Electrochemical Oxidative C(sp2)–H Bond Selenylation of Activated Arenes

Article abstract of DOI:10.1002/ejoc.201900992

Herein, we report an electrochemical oxidative C(sp²)–H selenylation of activated arenes. The reaction proceeds in an undivided electrochemical cell at Pt-electrodes in the presence of KI as the supporting electrolyte, which could suffer oxidat

Full text of DOI:10.1002/ejoc.201900992

A Journal of
Accepted Article
Title: Electrochemical oxidative C(sp2)-H bond selenylation of activated
arenes
Authors: Anne G Meirinho, Vinícius F Pereira, Guilherme M Martins,
Sumbal Saba, Jamal Rafique, Antonio L Braga, and Samuel
Rodrigues Mendes
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.
To be cited as: Eur. J. Org. Chem. 10.1002/ejoc.201900992
Link to VoR: http://dx.doi.org/10.1002/ejoc.201900992
Supported by

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10.1002/ejoc.201900992
COMMUNICATION
2
Electrochemical oxidative C(sp )-H bond selenylation of activated
arenes
[
a]
[a]
[b]
[b]
[c]
Anne G. Meirinho, Vinícius F. Pereira, Guilherme M. Martins, Sumbal Saba, Jamal Rafique,
Antonio L. Braga,[b]* Samuel R. Mendes[a]*
2
2
Abstract: Herein, we report an electrochemical oxidative C(sp )-H
oxidative C–Se bond formation through the C(sp )–H bond
activation of arenes (Scheme 1).3d,5 Alves and coworkers reported
the selenylation of anilines using CuI in DMSO.5a The same group
reported an alternative method using anilines and PhSeCl as
substrates, in glycerol under an inert atmosphere.5b Recently, we
reported the oxidative C–Se bond formation of arenes under
selenylation of activated arenes. The reaction proceeds in an
undivided electrochemical cell at Pt-electrodes in the presence of KI
as the supporting electrolyte, which could suffer oxidation at the
anode. Using this benign, atom-economic protocol, the desired
selenylated products were obtained regioselectively, in good to
excellent yields, using a half molar equiv. of the diselenides.
different conditions: using
I
2
/DMSO (under microwave
/ ethylene glycol (with conventional
irradiation),5 as well as KIO
c-d
3
heating).3d
Introduction
Synthetic organoselenium compounds are gaining interest
from the synthetic community, mainly due to their remarkable
potential in the areas of biology1 and material science.2 The
unsymmetrical organoselenides with nitrogen- or oxygen-
containing arenes are an important class of organoselenide
molecules (Figure 1).3 These motifs are frequently found in
several kinds of biologically relevant compounds, and tested for
their potential against several diseases, including Alzheimer,
Parkinson and cancer.1-4
Scheme 1. Methods for preparation of unsymmetrical organoselenides with
nitrogen- or oxygen-containing arenes.
In recent years, electrochemical organic transformations
have emerged as an attractive and suitable approach,6,7 which
has attracted the attention of research groups. In many cases,
synthetic electrochemistry has several advantages over
conventional synthesis, such as the direct use of the electrons as
a reagent, few reaction steps, mild reaction conditions, predictive
mechanistic studies can be carried out via cyclic voltammetry,
expensive reagents are regenerated in the catalytic cycle, high
atom economy, reverse polarity (umpolung), and scalability. Thus,
synthetic electrochemistry offers advantages over traditional
synthesis.8,9
Figure 1. Biologically relevant nitrogen- or oxygen-containing arenes with
organochalcogenides.
Due to the importance of these types of unsymmetrical
organoselenides, it is of great interest to develop new
methodologies for their preparation. There are few reports
available in literature for the synthesis of these selenides via
[
a]
A. G. Meirinho, V. F. Pereira, Prof. Dr. S. R. Mendes
SINCA – Departamento de Química, Universidade do Estado de
Santa Catarina, Joinville, 89219-719 SC, Brazil.
