Electrochemical Decarboxylative Trifluoromethylation of α, β-Unsaturated Carboxylic Acids with CF3SO2Na

Article abstract of DOI:10.1002/cctc.201900438

A new method for the synthesis of vinyl trifluoromethyl compounds from α, β-unsaturated carboxylic acids and CF₃SO₂Na has been developed. This electrochemical decarboxylative trifluoro-methylation was found to be highly stereoselective and afforded products in good yields with wide substrate scope under metal-free and external chemical oxidant-free conditions.

Full text of DOI:10.1002/cctc.201900438

Accepted Article
Title: Electrochemical Decarboxylative Trifluoromethylation of α, β-
Unsaturated Carboxylic Acids with CF3SO2Na
Authors: Fang-Yuan Li, Dian-Zhao Lin, Tian-Jun He, Wei-Qiang Zhong,
and Jing-Mei Huang
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10.1002/cctc.201900438
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Electrochemical Decarboxylative Trifluoromethylation of α, β-
Unsaturated Carboxylic Acids with CF3SO2Na
Fang-Yuan Li[a], Dian-Zhao Lin[a], Tian-Jun He[a], Wei-Qiang Zhong[a] and Jing-Mei Huang*[a]
Abstract: A new method for the synthesis of vinyl trifluoromethyl
compounds from α, β-unsaturated carboxylic acids and CF3SO2Na
has been developed. This electrochemical decarboxylative trifluoro-
methylation was found to be highly stereoselective and afforded
products in good yields with wide substrate scope under metal-free
and external chemical oxidant-free conditions.
under electrochemical conditions in 2014 .[10] Further, the works
on trifluoromethylative difunctionallization of alkenes by
electrolysis of CF3SO2Na were disclosed by Cantillo,[11] Lin,[12]
Lei,[13] Xu,[14] Pan,[15] and Kim,[16] respectively. Meanwhile, the
electrochemical trifluoromethyl/cyclization of N-arylacrylamides
with CF3SO2Na have also been demonstrated by Zeng, [17] Mo, [18]
and Ackermann, [19] respectively.
Nowadays, decarboxylative cross-coupling reactions have
emerged as an attractive approach for the construction of
carbon−carbon bonds.[20] The decarboxylative cross-coupling of
vinyl carboxylic acids with the Langlois reagent is envisioned as a
promising process for the construction of Cvinyl-CF3 bonds. In 2013,
Maiti’s group[21] reported a decarboxylative trifluoromethylation of
cinnamic acids with Langlois reagent in the presence of FeCl3 and
K2S2O8. Meanwhile, copper/silver-catalyzed or copper-catalyzed
decarboxylative trifluoromethylation reaction using TBHP as an
oxidant was disclosed by Duan[22] and Liu,[23] respectively. Later,
I2O5-treated Cvinyl-CF3 bonds construction was demonstrated by
Liu and his co-workers[24] in 2014. It is noticed that all the reported
methods had employed excess equivalents of oxidants, and
heating was necessary to furnish the reaction. Therefore, the
development of an environmentally benign method under the
metal-free, external chemical oxidant-free conditions for this
transformation is highly desirable.
Introduction
The incorporation of trifluoromethyl（CF3）moiety into organic
molecules can dramatically influence the latter's characteristics,
owing to the unique properties of the trifluoromethyl group, such
as the electronic properties, special size, lipophilicity, and metab-
olic stability.[1] As a consequence, CF3-containing compounds
widely exist in pharmaceuticals, agrochemicals, and materials.[2]
Great synthetic interest has been devoted to developing efficient
methods for the introduction of the CF3 group into organic
substrates. However, for the construction of Csp2-CF3 bonds,
especially for the Cvinyl-CF3 bonds,[3] fewer approaches are
available compared with a variety of processes for the construc-
tion of Csp3-CF3 bonds. In addition, several CF3 sources, for
instance, Togni reagent,[4] Umemoto reagent,[5] Ruppert−Prakash
reagent,[6] and the trifluoromethyl sulfinates (e.g. Langlois /Baran
reagent),[7] have been explored for trifluoromethylation process.
Due to their stabilities and commercial availabilities on a large
scale, the trifluoromethyl sulfinates have been proved to be ideal
trifluoromethyl donors for the protocol.
