Visible-Light photoredox decarboxylation of perfluoroarene iodine(III) Trifluoroacetates for C-H trifluoromethylation of (Hetero)arenes

Article abstract of DOI:10.1021/acscatal.7b03990

A scalable and operationally simple decarboxylative trifluoromethylation of (hetero)arenes with easily accessible C₆F₅I(OCOCF₃)₂ under photoredox catalysis has been developed. This method is tolerant of various (hetero)arenes and functional groups. Notably, C₆F₅I is recycled from the decarboxylation reaction and further used for the preparation of C₆F₅I(OCOCF₃)₂. The combination of photoredox catalysis and hypervalent iodine reagent provides a practical approach for the application of trifluoroacetic acid in trifluoromethylation reactions.

Full text of DOI:10.1021/acscatal.7b03990

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Letter
Visible-Light Photoredox Decarboxylation of Perfluoroarene Iodine(III)
Trifluoroacetates for C–H Trifluoromethylation of (Hetero)arenes
Bin Yang, Donghai Yu, Xiu-Hua Xu, and Feng-Ling Qing
ACS Catal., Just Accepted Manuscript • DOI: 10.1021/acscatal.7b03990 • Publication Date (Web): 01 Mar 2018
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Visible-Light Photoredox Decarboxylation of Perfluoroarene
Iodine(III) Trifluoroacetates for C–H Trifluoromethylation of
(Hetero)arenes
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Bin Yang,† Donghai Yu,‡ Xiu-Hua Xu,† and Feng-Ling Qing†,§,
*
†Key Laboratory of Organofluorine Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of
Organic Chemistry, Chinese Academy of Science, 345 Lingling Lu, Shanghai 200032, China
§College of Chemistry, Chemical Engineering and Biotechnology, Donghua University, 2999 North Renmin Lu,
Shanghai 201620, China
‡Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research (Ministry of Education of China),
College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha, Hunan 410081, China
ABSTRACT: A scalable and operationally simple decarboxylative trifluromethylation of (hetero)arenes with easily acces-
sible C6F5I(OCOCF3)2 under photoredox catalysis has been developed. This method is tolerant of various (hetero)arenes
and functional groups. Notably, C6F5I is recycled from the decarboxylation reaction and further used for the preparation
of C6F5I(OCOCF3)2. The combination of photoredox catalysis and hypervalent iodine reagent provides a practical ap-
proach for the application of trifluoroacetic acid in trifluoromethylation reactions.
KEYWORDS: trifluoromethylation, photocatalysis, decarboxylation, trifluoroacetic acid, iodine(III) reagent
The trifluoromethylated compounds have found wide
applications in materials, pharmaceuticals, and agro-
chemicals.1 Over the last decade, tremendous methods
have been developed for the incorporation of trifluorome-
thyl group into organic molecules,2 using electrophilic,3
nucleophilic,4 and radical5 trifluoromethylating reagents.
Nonetheless, some of the trifluoromethylating reagents
employed in these reactions2-5 are cost-prohibitive or gas-
eous, which limits their application on a large scale. Con-
sequently, the development of new trifluoromethylation
reactions with inexpensive and easily handled CF3 sources
is highly desirable.
scalable trifluoromethylation of aryl halides with
CF3CO2K.10a Zhang and co-workers reported a radical
Because of low cost and the ease of handling,6 trifluoro-
acetic acid (TFA) and its derivatives represent as attrac-
tive trifluoromethylating reagents. The decarboxylative
trifluoromethylation of TFA and trifluoroacetates has
been extensively studied.7-10 However, the decarboxylative
reactions normally require the electrochemical methods,7
stoichiometric transition-metals and high temperature,8
or strong oxidants9 (Scheme 1a). Recently, new advance-
ments have been reported to make the decarboxylative
trifluoromethylation more generally applicable. For ex-
ample, Buchwald demonstrated that the application of
continuous flow technology could enable the rapid and
Scheme 1. Trifluromethylation Reactions Using TFA
and Its Derivatives
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trifluoromethylation of arenes with TFA under the condi-
tion reactions. Importantly, the reactivity and selectivity
might be controlled by judicious choice of proper HIRs
and PCs.