E-mail: samuel.mendes@udesc.br, ORCID 0000-0002-2388-3008
Dr. G. M. Martins, Dr. S. Saba, Prof. Dr. A. L. Braga
Labselen, Departamento de Química, Universidade Federal de
Santa Catarina, Florianopolis, 88040-900, SC-Brazil.
http://labselen.ufsc.com/
To the best of our knowledge, the electrochemical oxidative
selenylation of arenes has not yet been explored. As part of our
continued interest in designing and developing eco-friendly
processes,10 as well as in the C(sp )–H bond selenylation of
2
[
b]
3d,5c-d
activated arenes,
herein we report, for the first time, the use
of an electrochemical oxidative approach to C-Se bond formation
2
E-mail: braga.antonio@ufsc.br
via the C(sp )–H bond functionalization of arenes (Scheme 1d).
[c]
Dr. J. Rafique
With this new approach, using KI as an efficient electrolyte and
source of iodine, in MeCN, we obtained the desired selenylated
products regioselectivity in good to excellent yields.
Instituto de Química, Universidade Federal do Mato Grosso do Sul,
Campo Grande, 79074-460, MS-Brazil. https://sintmol.ufms.br/
E-mail: jamal.rafique@ufms.br , jamal.chm@gmail.com
Our new alternative and environmentally benign protocol
requires a short reaction time and works effectively using various
activated arenes with only a half molar equiv. of diorganyl
Supporting information for this article is given via a link at the end of
the document.
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European Journal of Organic Chemistry
10.1002/ejoc.201900992
COMMUNICATION
diselenides (atom economic reaction), under an open-to-air
atmosphere.
However, when electrolysis was performed with TEBABr
and TBAI a good conversion was achieved, with conversion of
up to 85% (entries 2 and 3). It is well established that halide
ions can act as mediators in indirect electrosynthesis.5
Considering this and the results of entries 2 and 3, we decided
to explore the use of electrolytes containing iodide ions. With
NaI and KI salts, product 3a was obtained in excellent
conversion up to 99% (entries 4 and 5) and isolated by column
chromatography in 97% yield (entry 5). After 15 min a decrease
in conversion to 77% was observed (entry 6). Applying an
electric current of 15 mA a reduction in the conversion was
observed (45%, entry 7). Interestingly, with a 25% reduction in
the amount of electrolyte/redox mediator there was a 25%
reduction in product conversion (75%, entry 8). Other solvents
,6
Results and Discussion
The electrochemical selenylation of (hetero)arenes was
conducted using 2-naphthol (1a) and diphenyl diselenide (2a) in
an undivided cell, with screening under several reaction
conditions (Table 1). Initially, MeCN was used as the solvent
-1
applying a current of 20 mA (0.99 Fmol ) with platinum electrodes
at the anode and cathode. In an in-depth study of the electrolysis,
the reaction progress was constantly monitored by GC-MS. Firstly,
4
TBABF was used as the electrolyte, but the methodology was not
effective and only traces of product 3a were observed (entry 1),
with 1a and 2a remaining in the solution.
were also evaluated, such as a mixture of MeCN:H O (1:1),
2
DMSO, MeOH and DMF; however, no improvement was
observed (entries 9–12). Different potassium salts were
evaluated, such as KBr, KCl and KF, but no improvements
were observed (entries 13–15). With graphite electrodes the
conversion was 87% (entry 16), while with a graphite electrode
at the anode and platinum at the cathode the conversion was
Table 1. Optimization of the reaction conditions.[a]
8
6% (entry 17). Lastly, with platinum at the anode and graphite
Entry
Electrolyte
TBABF
Solvent
Current (mA)
Yield (%)[b]
at the cathode the conversion was 74% (entry 18). No reaction
was observed in the absence of electric current (entry 19).
