Visible-Light-Mediated Metal-Free Synthesis of Trifluoromethylselenolated Arenes

Article abstract of DOI:10.1002/anie.201806165

The first visible-light-mediated synthesis of trifluoromethylselenolated arenes under metal-free conditions is reported. The use of an organic photocatalyst enables the trifluoromethylselenolation of arene diazonium salts using the shelf-stable reagent trifluoromethyl tolueneselenosulfonate at room temperature. The reaction does not require the presence of any additives and shows high functional-group tolerance, covering a very broad range of starting materials. Mechanistic investigations, including EPR spectroscopy, luminescence investigations, and cyclic voltammetry allow rationalization of the reaction mechanism.

Full text of DOI:10.1002/anie.201806165

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Angewandte
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Accepted Article
Title: Visible Light-Mediated Metal-Free Synthesis of
Trifluoromethylselenolated Arenes: Scope and Mechanism
Authors: Clément Ghiazza, Vincent Debrauwer, Cyrille Monnereau,
Lhoussain Khrouz, Maurice Médebielle, Thierry Billard, and
Anis Tlili
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201806165
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10.1002/anie.201806165
Angewandte Chemie International Edition
COMMUNICATION
Visible Light-Mediated Metal-Free Synthesis of
Trifluoromethylselenolated Arenes: Scope and Mechanism
Clément Ghiazza,[a] Vincent Debrauwer,[a] Cyrille Monnereau,[b] Lhoussain Khrouz,[b] Maurice
Médebielle,[a] Thierry Billard* [a, c] and Anis Tlili*[a]
Abstract: The first visible light-mediated synthesis of
trifluoromethylselenolated arenes under metal free conditions is
reported herein. The use of an organic photocatalyst allows the
trifluoromethylselenolation of arene diazonium salts, using the shelf-
stable reagent trifluoromethyl tolueneselenosulfonate, at room
temperature. The reaction does not require the presence of any
additive and shows a large functional group tolerance covering a
very broad scope of starting materials. Mechanistic investigations,
including EPR, fluorescence and cyclic voltammetry allow the
rationalisation of the reaction mechanism.
our group has been active in the development and design of
new reagents for the introduction SeCF3 moiety into organic
substrates.[4e] More recently, we reported the synthesis as well
as use of new shelf-stable reagents for electrophilic
trifluoromethylselenolation,
tolueneselenosulfonate.[7]
namely
trifluoromethyl
With our continuous interest to discover and develop new
synthetic methodologies, we turned our attention to study the
formation of C(sp2)-SeCF3 bonds using the above-mentioned
compound. Regarding the state of the art, the use of nucleophilic
ammonium trifluoromethylselenide is the most studied approach
in conjunction with aryl halides under nickel[8] or palladium[9]
catalysis. Also, arene diazonium salts[10] and arylboronic acids[7b,
The combination of the trifluoromethyl group with chalcogens
has gained widespread interest in modern organofluorine
chemistry. The unique properties resulting from this conjunction
are the key factor for the perpetual and growing interest in life
sciences and materials,[1] as they affect the physicochemical
properties[2], most significantly their lipophilicity.[3]
11]
have been used as starting materials. Finally, discrete σ-
bonded copper-SeCF3 complexes have been employed in
stoichiometric fashion for the trifluoromethylselenolation of aryl
iodides and activated bromides.[12]
From a conceptual standpoint, we questioned whether
organic photoredox catalysis[13] might leverage the orthogonality
of transition-metal-catalyzed C(sp2)-SeCF3 bond formation under
mild reaction conditions.[14] We envisioned the use of arene
diazonium salts that exhibit mild reduction potentials. This class
of substrates can easily be prepared from readily available
anilines. Next, we selected Eosin Y[15] as an organic
photocatalyst, known as a potential reducer for arene diazonium
salts. The first test was performed by mixing the diazonium salt
1a with our shelf-stable reagent I in the presence of 5 mol% of
Eosin Y in DMSO at room temperature under irradiation of a
white led lamp. This initial attempt led to the formation of the
desired product in 77% yield (Table 1, Entry 1). The product was
also formed in DMF as solvent although with a significantly
lowered yield of 42% (Table 1, Entry 2). When THF or ACN were
tested, only traces of the product were formed. Blank reactions
were performed which did not lead to the formation of any traces
of the desired product proving the necessity for both, Eosin Y
and light irradiation in the reaction mechanism (Table 1, Entries
5-7).