In the past decade, electrochemistry has experienced a
26]
renaissance in the synthetic chemistry.[25,
However, the
research reports on electrochemical decarboxylation cross-
coupling of vinyl carboxylic acids to form new compounds are
limited.[27] To the best of our knowledge, the electrochemical
trifluoromethylation through decarboxylative cross-coupling of
vinyl carboxylic acids and CF3SO2Na to form a new Cvinyl-CF3
Countless methods have been applied to oxidize the
trifluoromethyl sulfinates (CF3SO2M) to release trifluoromethyl
radical (•CF3).[8] In particular, the application of the
electrochemical technology to initiate trifluoromethyl radical is
appealing due to its green and controllable characteristics. In
2002, Tommasino’s group introduced their work on the
trifluoromethylation of electron-rich aromatics and alkenes via
electrochemical technology.[9] In this study, CF3 radical was
generated from the anodic oxidation of CF3SO2K. Subsequently,
Baran's group chose Zn(SO2CF3)2 as a source of trifluoromethyl
radical and accomplished the trifluoromethylation of heteroarenes
bond is still unknown. Based on our previous works in the organic
28]
electrochemistry,[27b,
herein we report the first efficient
electrochemical decarboxylative trifluoromethylation of cinnamic
acids with the Langlois reagent.
Results and Discussion
To start our investigation, p-methoxycinnamic acid (1a) and
CF3SO2Na (2) were chosen as model substrates. Under constant
current at 5 mA and using LiClO4 as supporting electrolyte in an
undivided cell, the reaction of 1a and 2 afforded 81% yield of the
desired product 3a (Table 1, entry 1). In the absence of
trifluoroethanol (TFE) or increase the amount of TFE to one
equivalent in the reaction, a decreased yield was obtained (entries
2 and 3). Meanwhile, other additives, such as pivalic acid (PA),
K2CO3, and NaHCO3, gave the corresponding products in slightly
[a]
F.-Y. Li, D.-Z. Lin, T.-J. He, W.-Q. Wei, and Prof. Dr. J.-M. Huang
Key Laboratory of Functional Molecular Engineering of Guangdong
Province, School of Chemistry and Chemical Engineering, South
China University of Technology, Wushan, Tianhe, Guangzhou,
510640, P. R. CHINA, Email: chehjm@scut.edu.cn.
Supporting information for this article is given via a link at the end of the
document.
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10.1002/cctc.201900438
ChemCatChem
FULL PAPER
decreased yield (entries 4 and 5), while quite a similar yield was
produced with HOAc as a reaction additive (entry 4). The yield
decreased sharply to 16% in the absence of H2O, as the solubility
of sodium trifluoromethanesulfinate that is crucial for the reaction
conversion is decreased (entry 6). Change of the proportion of
H2O and 1,2-dimethoxyethane (DME) disfavored this protocol
(entries 7 and 8). The studies on the effect of solvent revealed
that the yield of the product decreased sharply when DMSO or
MeCN was used to replace DME (entries 9 and 10), while MeOH
disfavored this reaction (entry 11). Only a slight decrease in the
yield was observed in the solution of the mixture of THF and H2O
(entry 12). When a series of electrolytes (entries 13-16) were
examined, it was found that the LiClO4 was optimal for this
transformation. Next, the effect of the electrode material was
demonstrated. A comparable yield was obtained by replacing the
carbon felt anode with carbon rod anode (entry 17), while a trace
amount of target product was collected with the usage of platinum
plate anode (entry 18). Both Ni foam cathode and carbon felt
cathode showed lower reaction reactivity than the platinum plate
cathode (entries 19 and 20). In the end, the endeavors to increase
or decrease the operating current, such as 3 mA or 10 mA,
caused a decrease in the product yield (entries 21 and 22).
Predictably, no desired product could be detected without an
electric current (entry 23).
[a] Reaction conditions: 1a (0.2 mmol), 2 (0.6 mmol), DME/H2O (v/v = 4/1,
5 mL), TFE (0.1 mmol), 0.1 M LiClO4 as supporting electrolyte, anode:
carbon felt (1 × 1.5 cm2), cathode: Pt foil (1 × 1.5 cm2), constant current (5
mA), undivided cell, room temperature, 8 h. TFE = Trifluoroethanol, DME
= 1,2-dimethoxyethane. [b] Yield determined by 1H NMR analysis using
CH3NO2 as the internal standard, N.R. = no reaction. [c] Pivalic acid = PA.
