Electrochemical C-H cyanation of electron-rich (Hetero)arenes

Article abstract of DOI:10.1002/chem.201802247

A straightforward method for the electrochemical C-H cyanation of arenes and heteroarenes that proceeds at room temperature in MeOH, with NaCN as the reagent in a simple, open, undivided electrochemical cell is reported. The platinum electrodes are passivated by ad-sorbed cyanide, which allows conversion of an exceptionally broad range of electron-rich substrates all the way down to dialkyl arenes. The cyanide electrolyte can be replenished with HCN, opening opportunities for salt-free industrial C-H cyanation.

Full text of DOI:10.1002/chem.201802247

A Journal of
Accepted Article
Title: Electrochemical C-H Cyanation of Electron-Rich (Hetero)Arenes
Authors: Davit Hayrapetyan, Raja K. Rit, Markus Kratz, Kristina
Tschulik, and Lukas J Goossen
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To be cited as: Chem. Eur. J. 10.1002/chem.201802247
Link to VoR: http://dx.doi.org/10.1002/chem.201802247
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Electrochemical C–H Cyanation of Electron-Rich (Hetero)Arenes
Davit Hayrapetyan,[a] Raja K. Rit,[a] Markus Kratz,[b] Kristina Tschulik,[b] and Lukas J. Gooßen*[a]
Dedication ((optional))
Abstract: A straightforward method for the electrochemical C–H
cyanation of arenes and heteroarenes is reported that proceeds at
room temperature in MeOH, with NaCN as the reagent in a simple,
open, undivided electrochemical cell. The platinum electrodes are
passivated by adsorbed cyanide, which allow conversion of an
exceptionally broad range of electron-rich substrates all the way down
to dialkyl arenes. The cyanide electrolyte can be replenished with
HCN, opening opportunities for salt-free industrial C–H cyanation.
chemical processes based on anodic oxidation are thus of great
potential importance.
This increased interest has led to the discovery of new
electrochemical processes including cross-dehydrogenative
couplings,[39–42] C-H functionalizations,[43–48] synthetic utilization of
electrogenerated O-[49] and N-centered radicals,[50,51] as well as
electrochemical versions of cross-coupling reactions, such as the
Ni-catalyzed amination of haloarenes.[52]
Aromatic nitriles are abundant in pharmaceuticals and
agrochemicals.[1,2] Moreover, cyano groups are versatile synthons
that can be converted into diverse functionalities, such as acids,
amides, amines, imines, aldehydes, ketones, and heterocycles.[3]
Traditionally, aromatic nitriles are synthesized via functional
group interconversion, e.g. Cu-mediated Sandmeyer[4,5] or
Rosenmund-von Braun reactions.[6] Catalytic[7,8] and metal-free[9]
versions of these reactions have recently been developed.[10–13]
C–H cyanations of arenes compare favorably to these processes,
since they do not require pre-functionalized substrates. However,
Friedel-Crafts-type reactions require highly reactive, toxic
reagents such as Br–CN or NC–CN along with aggressive
mediators that are often used in stoichiometric quantities.[14]
Transition metal-catalyzed C–H cyanations generally rely on
directing groups that are hard to install and remove.[15–32] Non-
directed C–H cyanations have been achieved using hypervalent
iodine reagents[33,34] at the cost of poor atom economy. Another
modern approach to C–H cyanation employs photoredox
catalysis and TMSCN under oxidative conditions.[35]
Known approaches
A. Electrophilic aromatic substitution
Friedel-Crafts conditions
Electrophilic
CN source
Electrophilic
CN source = BrCN
B. Via cation-radical mechanism
TMSCN
hypervalent Iodine
reagent
photocatalyst, light
TMSCN
O2
This work
Pt-Pt, undivided cell
Organic electrochemistry has recently attracted tremendous
attention because the electrochemical oxidation or reduction of
substrates can sustainably activate these for further
functionalization without sensitive or waste-intensive reagents
and in an even more energy-efficient fashion than
photochemistry.[36,37] Moreover, the large-scale electrochemical
hydrogen generation processes that make use of excess wind
energy leave the anode reaction unused, so that stoichiometric
amounts of oxygen are generated.[38] The discovery of efficient
NaCN
electricity
Scheme 1. Methods for arene C–H cyanation.