Thus, even though efforts have been made for a long time to
incorporate trifluoromethyl-chalcogen groups into organic
molecules, a real renaissance has been seen in the last
decade.[4] Within that framework, reagents development and
design as well as discrete catalyst synthesis were the key points
for such achievements. Indeed, on the one hand, catalysis
allowed encompassing very large panels of fluorinated moieties.
On the other hand, the developed reagents constitute one of the
major toolbox for synthetic organofluorine chemistry. Taking
advantage of those new tools, several research groups
investigated the synthesis of a plethora of different reagents for
the introduction of trifluoromethyl-chalcogen moieties. During
this span, trifluoromethylthiolation reactions have been well
developed,[4d-j] whereas trifluoromethylselenolation reactions are
still underdeveloped although selenolated compounds are
involved in a large panel of applications[5] and could be
considered as one on the most lipophilic group.[6] In this regard,
[a]
C. Ghiazza, V. Debrauwer Dr. M. Médebielle, Dr. T. Billard, Dr. A.
Tlili
With these optimized conditions in hand, we turned our focus
to the scope of the reaction (Scheme 1). The system is tolerant
to electron donating groups and shows that 1a and 1b are
converted to their corresponding trifluoromethylselenolated
product in good to excellent yields (up to 83%). In addition, steric
hindrance is tolerated to a significant extent. Indeed, the
presence of one or two substituents in the ortho position,
including methoxy (1c), methyl (2d) and even SMe substituents
(2e) were tolerated under these conditions. Taking advantage of
the metal free conditions, halogenated derivatives such as
iodine (1f) and fluorine (1g) containing arenes were selectively
converted into their corresponding products in very good to
excellent yields (up to 78%). Electron-deficient arene diazonium
Institute of Chemistry and Biochemistry (ICBMS–UMR CNRS 5246)
Univ Lyon, Université Lyon 1, CNRS, CPE-Lyon, INSA
43 Bd du 11 Novembre 1918, 69622 Villeurbanne, France
E-mail: thierry.billard@univ-lyon1.fr
anis.tlili@univ-lyon1.fr
www.FMI-Lyon.fr
Dr. C. Monnereau, L. Khrouz
Univ Lyon, Ens de Lyon, CNRS UMR 5182, Université Lyon 1,
Laboratoire de Chimie, F-69342, Lyon, France
Dr. T. Billard
[b]
[c]
CERMEP – in vivo imaging
Groupement Hospitalier Est
59 Bd Pinel, 69003 Lyon, France
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10.1002/anie.201806165
Angewandte Chemie International Edition
COMMUNICATION
salts were also tolerated and their corresponding
trifluoromethylselenolated arenes analogues were formed in
very good to excellent yields (up to 83%) including nitro (1i) and
electrophilic functional groups, such as nitrile, ester and ketone
Having successfully demonstrated the versality of our
approach with respect to trifluoromethylselenolation and its
tolerance towards a variety of functional group, we next focused
on extending the methodology to higher homologs. In general,
moieties (1h, 1j, 1k). More interestingly, the presence of acid (1l), moderate to excellent yields were isolated starting from reagents
free hydroxy (2m) as well as amide derivatives (2n and 2o)
underwent selective trifluoromethylselenolation. Finally,
II or III. Substitution reactions follow a similar trend as with
trifluoromethylselenolation (Scheme 2).
a
heterocyclic compounds including thiophene derivative (2p) as
well as quinoline derivatives (2q, 2r) were successfully
transformed.