With the optimized conditions in hand, we investigated the
scope of the electrochemical selenylation of arene derivatives
1
2
3
4
5
6
7
8
9
4
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
20
20
20
20
20
20
15
20
20
20
20
20
20
20
20
20
20
20
0[j]
Trace
85
TEBABr
TBAI
NaI
KI
(
Scheme 2). Initially, a variety of diphenyl diselenides bearing
82
electron-donor and electron-withdrawing groups as well as
aliphatic and benzylic diselenides were subjected to the
reaction, providing the corresponding products in good to
excellent yields (68 – 97%, Scheme 2).
95
99(97)[c]
77[d]
45
KI
KI
KI[e]
KI
75
MeCN/H
2
O[f]
52
10
11
12
13
14
15
16
17
18
19
KI
DMSO
MeOH
DMF
20
KI
75
KI
92
KBr
KCl
KF
KI
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
21
15
Trace
87[g]
86[h]
74[i]
0
KI
KI
KI
Scheme 2. Scope of the electrochemical C–H selenation of 2-naphthol.
Conditions: platinum electrodes, constant current (20 mA), 1a (0.25 mmol), 2
(0.125 mmol), KI (0.12 mmol), MeCN (5 mL), rt, air. Yields isolated by column
chromatography.
[
a] Conditions: 2-naphthol 1a (0.25 mmol), diphenyldiselenide 2a (0.125
mmol), electrolyte (0.12 mmol), solvent (5 mL), constant current, 20 min, rt.
b] Conversion by GC-MS. [c] Isolated by column chromatography. [d]
Reaction time of 15 min. [e] 0.09 mmol of KI. [f] MeCN/H O (1:1). [g] C(+)|C(-).
h] C(+)|Pt(-). [i] Pt(+)|C(-). [j] No electric current.
[
2
[
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European Journal of Organic Chemistry
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COMMUNICATION
Next, we explored the scope of (hetero)arene derivatives
Scheme 3). The electrochemical selenylation of N,N-
radical scavenger TEMPO was used under standard conditions,
no suppression was noted and 3a was obtained in 99%
conversion (Scheme 5A). This suggests that probably the
reaction is not dependent on radical intermediates and may follow
(
dimethylaniline derivatives and 1H-indole were successfully
achieved in yields of up to 90% (5a – 5h, 5o). On the other hand,
the experiments with 1,3,5-trimethoxybenzene and 5,6,7,8-
tetrahydronaphthalen-2-ol derivatives were not efficient, with
product yields of 41% (5i) and 44% (5j), respectively. Additionally,
an ionic route. In order to investigate the role of KI, and
-
considering that iodine (I
2
) can be obtained from iodide ions (I ) by
anodic oxidation and act as
a
redox mediator in
2
-methoxynaphthalene, 2-acetylaminonaphthalene and 2-
electrosynthesis,5,6,11 the reactions illustrated in schemes 5B-D
were performed. Experiment 5B provided the product 3a in 69%
conversion, suggesting a mechanistic route via the phenylselenyl
halide intermediate. Organochalcogens and iodide have several
naphthylamine derivatives were completely suppressed, with only
the starting material remaining in the reaction medium (5m – 5n).
applications as electrophilic substrates, being important for new
carbon-chalcogen bonds formation.10e-g,
12
In addition,
electrochemical oxidation of iodine in acetonitrile generates
+
+
3
CH CNI in situ (equivalent of I ), which can react with aromatic
compounds to provide the iodinated products.13 GC-MS analysis
was performed as the reaction progressed and the halogenated
intermediate 7a was observed, which was totally consumed by
the end of the reaction. Thus, we investigated the formation and
reactivity of 7a, as illustrated in Scheme 5C-D. The halogenated
product of 2-naphthol via electrosynthesis was obtained in 57%
conversion (Scheme 5C) leaving 2-naphthol even after 3 h of
reaction. The selenylation of 7a was obtained in 85% conversion
(
Scheme 5D) suggesting another possible mechanistic route,
which would pass through iodination of the aromatic compound.
Starting from substrate 7a under standard conditions without an
electric current, product 3a was obtained in 22% conversion after
20 min and in 97% conversion after 24 h (Scheme 5E), indicating
that the reaction mechanism could also pass through the
intermediate compound 7a.