Aromatic C–H cyanations would strongly benefit from an
electrochemical oxidation process, because nucleophilic cyanide
sources are abundant, whereas electrophilic cyanide reagents
are hard to store and handle. Electrochemical coupling of NaCN
and an arene would furnish the benzonitrile along with hydrogen
and one equivalent of base. On industrial scales, HCN could be
constantly added to regenerate the NaCN. The resulting net
reaction between HCN and Ar–H would deliver Ar–CN along only
with valuable hydrogen gas. Ideally, the reaction can be
performed at a high constant current using a simple two-electrode
setup in an undivided cell.
[a]
[b]
Dr. Davit Hayrapetyan, Dr. Raja K. Rit and Prof. Dr. Lukas J. Gooßen
Evonik Chair of Organic Chemistry
Ruhr-Universität Bochum
Universitätsstr. 150, ZEMOS, 44801 Bochum, Germany
E-mail: lukas.goossen@rub.de.
Markus Kratz and Prof. Dr. Kristina Tschulik
Micro- & Nano-Electrochemistry, Center for Electrochemical
Sciences (CES)
Our mechanistic blueprint for this transformation involved
stepwise anodic oxidation of the arene, first to the radical cation
3,[53–55] which is susceptible to attack by the cyanide nucleophile
leading to cyclohexadienyl radical 4, which would undergo further
oxidation to the benzonitrile 2 Research in this field has so far
been limited to electroanalytical studies, although attempts have
been made towards preparative anodic cyanation. Andreades
Ruhr-Universität Bochum,
Universitätsstr. 150, ZEMOS, 44801 Bochum, Germany.
Supporting information for this article is given via a link at the end of
the document.((Please delete this text if not appropriate))
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employed an elaborate set-up with three-electrode cells with
rotating Pt anodes,[53] and achieved yields below 20% for
moderately electron-rich substrates. Tajima achieved higher
yields for anisole, but needed to use a polymeric CN source.[55]
Yoshida[54] and Maekawa[56] used an undivided electrochemical
cell, but converted only a narrow range of methyl- and silyl-
substituted anisoles, resulting in product mixtures.
bearing a range of functional groups, including carboxylic acids,
esters, primary and secondary amides, were smoothly converted
in good yields. Beyond aryl ethers, suitable substrates include
unsubstituted and substituted naphthalene, anthracene, biphenyl,
and mesitylene, as well as heterocycles such as benzothiophenes
and methoxypyridines. For all these substrates, the
regioselectivity for cyanation was high. Monosubstituted arenes,
such as anisole and its 2-methyl and 2-phenyl derivatives,
expectedly gave mixtures of regioisomers. Notably, allyl and
alkynyl groups remained intact, as did chloro and bromo
substituents, all of which open up opportunities for orthogonal
functionalization. Unprotected pyrrole and indole derivatives
underwent oxidative degradation, and tosamide or carbamate
protecting groups suppressed their reactivity (see the supporting
information for details). The performance limit of the reaction is
reached with m-xylene. This is surprising, since such moderately
electron-rich compounds have so far only been converted using
chemically inert boron-doped diamond electrodes.[57] Electron-
deficient arenes could not yet be converted. The practical utility of
the protocol was also validated by the regioselective cyanation of
derivatives of the anti-inflammatory drug naproxen.
a. Perspective industry process: combining electrolytic H2 evolution with anodic cyanation
HCN
NaCN
MeOH
NaOMe
H2
1
2
b. Proposed mechanism for the anodic cyanation
Pt
A N O D E
-e, -H
-e
.
.
3
4
2
1
CN
2 MeO+ H2
2 MeOH
Table 1. Optimization of reaction conditions.[a]
+ 2e
C A T H O D E
Pt
Pt-Pt, undivided cell
constant current
Scheme 2. Proposed reaction mechanism.