O
O
Eosin Y (5 mol%)
SeRF
N2 BF4
S
+
SeRF
R
R
DMSO ( 2 mL )
White led, rt, 16h
1
3 RF = CF2CF3
4 RF = CF2CF2CF3
II RF = CF2CF3
III RF = CF2CF2CF3
Table 1. Reaction optimisation
O
O
Eosin Y (5 mol%)
SeCF3
N2 BF4
S
SeCF3
+
SeCF2CF3
DMSO ( 2 mL )
White led, rt, 16h
SeCF2CF3
SeCF2CF3
EtO
HO
1a
I
2a
MeO
O
O
Entry[a]
Deviation from standard conditions
Yield [%] [b]
3b, 38 % (49 %)
3j, 71% (80 %)
3l, 57 % (67 %)
SeCF2CF2CF3
1
2
3
4
5
6
7
None
77
42
<1
<1
0
SeCF2CF3
DMF instead of DMSO
THF instead of DMSO
ACN instead of DMSO
No Eosin Y
N
MeO
3r, 56 %
4b, 42 % (46 %)
No light
0
SeCF2CF2CF3
No light and no Eosin Y
0
SeCF2CF2CF3
EtO
O
[a] Reactions were performed with TsSeCF3 (0.3 mmol,
3
equiv.), arene
HO
diazonium (0.1 mmol, 1 equiv.), Eosin Y (5 mol%), and solvent (1 mL). The
reaction mixture was stirred at rt for 16 hours under inert conditions. [b]
Determined by 19F NMR spectroscopy with PhOCF3 as an internal standard.
O
4j, 56 % (63 %)
4l, 38 % (47 %)
Scheme 2. [a] Reactions were performed with TsSeRF (0.6 mmol, 3 equiv.),
arene diazonium salt (0.3 mmol, 1 equiv.), Eosin Y (5 mol%), and DMSO (2
mL). The reaction mixture was stirred at room temperature for 16 hours under
inert conditions. Yields shown are those of isolated products; yields
determined by 19F NMR spectroscopy with PhOCF3 as internal standard are
shown in parentheses.
O
O
Eosin Y (5 mol%)
SeCF3
N2 BF4
S
SeCF3
+
R
R
DMSO ( 2 mL )
White led, rt, 16h
1
I
2
SeCF3
SeCF3
OMe
SeCF3
SeCF3
We then turned our attention to characterize the reaction
mechanism. Occurrence of a possible electron or energy
transfer process using Stern-Volmer (SV) quenching
experiments between eosin Y and the aryldiazonium species
was first investigated. Although thermodynamically, excited state
of Eosin Y is able to reduce the trifluoromethylselenolating agent
in DMSO (see SI for cyclic voltammetry studies), no changes
were observed regarding the emission at 530 nm.
MeO
2b, 55 %
2a, 67 % (83 %)
2c, 44 % (56 %)
2d, 54 % (59 %)
SMe
SeCF3
SeCF3
SeCF3
SeCF3
I
F
NC
2g, 52 % (78 %) 2h, 70 % (75 %)
2e, 43 % (49 %)
2f, 40 % (65 %)
O
SeCF3
SeCF3
SeCF3
SeCF3
In contrast, we demonstrated that diazonium salts quenched
the luminescence of Eosin Y under the reaction conditions, as
proposed by König[15d] and von Wangelin.[15e] Indeed, a decrease
of the emission was observed at higher concentrations of 1a
(see SI) which at first sight could be fitted with acceptable
correlation with SV fitting model. However, it was found that
quenching was irreversible as it translated into a progressive
decay of eosin absorbance (see SI), thus ascertaining the
EtO
HO
O2N
O
O
O
2i, 77 % (83 %)
2j, 77% (79 %)
2k, 64 % (65 %)
SeCF3
2l, 70 % (77 %)
SeCF3
SeCF3
O
H2N
N
H
HO
O
2m, 69 %
2n, 59 % (65 %)
2o, 59 % (65 %)
occurrence of
experiments conditions. Interestingly, only
a
photobleaching process under the SV
marginal
MeO2C
F3CSe
SeCF3
S
a
N
photobleaching of eosin Y occurred when irradiation was
performed in the absence of de diazonium quencher, in
otherwise similar experimental conditions (see SI). This led us to
the following conclusions that: i) electron transfer occurs from
eosin Y to aryldiazonium, and can be fitted to a dynamic SV
model; ii) this transfer occurs irreversibly and translates into
degradation of the “photocatalyst”.
N
SeCF3
2p, (45 %)
2q, 45 % (46 %)
2r, 48 % (62 %)
Scheme 1. [a] Reactions were performed with TsSeCF3 (0.6 mmol, 3 equiv.),
arene diazonium (0.2 mmol, 1 equiv.), Eosin Y (5 mol%), and DMSO (2 mL).