Scheme 3. Scope of the electrochemical C–H selenation of (hetero)arenes.
Conditions: platinum electrodes, constant current (20 mA), 4 (0.25 mmol), 2
(0.125 mmol), KI (0.12 mmol), MeCN (5 mL), rt, air. Yields isolated by column
chromatography.
In order to evaluate the importance of the present method, the
electrochemical selenation of 2-naphthol was carried out in gram-
scale synthesis (5 mmol), affording the product 3a in 86% yield
after 8.5 h (Scheme 4). The reaction proved effective on a large
scale, highlighting its potential for industrial application.
Scheme 5. Control experiments. Standard conditions: platinum electrodes,
constant current (20 mA), 1a (0.25 mmol), 2a (0.125 mmol), KI (0.12 mmol),
MeCN (5 mL), 20 min, rt, air. Conversion yields obtained by GC-MS.
Scheme 4. Gram-scale synthesis. Conditions: platinum electrodes, constant
current (20 mA), 1a (5 mmol), 2a (2.5 mmol), KI (2.4 mmol), MeCN (100 mL), rt,
air. Yields isolated by column chromatography.
In addition, to obtain further information regarding the
mechanism, cyclic voltammetry was performed and the anodic
To gain a better understanding of the reaction mechanism,
few control experiments were performed (Scheme 4). When the
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European Journal of Organic Chemistry
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COMMUNICATION
peak potentials (Epa) of 2-naphthol, potassium iodide and diphenyl
diselenide were obtained (Figure 2). It can be observed that
potassium iodide is the first compound to oxidize and two peaks
are present, at 0.79 and 0.91 V, which can be assigned to the
-
-) and the
),
oxidation of the iodide ion (I ) to form the triiodide ion (I
3
oxidation of the triiodide ion (I
3
-) to produce molecular iodine (I
2
1
4
respectively. The oxidation peaks of diphenyl diselenide (1.66
V) and 2-naphthol (2.0 V) were then observed. It should be noted
that the Epa value for 2-naphthol exceeds the working value of the
solvent used. With this result, we can assume that the oxidation
of iodide ion is favored, which gives us some insight into the
reaction mechanism.
1000
Scheme 6. Proposed mechanism for selenation of (hetero)arenes.
2
-naphthol
KI
800
600
400
200
0
PhSeSePh
Conclusions
In conclusion, we have developed an alternative,
synthetically attractive, robust and safe scalable method for the
synthesis of selenylated arenes via electrochemically oxidative
2
C(sp )-H bond selenylation. This regioselective procedure
afforded the desired products in good to excellent yields using Pt
electrodes, in the presence of KI as an electrolyte, and using a
half molar equiv. of diselenides without the exclusion of air and
moisture in a shorter reaction time.
-0,5
0,0
0,5
1,0
1,5
2,0
E (V) vs NHE
The key features of this benign and robust protocol are: (1)
electrochemical approach; (2) open to the air; (3) atom-economic;
(4) gram-scalable; (5) non-toxic and easily handleable reagents;
Figure 2. Cyclic voltammetry of 2-naphthol, KI and diphenyldiselenide in
MeCN. Working electrode: carbon; counter electrode: platinum; reference
+
-1
-1
4 6
electrode: Ag/Ag ; electrolyte: n-Bu NPF (0.1 molL ); scan rate: 200 mVs .
(
6) regioselective; and (7) applicable to a wide range of
biologically relevant arenes.