NaCN, solvent
1a
2a
In search for an effective lab-scale electrochemical cyanation
method, we chose 1,3-dimethoxybenzene (1a) as a model
substrate and applied a simple experimental setup consisting of
an undivided cell with Pt sheet electrodes (see supporting
information). Our choice of cyanide source fell on NaCN since its
ionic character allows avoiding the use of additional expensive
supporting electrolytes (such as Bu4NBF4) and its non-volatile
character is much preferable from the safety point of view.
Electrolysis in polar solvents such as CH3CN, DMF and DMSO
was not successful, likely due to the poor solubility of NaCN
(Table 1, entry 1). We were pleased to observe the formation of
the desired product 2a in good yields, when aqueous mixtures of
CH3CN and DMSO were used as solvent (entries 2-3). In contrast,
degradation of the starting material was observed in aqueous
MeOH (entry 4). However, using MeOH with a low water content,
the desired cyanated product 2a was obtained in 84% yield as a
single isomer in (entry 5). A reaction time of 4 h, and a relatively
high current density of 10 mA/cm2 was optimal (entries 6-7).
Variation of the electrode material did not lead to further
improvents. Notably, the yield for inert boron doped diamond
electrodes,[57] that had previously been shown to be superior to
catalytically active platinum, were almost ineffective. It is
noteworthy that the yield achieved for 2a is comparable with that
obtained in the Lewis acid-catalyzed electrophilic aromatic
substitution with BrCN (79% vs. 82%), but our regioselectivity is
superior (>99/1 vs. 95/5).[14]
Entry
1[c]
Current
(mA)
Time (h)
Solvent
Yield of 2a
(%)[b]
–
–
CH3CN, DMF, or
DMSO
0
2
3
4
5
6
7
20
20
20
20
10
30
4
4
4
4
4
4
CH3CN/H2O (9:1)
DMSO/H2O (9:1)
MeOH/H2O (9:1)
MeOH
84
69
0
84(79)[d]
66
MeOH
MeOH
65
[a] Electrolysis was performed in a 20mL undivided cell equipped with Pt
sheet electrodes: 2 cm2 anode and 2 cm2 cathode. The mixture of 1 mmol of
1,3-dimethoxybenzene and 5 eq. of NaCN was dissolved in 10 mL of solvent
and constant current was passed for indicated time. [b] Yields were
determined by GC analysis using mesitylene as internal standard. [c] Poor
conductivity. [d] Isolated yield in parentheses.
Remarkably, allyl phenyl ether (1c) afforded 2c exclusively,
whereas in Sandmeyer cyanations, which also involve arene
radical cation intermediates, complete intramolecular radical
capture occurs, leading to cyclized products.[58,59] This can be
explained by the -delocalized character of the cation radical
species 3.[60,61] In contrast, the radical in Sandmeyer-type
Having thus found effective reaction conditions, we next
investigate the generality of the reaction (Table 2). Aryl ethers
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reactions is localized in an sp2 orbital. The successful
syntheses of 2c, 2f, and 2i are showcase examples
demonstrating the potential orthogonality of traditional and
electrochemical reactivity.
The scalability of the reaction was demonstrated by a
cyanation of 1,3-dimethoxybenzene (1a) on gram scale without
loss of yield or selectivity for product 2a. On larger scales, the use
of excess cyanide salt would be problematic. Since cyanide is
consumed and base is liberated in the course of this reaction, it
should be possible to bring the electrolyte back to its original
composition by adding HCN or one of its synthons. Indeed, we
were able to recycle the electrolyte several times by adding the
HCN synthon trimethylsilyl cyanide after extracting the product
from the MeOH phase (Scheme 2a, runs 1: 72%, 2: 72%, 3: 70%,
4: 73%). This demonstrates the feasibility of a waste-free process
in which arenes for C–H cyanation coupled with hydrogen
generation.