The reaction mixture was stirred at room temperature for 16 hours under inert
conditions. Yields shown are those of isolated products; yields determined by
19F NMR spectroscopy with PhOCF3 as internal standard are shown in
parentheses.
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10.1002/anie.201806165
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COMMUNICATION
In parallel, we monitored the stability of trifluoromethyl
tolueneselenosulfonate I in solution. We observed that reagent I
in DMSO under light quantitatively furnishes the (CF3Se)2 dimer
within 1 hour. After adding the photocatalyst and the diazonium
salt 1a, we could observe the formation of the desired product in
80 % yield. In turn, the homolysis of S-Se bond under light could
take place. The radical trifluoromethylselenyl dimerizes very
quickly to furnish (CF3Se)2, which could also be considered as
an active reagent for the trifluoromethylselenolation.
were performed including EPR, fluorescence and cyclic
voltammetry. EPR spectroscopy allows us to identify two key
intermediates, the formation of trifluoromethylselenyl radical as
well as a trivalent selenium radical species B. Overall, based on
the different experiments, a plausible mechanism has been
proposed. New methodologies exploiting the formation of
trifluoromethylselenyl radical are under investigations in our
laboratory and will be reported in due course.
In this context, in order to investigate the formation of the
trifluoromethylselenyl radical, we decided to undertake EPR
experiments. We irradiated with green light (λ = 530 nm) a
mixture of trifluoromethyl tolueneselenosulfonate I, Eosin Y and
α-Phenyl-N-tert-Butylnitrone (BPN) as radical trap. The clean
formation of a single spin adduct was obtained, supporting the
formation of trifluoromethylselenyl radical (g=2.003, aN=15.1G
and aH=2.7G). Furthermore, when a mixture of trifluoromethyl
tolueneselenosulfonate I, diazonium salt 1a, Eosin Y, and BPN
as radical trap was irradiated with green light, we observed the
formation of two spin adducts. In addition to the
trifluoromethylselenyl radical, g=2.004, aN=13.6G and aH=1.5G,
this values are slightly shifted due to the different physical
environment of the radicals. A new species was observed
consistant with a trivalent selenium radical species A (Figure 2).
It should be mentioned that the presence of other radical traps
including DMPO (5,5-Dimethyl-1-Pyrroline N-oxide) as well as
MNP (2-Methyl-2-Nitrosopropane) confirms the same tendency
in accordance with the two suggested species, the presence of
trifluoromethylselenyl radical as well as the intermediate trivalent
selenium radical species A (See SI).
Photochemical quantum yields of the reaction were next
investigated, following the methodology depicted in SI. In the
reaction conditions it was determined to be Φ = 1.07. Although
this yield remains close to unity, therefore precluding a strict
discrimination between step-wise reaction and chain
propagation, we however believe, given the observed rapid
photobleaching of eosin
Y in the reaction conditions, as
aforementioned, that it most likely supports a radical chain
process.
Figure 1. EPR spin-traping spectra on irradiation (λ = 530 nm) in the
presence of BPN in DMSO at room temperature. Blue: experimental, red
simulated
In light of the obtained results related to the reaction
mechanism, we could propose the following (Scheme 3): the
diazonium salt is reduced via a SET by the exited Eosin Y. The
formed arene radical could react with the CF3SeSeCF3 dimer
obtained after homolysis of reagent I, furnishing a trivalent
selenium radical B. The intermediate B is then oxidized by the
arene diazonium salt to furnish the electrophilic species C. The
formed intermediate C reacts with DMSO to form the desired
product and adduct D. Interestingly, a signal has been observed
by 19F NMR and could be assigned to the adduct D.