[d] Graphite rod (diameter: 0.5cm, height: 1.5 cm). [e] Platinum plate (1 ×
1.5 cm2). [f] Ni foam electrode (0.01 x 1 × 1.5 cm3).
With the optimized conditions in hand, we proceeded to
investigate the substrate generality and limitation of our reaction.
As shown in Table 2, the reactions of a series of α, β-unsaturated
carboxylic acids with CF3SO2Na proceeded smoothly and the
desired products were obtained in moderate to good yields in
most cases. For substrates bearing electron-donating groups on
the aryl ring, such as OMe, 3,4-(-OCH2O-), OC(=O)CH3, and CH3,
this coupling reaction worked well to give the corresponding Prod-
ucts in the yields of 52-82% (3a-3h). A decrease in the yield was
observed for the substrate bearing a m/o-OMe or m/o-CH3
substituent compared to the substrate bearing a p-OMe or p-CH3
substituent on the aryl ring, which implied that the steric effect has
an influence on this protocol. It is found that halogen substituents
could be well tolerated under the electrochemical conditions (3i-
3l), which provides the opportunity for further derivatizations of
the products. Meanwhile, cinnamic acids with electron with-
drawing groups (COOH, CN, CF3) on the phenyl ring were still
suitable for this process and gained desired products in moderate
yields (3m-3p).It was noteworthy that the substrate with p-CHO
on the aromatic ring could avoid excessive oxidation under the
electrochemical conditions and provided the desired product in
48% of yield (3q). However, only a trace amount of the desired
product for the substrate containing NO2 group could be detected
in the reaction (3r), which was rationalized by the reduction of the
nitro group on the cathode. In addition, nitrogen- and sulfur-
containing heterocyclic analogues gave desired products in the
yields of 43% (3s) and 53% (3t), respectively. Finally, the 1.2
mmol-scale reaction was implemented. When the reaction with 1e
(1.2 mmol) was carried out, the corresponding product 3e was
collected in the yield of 70% (see the Supporting Information for
details). Notably, the trifluoromethylation reaction was also found
to be highly stereoselective, and in most cases, the E/Z ratios of
the CF3-functionalized alkenes were determined as 99:1 or even
higher.
Table 1. Optimization of the Reaction Conditions[a]
Entry
1
Variation from the standard conditions
none
Yield(%)[b]
81
2
in the absence of TFE
TFE (1.0 equiv)
63
3
68
4[c]
PA or HOAc instead of TFE
NaHCO3 or K2CO3 instead of TFE
without H2O
64 or 80
58 or 46
16
5
6
7
DME/H2O (v/v, 5/1)
54
8
DME/H2O (v/v, 3/1)
66
9
DMSO instead of DME
MeCN instead of DME
MeOH instead of DME
THF instead of DME
n-Bu4NClO4 instead of LiClO4
NaClO4 instead of LiClO4
n-Bu4NBF4 instead of LiClO4
NH4BF4 instead of LiClO4
graphite rod anode
34
10
11
12
13
14
15
16
17[d]
18[e]
19[f]
20
21
22
23
43
trace
72
52
69
In an attempt to understand the reaction mechanism, some
control experiments were carried out (Scheme 1). First, with the
addition of a radical scavenger, 2,2,6,6-tetramethylpiperidine-1-
oxyl (TEMPO), 1,1-diphenylethene or 2,6-di-tert-butyl-4-methyl-
phenol (BHT) (Scheme 1, eq 1 and eq 2), only a trace amount of
desired product was obtained, indicating the reaction presumably
involved a radical pathway. To our delight, in the reaction with
BHT (Scheme 1, eq 2) as a radical scavenger, the BHT−CF3
adduct was detected by GC-MS (see the Supporting Information
for details), which implied that CF3 radical intermediate was prod-
52
56
77
platinum plate anode
Ni foam cathode
trace
58
carbon felt cathode
43
10 mA instead of 5 mA, 4 h
2.5 mA instead of 5 mA, 16 h
no electric current
56
62
N.R.
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10.1002/cctc.201900438
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Table 2. Substrate Scope of α, β-Unsaturated Carboxylic Acids [a]
V vs SCE, while the oxidation peak of the cinnamic acid 1a was
observed at 1.32 V vs SCE. These results indicated that
CF3SO2Na might be oxidized by anode before 1a to produce a
CF3 radical.