Table 2. Scope of the reaction.[a]
Pt-Pt, undivided cell
Ar-H
Ar-CN
NaCN, MeOH
1
2
Cyclic voltammetry (CV) experiments were performed to gain
further electrochemical insights into the demonstrated redox
reactions and to evaluate the viability of our mechanistic
hypothesis (Figure 1). The CV of NaCN shows that cyanide
oxidation starts only at potentials above 2V. The electrochemical
oxidation of the arene 1a in the presence of NaClO4 as a
supporting electrolyte shows a current peak at around 1.4 V
followed by a steady increase. The first peak is attributed to
oxidation of the arene at the electrode with formation of surface
adsorbed polymer product. The peak-like shape of the signal and
the absence of Faradaic current signals in the reverse scan
confirms the irreversibility of this side process.[62] The signal
appears independently of the type of supporting electrolyte used.
In the presence of cyanide and the arene, this unwanted process
is suppressed. The first Faraday current is now observed at 1.5 V
and resamples the irreversible electrochemical arene oxidation
with formation of the radical cation. We attribute the suppression
of the unwanted polymer coating to the passivation of the Pt
working electrode by adsorption of cyanide[63] (see SI for the
detail). These electrochemical investigations supports a reaction
mechanism via electrochemical arene oxidation followed by
cyanide capture. A reaction pathway via CN radical or dicyan
formation can be excluded. A passivation of the Pt surface by CN-,
which blocks typical side reactions at catalytic electrodes would
explain the exceptional substrate scope of the process.
2
4
6
2b, R = Me, 53%, o/p = 1:1
2c, R = allyl, 60%, o/p = 1:1
2d, 84%
2/4/6 = 1:1:1
2a, 79%
10 mmol scale: 75%
2e, R = Me, 57%
2f, R = 2-methyl-allyl, 40%
2g, R = MOM, 58%
2h, R = Bn, 43%
2i, 49%
2j, 44%
2k, 31%
2l, X= OH, 78%
2m, X= OMe, 80%
2n, X= NH2, 80%
2o, X= N(CH2)4, 86%
2p, 57%
p
o
2s, 65%, o/p = 1:1
2q, 78%
2r, 68%
o
p
2t, 71%
2u, 80%, o/p =1:2
2v, R = Me, 34%
2w, R = H, 46%b
2x, 51%
2y, 73%
2z, 40%
2aa, 70%
2ab, 68%
[a] Reaction conditions: 1 (1 mmol), NaCN (5 mmol), MeOH (10 mL), Pt-Pt
sheet electrodes: 2 cm2 anode and 2 cm2 cathode, 20 mA, 25 °C, 4 h. [b]
320mA current and MeOH/MeCN (1:1) were used.
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Figure 1. Cyclic voltammetry (non-internal reference-corrected) of the single
reactants (black and red), oxidation of 1a (green) and the cyanation reaction
(blue). For all CV experiments a 2 mm diameter Pt-disc electrode was used
employing a scan rate of 100 mV/s in MeOH.
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In conclusion, the electrochemical C–H cyanation of arenes is
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undivided electrochemical cells equipped with platinum sheet
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Experimental Section
A 20 mL reaction vial was charged with (hetero)arene 1 (1 mmol), NaCN
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Davit Hayrapetyan, Raja K. Rit, Markus
Kratz, Kristina Tschulik, and Lukas J.
Gooßen*
'HCN'
Pt-Pt
undivided cell
27 examples, up to 80% yield
NaCN
MeOH
NaOMe
H2
Page No. – Page No.
Electrochemical C–H Cyanation of
Electron-Rich (Hetero)Arenes
The electrochemical C–H cyanation of arenes is shown to constitute an
advantageous synthetic alternative to traditional, waste-intensive cyanation
methods. It gives high yields using simple, undivided electrochemical cells
equipped with platinum sheet electrodes, proceeds well even in the presence of air
and moisture, and allows waste-free regeneration of the electrolyte.
This article is protected by copyright. All rights reserved.