O
O
S
SeCF3
I
hv
F3
C
Se
F3CSe SeCF3
N2
BF4
SeCF3
SET
R
R
R
N
2 BF4
+
B
Eos
BF4
Eos
R
*
SET
hv
CF3
Se
O
Eos
S
SeCF3
SeCF3
In conclusion, we demonstrated that the synthesis of
trifluoromethylselenolated arenes could be mediated with visible
light under metal free conditions. The reactions have been
performed with arene diazonium salts and trifluoromethyl
R
R
BF4
C
SeCF3
O
S
D
BF4
Scheme 3. Proposed mechanism
tolueneselenosulfonate,
temperature. The reaction
unprecedented reactivity. Moreover, mechanistic investigations
a
shelf stable reagent, at room
scope demonstrated an
Experimental Section
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10.1002/anie.201806165
Angewandte Chemie International Edition
COMMUNICATION
To a flame-dried flask under nitrogen atmosphere equipped with a
magnetic stir bar are added I, II or III (0.6 mmol, 3 equiv.), arene
diazonium salt 1 (0.2 mmol, 1.0 equiv.), Eosin Y (0.01 mmol, 5mol%) and
[5]
a) A. Angeli, D. Tanini, C. Viglianisi, L. Panzella, A. Capperucci, S.
Menichetti, C. T. Supuran, Biorg. Med. Chem. 2017, 25, 2518-2523; b)
M. Bodnar, P. Konieczka, J. Namiesnik, J. Environ. Sci. Health, Part C:
Environ. Carcinog. Ecotoxicol. Rev. 2012, 30, 225-252; c) K. M. Brown,
J. R. Arhur, Public Health Nutr. 2001, 4, 593-599; d) A. J. Pacuła, K. B.
Kaczor, A. Wojtowicz, J. Antosiewicz, A. Janecka, A. Długosz, T.
Janecki, J. Ścianowski, Biorg. Med. Chem. 2017, 25, 126-131; e) M. P.
Rayman, Lancet 2000, 356, 233-241; f) L. V. Romashov, V. P.
Ananikov, Chem. Eur. J. 2013, 19, 17640-17660; g) N. Singh, A. L.
Sharpley, U. E. Emir, C. Masaki, M. M. Herzallah, M. A. Gluck, T. Sharp,
C. J. Harmer, S. R. Vasudevan, P. J. Cowen, G. C. Churchill,
Neuropsychopharmacology 2016, 41, 1768-1778; h) L. A. Wessjohann,
A. Schneider, M. Abbas, W. Brandt, Biol. Chem. 2007, 388, 997-1006;
i) F.-h. Cui, J. Chen, Z.-y. Mo, S.-x. Su, Y.-y. Chen, X.-l. Ma, H.-t. Tang,
H.-s. Wang, Y.-m. Pan, Y.-l. Xu, Org. Lett. 2018, 20, 925-929; j) J. B. T.
Rocha, B. C. Piccoli, C. S. Oliveira, ARKIVOC 2017, 457-491; k) Y.
Tang, S. Zhang, Y. Chang, D. Fan, A. D. Agostini, L. Zhang, T. Jiang, J.
Med. Chem. 2018, 61, 2937-2948.
anhydrous dimethyl sulfoxide (2 mL). The reaction is stirred at 25°C
19
under white led irradiation for 16 hours. Conversion is checked by
F
NMR with PhOCF
as internal standard. The reaction mixture is
3
partitioned between Et O and water. The aqueous layer is extracted with
2
Et O and the combined organic layers are dried over MgSO , filtered and
2
4
concentrated to dryness. The crude residue is purified by
chromatography to afford the desired product 2, 3 or 4.
Acknowledgements
C.G. held a doctoral fellowship from la region Rhône Alpes. The
authors are grateful to the CNRS, ICBMS (UMR 5246), ICL
(Institut de Chimie de Lyon) for financial support. The French
Fluorine Network as well as the fédération RENARD and The
Département de Chimie Moléculaire, Université Grenoble Alpes
are also acknowledged for their support.
[6]
[7]
Q. Glenadel, E. Ismalaj, T. Billard, Eur. J. Org. Chem. 2017, 530-533.
a) C. Ghiazza, V. Debrauwer, T. Billard, A. Tlili, Chem. Eur. J. 2018, 24,
97-100; b) Q. Glenadel, C. Ghiazza, A. Tlili, T. Billard, Adv. Synth. Catal.
2017, 359, 3414-3420; c) C. Ghiazza, A. Tlili, T. Billard, Beilstein J. Org.
Chem. 2017, 13, 2626-2630.
[8]
[9]
a) A. B. Dürr, H. C. Fisher, I. Kalvet, K.-N. Truong, F. Schoenebeck,
Angew. Chem. Int. Ed. 2017, 56, 13431-13435; Angew. Chem. 2017,
129, 13616-13620; b) J.-B. Han, T. Dong, D. A. Vicic, C.-P. Zhang, Org.