o
tions of Ag2CO3/K2S2O8 at 120 C.10b Very recently, Su and
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Li realized a novel photocatalytic C–H trifluoromethyla-
tion of (hetero)arenes with TFA using a Rh-modified TiO2
nanoparticles as a photocatalyst.10c However, these modi-
fications could not fundamentally solve the problems,
such as high temperature10a,b or strong oxidants.10b,c In
1990, Yoshida and co-workers disclosed an alternative
decarboxylative trifluoromethylation of aromatic com-
pounds with bis(trifluoroacetyl) peroxide under mild
conditions (Scheme 1b).11a This decarboxylative strategy
has recently been adopted by Bräse11b and Sodeoka11c for
radical trifluoromethylation of arenes and alkenes using
the reagent combination of trifluoroacetic anhydride
(TFAA)/urea–hydrogen peroxide (UHP). A significant
breakthrough of decarboxylative trifluoromethylation of
trifluoroacetic acid (TFA) and its derivatives was made by
Stephenson and co-workers.12 They demonstrated that the
pyridine N-oxide/TFAA adduct was used to promote a
high-yield and scalable trifluoromethylation reaction un-
der photoredox catalysis (Scheme 1c). Despite the above
achievements, the development of new trifluoromethyla-
tion reactions with TFA derivatives is still highly desirable.
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Scheme 2. Decarboxylative Trifluoromethylation
with Hypervalent Iodine Trifluoroacetates
To test our hypothesis, 1,4-dichlorobenzene (1a) was
chosen as the model substrate to react with
C6H5I(OCOCF3)2 (PIFA) in the presence of Ru(bpz)3(PF6)2
in CH3CN under blue light-emitting diodes (LEDs). To
our disappointment, no trifluoromethylated product was
detected (Table 1, entry 1). Considering the fact that in-
troduction of fluorine atom(s) or trifluoromethyl group
into the aromatic ring of HIRs can distinctly increase
their oxidizability and solubility,19 we then examined a
series of fluorinated ArI(OCOCF3)2 (entries 2-5). To our
delight, the desired reaction occurred using fluorinated
HIRs, and C6F5I(OCOCF3)2 (FPIFA) was optimal to give
the desired product 2a in 42% yield (entry 5). Switching
Ru(bpz)3(PF6)2 to other PCs showed that Ru(bpy)3(PF6)2
gave the highest yield (entries 6-9). When this reaction
was performed in DMF or DCM, no desired product was
formed (entries 10 and 11). Furthermore, the addition of
base, such as CF3COONa or KF, had no or little effect on
the yield (entries 12 and 13). Finally, decreasing the
amount of FPIFA to 2.5 equivalents resulted in a compa-
rable yield (entry 14). The control experiments showed
that the blue LEDs irradiation was required for this reac-
tion (entry 15). 2a was formed in low yield in the absence
of a PC (entry 16), which is consistent with Marouka’s
work.16b,20
Hypervalent iodine(III) reagents (HIRs) are widely used
in organic synthesis because of their low toxicity, strong
electrophilicity, and valuable oxidizing properties.13 Re-
cently, hypervalent iodine(III) carboxylates have evolved
as powerful reagents to participate in the decarboxylative
alkylation, alkenylation, and acylation under transition-
metal catalysis14 or visible-light photoredox catalysis.15
However, the decarboxylative trifluoromethylation with
hypervalent iodine(III) trifluoroacetates (HITFAs) is
largely ignored and remains to be a challenge. In 1991,
Togo and Yokoyama reported a decarboxylative alkylation
of heteroaromatic bases with carboxylic acids in the pres-
ence of HITFAs.16a This work clearly demonstrated that
the decarboxylation of HITFAs for the formation of a CF3
racial was much harder than that of the nonfluorinated
HIRs. Very recently, Maruoka described a photolytically
induced C−H difluoromethylation of heteroarenes with
hypervalent iodine(III) difluoroacetates, but the decar-
Table 1. Optimization of Reaction Conditionsa
boxylative
trifluoromethylation
with
3,5-(t-
Bu)2C6H3I(OCOCF3)2 was relatively inefficient.16b In con-
tinuation of our research interest in visible-light-induced
fluoroalkylation reactions,17 we herein disclose a scalable
and operationally simple decarboxylative trifluromethyla-
tion of (hetero)arenes with the commercially available
C6F5I(OCOCF3)2 under photoredox catalysis (Scheme 1d).
This HIR is easily accessible from C6F5I and TFA in the
presence of Oxone,18 and C6F5I could be recycled from the
decarboxylation reaction.
yield (%)b 2a-
mono/2a-di
0/0
entry photocatalyst
ArI(OCOCF3)2 slovent
1
Ru(bpz)3(PF6)2
Ru(bpz)3(PF6)2
Ru(bpz)3(PF6)2
Ru(bpz)3(PF6)2
Ru(bpz)3(PF6)2
Ru(bpm)3Cl2
PIFA
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
On the basis of visible-light-induced decarboxylation
reactions15 and our experience in decarboxylative hy-
droaryldifluoromethylation,17d we proposed a photoredox
catalytic cycle for decarboxylative trifluoromethylation.