Based on the data collected (Scheme 5 and Figure 2) and
previous reports,5,10e-g
plausible mechanism for the
a
electrochemical selenylation of 2-naphthol with diphenyl
diselenide was proposed (Scheme 6). Two possible reaction
pathways were considered. In pathway A, the reaction begins with
the anodic oxidation of the iodide ion to form the iodonium ion
mediator, followed by electrophilic substitution at the C-1 position
of 2-naphthol and the loss of a proton, providing intermediate 7a,
which is rapidly captured by the diselenide, affording the final
product 3a and iodine. The iodine undergoes cathodic reduction
by regenerating the iodide ion for the catalytic cycle. In pathway
B, the reaction begins with the anodic oxidation of the iodide ion
to form the iodine mediator, followed by the oxidation of the
diselenide to form the intermediate 6b, which attacks C-1 of the
Experimental Section
General Procedure: Arene (1a or 4, 0.25 mmol), diselenide (2, 0.125
mmol), KI (0.12 mmol) and 5.0 mL MeCN were placed in an undivided
three-necked flask (25 mL) at rt under stirring. The flask was equipped with
2
platinum electrodes (1.0×1.0 cm ) as the anode and as the cathode. The
reaction mixture was electrolyzed under constant current mode (20 mA).
The reaction progress was monitored by TLC. After the completion of the
reaction, 15% sodium thiosulphate solution (5 mL) was added and the
resulting mixture was extracted with EtOAc (3  10 mL). The combined
organic phases were washed with water (1  10 mL) and brine (1  10mL),
and dried over anhydrous MgSO
under reduced pressure. The product was purified chromatographically
hexanes/EtOAc, 90:10).
4
. After filtration, the solvent was removed
2-naphthol to give the final product 3a followed by elimination of
(
a proton and iodide ion.
Acknowledgements
This study was financed in part by the Coordenação de
Aperfeiçoamento de Pessoal de Nível Superior - Brasil (CAPES)
–
Finance Code 001. We gratefully acknowledge CNPq,
CERSusChem GSK/FAPESP (grant 2014/50249-8), PAP
UDESC-FAPESC, INCT-Catálise and FAPESC-Pronex for
financial support. J.R. and S.R.M. would like to acknowledge
CNPq for funding, protocols 433896/2018-3 and 431391/2016-5,
respectively.
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European Journal of Organic Chemistry
10.1002/ejoc.201900992
COMMUNICATION
Bolaños, Eur. J. Med. Chem. 2017, 138, 761-773; c) F. A. R. Barbosa,
R. F. S. Canto, S. Saba, J. Rafique, A. L. Braga, Bioorg. Med. Chem.
Conflict of Interest
2
016, 24, 5762-5770.
The authors declare no conflict of interest.
[
[
5]
6]
a) V. G. Ricordi, S. Thurow, F. Penteado, R. F. Schumacher, G. Perin, E.
J. Lenardão, D. Alves, Adv. Synth. Catal. 2015, 357, 933-939; b) S.
Thurow, F. Penteado, G. Perin, R. G. Jacob, D. Alves, E. J. Lenardão,
Green Chem. 2014, 16, 3854-3859; c) S. Saba, J. Rafique, A. L. Braga,
Catal. Sci. Technol. 2016, 6, 3087-3098; d) L. T. Silva, J. B. Azeredo, S.
Saba, J. Rafique, A. J. Bortoluzzi, A.L. Braga, Eur. J. Org. Chem. 2017,
Keywords: Sustainable Chemistry • Electrochemistry • Selenide
2
•
Arenes • C(sp )-H bond selenylation.
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European Journal of Organic Chemistry
10.1002/ejoc.201900992
COMMUNICATION
Entry for the Table of Contents
COMMUNICATION
2
C(sp )-H bond selenylation
Electrochemistry*
A. G. Meirinho, V. F. Pereira, G. M.
Martins, S. Saba, J. Rafique, A. L.
Braga, S. R. Mendes
Electrochemical C-H bond selenylation of (hetero)arenes: By using an
electrochemical oxidative C(sp )-H selenylation of activated arenes approach, the
desired selenylated products were regioselectively obtained in good to excellent
yields. The reaction is mediated by the iodine, obtained from the oxidation of KI at
the anode.
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2
2
Electrochemical oxidative C(sp )-H
bond selenylation of activated arenes.
This article is protected by copyright. All rights reserved.