Lett. 2017, 19, 3919-3922.
Keywords: Visible light • Trifluromethylselenolation • Metal-free
• Radical • Trifluoromethyl tolueneselenosulfonate
M. Aufiero, T. Sperger, A. S. K. Tsang, F. Schoenebeck, Angew. Chem.
Int. Ed. 2015, 54, 10322-10326; Angew. Chem. 2015, 127, 10462-
10466.
[1]
a) M. Hird, Chem. Soc. Rev. 2007, 36, 2070-2095; b) J. Wang, M.
Sánchez-Roselló, J. L. Aceña, C. del Pozo, A. E. Sorochinsky, S.
Fustero, V. A. Soloshonok, H. Liu, Chem. Rev. 2014, 114, 2432-2506;
c) Y. Zhou, J. Wang, Z. Gu, S. Wang, W. Zhu, J. L. Aceña, V. A.
Soloshonok, K. Izawa, H. Liu, Chem. Rev. 2016, 116, 422-518; d) R.
Berger, G. Resnati, P. Metrangolo, E. Weber, J. Hulliger, Chem. Soc.
Rev. 2011, 40, 3496-3508; e) D. Chopra, T. N. G. Row,
CrystEngComm 2011, 13, 2175-2186; f) T. Fujiwara, D. O’Hagan, J.
Fluorine Chem. 2014, 167, 16-29; g) E. P. Gillis, K. J. Eastman, M. D.
Hill, D. J. Donnelly, N. A. Meanwell, J. Med. Chem. 2015, 58, 8315-
8359; h) W. K. Hagmann, J. Med. Chem. 2008, 51, 4359-4369; i) M.
Pagliaro, R. Ciriminna, J. Mater. Chem. 2005, 15, 4981-4991; j) P.
Jeschke, Pest Manage. Sci. 2010, 66, 10-27.
[10] a) C. Matheis, T. Krause, V. Bragoni, L. J. Goossen, Chem. Eur. J.
2016, 22, 12270-12273; b) P. Nikolaienko, M. Rueping, Chem. Eur. J.
2016, 22, 2620-2623; c) T. Dong, J. He, Z.-H. Li, C.-P. Zhang, ACS
Sustainable Chem. Eng. 2018, 6, 1327-1335.
[11] Q. Lefebvre, R. Pluta, M. Rueping, Chem. Commun. 2015, 51, 4394-
4397.
[12] C. Chen, L. Ouyang, Q. Lin, Y. Liu, C. Hou, Y. Yuan, Z. Weng, Chem.
Eur. J. 2014, 20, 657-661.
[13] a) Visible Light Photocatalysis in Organic Chemistry (Eds.: C. R. J.
Stephenson, T. P. Yoon, D. W. C. MacMillan), Wiley, Weinheim,
Germany, 2018; b) M. H. Shaw, J. Twilton, D. W. C. MacMillan, J. Org.
Chem. 2016, 81, 6898-6926; c) N. A. Romero, D. A. Nicewicz, Chem.
Rev. 2016, 116, 10075-10166.
[2]
[3]
[4]
a) P. Kirsch in Modern Fluoroorganic Chemistry, Wiley-VCH, Wheineim,
2013; b) R. A. Cormanich, D. O'Hagan, M. Bühl, Angew. Chem. Int. Ed.
2017, 56, 7867-7870; Angew. Chem. 2017, 129, 7975-7978; c) B. E.
Smart, J. Fluorine Chem. 2001, 109, 3-11.
[14] a) T. Koike, M. Akita, Chem 2018, 4, 409-437; b) L. L. Zhang Panpan,
Shen Qilong, Acta Chim. Sinica 2017, 75, 744-769; c) Y. Guo, M.-W.
Huang, X.-L. Fu, C. Liu, Q.-Y. Chen, Z.-G. Zhao, B.-Z. Zeng, J. Chen,
Chin. Chem. Lett. 2017, 28, 719-728; d) G. Dagousset, A. Carboni, G.