As shown in Scheme 2, we assumed that photoredox cata-
lyst (PC) involved single electron transfer (SET) appro
aches could provide the CF3 radial (via radical intermedi-
ates A and B), which could be used for trifluoromethyla-
2
3
4
5
6
7
HIR-1
HIR-2
HIR-3
FPIFA
FPIFA
FPIFA
11/0
23/0
16/0
42/trace
51/3
Ru(bpy)3(PF6)2
60/12
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Ir(ppy)3
FPIFA
FPIFA
FPIFA
FPIFA
FPIFA
FPIFA
FPIFA
FPIFA
FPIFA
CH3CN
CH3CN
DMF
31/0
29/0
0/0
1
2
3
4
5
6
7
8
Ir(Fppy)3
10 Ru(bpy)3(PF6)2
11 Ru(bpy)3(PF6)2
12c Ru(bpy)3(PF6)2
13d Ru(bpy)3(PF6)2
14e Ru(bpy)3(PF6)2
15f Ru(bpy)3(PF6)2
DCM
0/0
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
60/12
62/13
62/15
0/0
16
8/0
─
aReaction conditions: 1a (0.1 mmol), ArI(OCOCF3)2 (0.3
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mmol), photocatalyst (0.002 mmol), solvent (1.5 mL), blue
LEDs, under N2, 35 °C, 12 h. bYields determined by 19F NMR
using trifluoromethoxybenzene as an internal standard.
cCF3COONa (0.1 mmol). dKF (0.1 mmol). eFPIFA (0.25 mmol).
fNo light.
With the optimized reaction conditions in hand (Table
1, entry 14), the scope of this photoredox-catalyzed decar-
boxylative trifluoromethylation was investigated (Scheme
3). Various monosubstituted or disubstituted arenes bear-
ing different functional groups such as halogen, acetyl,
ester, tert-butyl, and nitrile underwent this reaction to
afford the corresponding products in moderate to good
yields (2a-2n). In some cases the trifluoromethylated
products were obtained as mixture of isomers, which is
consistent with the general radical trifluoromethylation of
arenes.5a,10b,10c Moreover, 1,3,5-tricyanobenzene 1o was
smoothly converted to the corresponding trifluorometh-
ylated products (2o). The extension of this decarboxyla-
tive trifluoromethylation to heteroarenes was delightfully
successful. Electro-rich heteroarenes including furans and
thiophenes (1p-1s) were compatible with the reaction
conditions. Meanwhile, electron-deficient heteroarenes
(pyridines, pyrimidines, pyrazines, and thizaoles, 1t-1ab)
were also amenable to the reaction. Notably, the trifluo-
romethylation of these heteroarenes exhibited excellent
site-selectivity at the electro-richer position (2t-2ab). Un-
fortunately, pyrroles and benzopyrroles were not visible
for this protocol. In the case of quinoxalines (1ac and 1ad),
the trifluoromethylation took place at the C-5 position or
both C-5 and C-8 positions (2ac and 2ad), whereas the
trifluoromethylation occurred at the C-5 or C-6 position
in Baran’s CF3SO2Na/t-BuOOH system.5b The structure of
compounds 2aa, 2ab-b, and 2ac-di were confirmed by X-
ray analysis (see the supporting information).21 Finally, we
extended the substrate scope to styrenes. Treatment of
styrenes (1ae-1ag) with FPIFA (1.1 equiv) under the stand-
ard reaction conditions afforded the aminotrifluorometh-
ylated products (2ae-2ag) in moderate to good yields.22
Scheme 3. Substrate Scope of Decarboxylative Tri-
fluoromethylation with FPIFAa
aReaction conditions: 1 (0.5 mmol), FPIFA (1.25 mmol),
Ru(bpy)3(PF6)2 (0.01 mmol), CH3CN (7.5 mL), blue LEDs, 35
°C, under N2, 12 h, isolated yields. The isomer ratio was
determined by 19F NMR using trifluoromethoxybenzene as an
b
internal standard. Yields determined by 19F NMR using tri-
c
fluoromethoxybenzene as an internal standard. FPIFA (0.55
mmol).