Scheme 1. Control Experiments
[a] Reaction conditions: 1 (0.2 mmol), 2 (0.6 mmol), DME/H2O (v/v = 4/1, 5
mL), TFE (0.1 mmol), 0.1 M LiClO4 as supporting electrolyte, anode: carbon
felt (1 × 1.5 cm2), cathode: Pt foil (1 × 1.5 cm2), constant current (5 mA),
undivided cell, room temperature, isolated yield. [b] Reaction time,
indicated by TLC. [c] Ratio of E/Z was determined by 19F NMR and 1H NMR
of the crude product mixture. [d] THF instead of DME, NH4BF4 instead of
LiClO4.
Figure 1. Cyclic voltammograms of 0.1 M LiClO4 solution in DME/H2O (v/v, 4:1),
at room temperature. (a) none; (b) sodium trifluoromethanesulfinate (0.005 M);
(c) p-methoxycinnamic acid (0.005 M). The voltammogram was obtained with
Pt wire as auxiliary electrode and a saturated calomel electrode (SCE) as a
reference electrode. The scan rate was 0.1 V/s on a platinum disk electrode (d
= 2 mm).
uced in this transformation. Meanwhile, when p-methoxy-styrene
took the place of p-methoxycinnamic acid as the coupling partner
under the standard conditions (Scheme 1, eq 3), no desired
product was produced, suggesting that p-methoxystyrene was not
the reaction intermediate. Moreover, when methyl-4-methoxy-
cinnamate and 2 were subjected to this protocol, (Scheme 1, eq
4), the expected product was not detected, which demonstrated
that the carboxylic group was necessary for the reaction. Cyclic
voltammetry (CV) experiments were also implemented. As shown
in Figure 1, the oxidation peak of CF3SO2Na was observed at 0.98
Based on the mechanistic investigations above and the prece-
dent reports,[10,
a plausible radical-based pathway for this
27a]
process is proposed, as depicted in Scheme 2. The intermediate
A is generated by the oxidation of sodium trifluoromethane-
sulfinate on the anodic electrode and goes through rapid cleavage
to form the fluoroalkyl radical B. Subsequently, this highly active
radical B reacts with 1a to give the radical species C, which is
easy to be decarboxylated to furnish the desired product 3a under
the reaction conditions.
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Scheme 2. Proposed Reaction Mechanism
Conclusions
In summary, an electrochemical decarboxylative trifluoromethyl-
lation of cinnamic acids with the Langlois reagent to synthesize
vinyl trifluoromethyl compounds has been developed. With a wide
substrate scope and an excellent functional-group tolerance, this
protocol proceeds smoothly under ambient conditions and refra-
ins from using any metal and chemical oxidants. Mechanism
insights reveal that this reaction goes through a radical pathway.
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Into a round bottom flask, p-methoxycinnamic acid 1a (0.2 mmol, 1.0
equiv), Langlois reagent 2 (0.6 mmol, 3.0 equiv), and trifluoroethanol (TFE)
(0.1 mmol, 0.5 equiv) were dissolved in 5 mL 1,2-dimethoxyethane/H2O
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We are grateful to the National Natural Science Foundation of
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Keywords: decarboxylation • electrochemistry • external
chemical oxidant-free • metal-free• trifluoromethylation
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This article is protected by copyright. All rights reserved.

10.1002/cctc.201900438
ChemCatChem
FULL PAPER
FULL PAPER
Fang-Yuan Li[a], Dian-Zhao Lin[a], Tian-
Jun He[a], Wei-Qiang Zhong[a] and Jing-
Mei Huang*[a]
Page No. – Page No.
Electrochemical Decarboxylative
Trifluoromethylation of α, β-
Unsaturated Carboxylic Acids with
CF3SO2Na
The electrochemical decarboxylative trifluoromethylation of α, β-unsaturated
carboxylic acids with Langlois reagent was disclosed. The reaction refrained from
using metal and external oxidants and afforded the corresponding products in
moderate to good yields with a wide range of functional groups tolerated under
ambient conditions. In most cases, the E/Z ratios of the CF3-functionalized alkenes
were determined as 99:1 or even higher.
This article is protected by copyright. All rights reserved.