Masson, E. Magnier in Modern Synthesis Processes and Reactivity of
Fluorinated Compounds (Eds.: H. Groult, F. R. Leroux, A. Tressaud),
Elsevier, 2017, pp. 389-426; e) T. Chatterjee, N. Iqbal, Y. You, E. J.
Cho, Acc. Chem. Res. 2016, 49, 2284-2294; f) T. Koike, M. Akita, Top.
Catal. 2014, 57, 967-974.
a) A. Leo, C. Hansch, D. Elkins, Chem. Rev. 1971, 71, 525-616; b) L.
Bruno, W. Zhong, C. Guillaume, P. Vincent, F. C. Q., W. Neil, W. W.
Alex, Angew. Chem. Int. Ed. 2016, 55, 674-678; Angew. Chem. 2016,
128, 684-688.
a) F. R. Leroux, B. Manteau, J.-P. Vors, S. Pazenok, Beilstein J. Org.
Chem. 2008, 4, 13; b) T. Besset, P. Jubault, X. Pannecoucke, T.
Poisson, Org. Chem. Front. 2016, 3, 1004-1010; c) A. Tlili, F. Toulgoat,
T. Billard, Angew. Chem. Int. Ed. 2016, 55, 11726-11735; Angew.
Chem. Int. Ed. 2016, 128, 11900–11909; d) V. N. Boiko, Beilstein J.
Org. Chem. 2010, 6, 880-921; e) A. Tlili, T. Billard, Angew. Chem. Int.
Ed. 2013, 52, 6818-6819; Angew. Chem. 2013, 125, 6952-6954; f) F.
Toulgoat, S. Alazet, T. Billard, Eur. J. Org. Chem. 2014, 2415-2428; g)
X.-H. Xu, K. Matsuzaki, N. Shibata, Chem. Rev. 2015, 115, 731-764; h)
H.-Y. Xiong, X. Pannecoucke, T. Besset, Chem. Eur. J. 2016, 22,
16734-16749; i) S. Barata-Vallejo, S. Bonesi, A. Postigo, Org. Biomol.
Chem. 2016, 14, 7150-7182; j) F. Toulgoat, T. Billard in Modern
Synthesis Processes and Reactivity of Fluorinated Compounds:
Progress in Fluorine Science (Eds.: H. Groult, F. Leroux, A. Tressaud),
Elsevier Science, London, United Kingdom, 2017, pp. 141-179; k) A.
Tlili, E. Ismalaj, Q. Glenadel, C. Ghiazza, T. Billard, Chem. Eur. J. 2018,
24, 3659-3670.
[15] a) V. Srivastava, P. P. Singh, RSC Advances 2017, 7, 31377-31392; b)
M. Majek, F. Filace, A. J. v. Wangelin, Beilstein J. Org. Chem. 2014, 10,
981-989; c) D. P. Hari, B. Konig, Chem. Commun. 2014, 50, 6688-
6699; d) D. P. Hari, P. Schroll, B. König, J. Am. Chem. Soc. 2012, 134,
2958-2961; e) M. Majek, A. J. von Wangelin, Chem. Commun. 2013, 49,
5507-5509; f) V. Quint, F. Morlet-Savary, J.-F. Lohier, J. Lalevée, A.-C.
Gaumont, S. Lakhdar, J. Am. Chem. Soc. 2016, 138, 7436-7441; g) A.
Talla, B. Driessen, J. W. Straathof Natan, L. G. Milroy, L. Brunsveld, V.
Hessel, T. Noël, Adv. Synth. Catal. 2015, 357, 2180-2186.
This article is protected by copyright. All rights reserved.

10.1002/anie.201806165
Angewandte Chemie International Edition
COMMUNICATION
COMMUNICATION
C. Ghiazza, V. Debrauwer, C.
Monnereau, L. Khrouz, M. Médebielle,
T. Billard* and A. Tlili*
Page No. – Page No.
Visible-Light Mediated Metal-Free
Synthesis of
Trifluoromethylselenolated Arenes:
Scope and Mechanism
Light can make it: Visible light-mediated synthesis of trifluoromethylselenolated
arenes under metal-free conditions is reported herein. The reaction scope
encompasses a large panel of functional groups. Moreover, mechanistic
investigation has been undertaken pointing out the presence of
trifluoromethylselenyl radical.
This article is protected by copyright. All rights reserved.