To extend the application of this reaction, we then ex-
amined the analogous fluoroalkylation reactions with
HIRs. Several C6F5I(OCORf)2 (HIR-4/5/6) were synthe-
sized23 and subjected to the C–H fluoroalkylation of (het-
ero)arenes. To our delight, these reactions proceeded
smoothly under the standard conditions, resulting in the
pentafluoroethylated, heptafluoropropylated, and difluo-
romethylated products (2ah-2al) in moderate yields
(Scheme 4). Unlike the trifluoromethylation reactions,
perfluoroalkylation reactions only afforded monosubsti-
tuted products, probably owing to the higher electronega-
tivity of perfluoroalkyl group.24
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ing information) affords Ru(bpy)33+ and the iodanyl radi-
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cal A. The Stern-Volmer fluorescence quenching studies
confirmed that FPIFA could quench *Ru(bpy)3 effective-
2+
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ly (Figure 1). Subsequently, intermediate A undergoes a
homolytic scission of the I-O bond to generate pen-
tafluoroiodobenzene and a trifluoroacetoxy radical B. In
this step, the difference of the calculated I-O bond homo-
lytic dissociation enthalpy between intermediates A and
A’ (Scheme 7) reveals that the radical intermediate A’
from PIFA is harder to proceed a homolytic scission,
which partly interprets why PIFA could not undergo the
decarboxylative trifluoromethylation reaction (Table 1,
entry 1). The resulting radical B extrudes CO2 to generate
the CF3 radical, which is then added to arenes 1 for the
formation of intermediate D. Radical D might be oxidized
by Ru(bpy)33+ (path a) and/or FPIFA (path b) to afford the
corresponding cation E. Finally, intermediate E undergoes
deprotonation or nucleophilic attack to give the desired
products 2.
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Scheme 4. Substrate Scope of Decarboxylative Per-
fluoroalkylation Reactiona
aReaction conditions: 1 (0.5 mmol), C6F5I(OCORf)2 (1.25
mmol), Ru(bpy)3(PF6)2 (0.01 mmol), CH3CN (7.5 mL), blue
LEDs, 35 °C, under N2, 12 h, isolated yields. bYields deter-
mined by 19F NMR using trifluoromethoxybenzene as an in-
ternal standard.
To demonstrate the scalability of the present photo-
catalytic reaction, the decarboxylative trifluoromethyla-
tion of 1v with FPIFA was carried out on a 10.0 mmol scale
(Scheme 5). The desired product 2v was isolated in 63%
yield (1.3 g), which was slightly inferior to the correspond-
ing reaction presented in Scheme 3. Simultaneously, pen-
tafluoroiodobenzene was recycled in 78% yield (5.7 g) and
could be used for the preparation of FPIFA (see the sup-
porting information).
Figure 1. Ru(bpy)3(PF6)2 Emission Quenching with
FPIFA and 1a.
Scheme 5. A Gram-Scale Decarboxylative Trifluoro-
methylation Reaction
Scheme 7. DFT-Calculated I-O Bond Dissociation En-
thalpy for Intermediates A and A’ in CH3CN
(M062X/6-311++G**)
To compare the current photoredox catalysis decarbox-
ylation trifluoromethylation protocol with Maruoka’s
photolysis difluoromethylation without photocatalyst,16b
the DFT calculations of the I-O bond dissociation enthal-
py of PFIPA and 3,5-(t-Bu)2C6H3I(OCOCF2H)2 (HIR-7)16b
were conducted. As shown in Scheme 8, the calculated I-
O bond homolytic dissociation enthalpy of FPIFA (ΔH =
51.0 Kcal/mol) is much higher than that of CF2H-
containing HIR-7 (ΔH = 28.5 Kcal/mol). These results
explain why a photocatalyst was required for the for-
mation of intermediate A from FPIFA (Scheme 6).
Scheme 6. Proposed Reaction Mechanism
On the basis of the results in Table 1 as well as previous
reports,15,17d a plausible reaction mechanism is proposed in
Scheme 6. First, irradiation of Ru(bpy)32+ with visible light
gives the excited-state *Ru(bpy)32+. Then, SET oxidation of
*Ru(bpy)32+ [E1/2(RuII*/RuIII) = -0.81 V vs SCE in CH3CN]25
by FPIFA (Epc = -0.08 V vs SCE in CH3CN, see the support-
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Scheme 8. DFT-Calculated I-O Bond Dissociation En-
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311++G**)
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In conclusion, we have developed a practical visible-
light-induced decarboxylative trifluoromethylation of
(hetero)arenes using the easily accessible FPIFA as the
trifluoromethylating reagent. This method is tolerant of
various (hetero)arenes and functional groups. The com-
bination of photoredox catalysis and HIRs provides a
practical approach for the application of TFA as a trifluo-
romethyl source.
AUTHOR INFORMATION
Corresponding Author
flq@mail.sioc.ac.cn
Notes
The authors declare no competing financial interest.
ASSOCIATED CONTENT
Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: XXX
Detailed experimental procedures, characterization data,
mechanistic study data, copies of 1H, 19F and 13C NMR spectra,
and X-ray crystal structure of 2aa, 2ab-b, 2ab-di.
ACKNOWLEDGMENT
National Natural Science Foundation of China (21421002,
21332010), Strategic Priority Research Program of the Chinese
Academy of Sciences (XDB20000000), and Youth Innovation
Promotion Association CAS (No. 2016234) are greatly
acknowledged for funding this work.
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