Electrochemically Oxidative C-C Bond Cleavage of Alkylarenes for Anilines Synthesis

Article abstract of DOI:10.1021/acscatal.8b04351

In contrast to the recent breakthrough in electrochemical C-H aminations, the electrochemically oxidative C-N bond formation through a C-C bond cleavage is rarely studied. This work describes an electrochemical C-C amination of alkylarenes for the efficie

Full text of DOI:10.1021/acscatal.8b04351

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Letter
Electrochemically Oxidative C-C Bond
Cleavage of Alkylarenes for Anilines Synthesis
Yeerlan Adeli, Kaimeng Huang, Yujie Liang, Yang-Ye Jiang,
Jianzhong Liu, Song Song, Cheng-Chu Zeng, and Ning Jiao
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Electrochemically Oxidative C-C Bond Cleavage of Alkylarenes for
Anilines Synthesis
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Yeerlan Adeli,† Kaimeng Huang,† Yujie Liang,† Yangye Jiang,§ Jianzhong Liu,† Song Song,† Cheng-
Chu Zeng*,§ and Ning Jiao*,†,‡
†State Key Laboratory of Natural and Biomimetic Drugs, School of Pharmaceutical Sciences, Peking University Xue Yuan
Rd. 38, Beijing 100191, China
§Beijing Key Laboratory of Environmental and Viral Oncology, College of Life Science & Bioengineering, Beijing Universi-
ty of Technology, Beijing 100124, China
‡ Shanghai Key Laboratory of Green Chemistry and Chemical Processes, East China Normal University, Shanghai 200062,
China
ABSTRACT: In contrast to the recent breakthrough in electrochemical C-H aminations, the electrochemically oxidative C-N bond
formation through a C-C bond cleavage is rarely studied. This work describes an electrochemical C-C amination of alkylarenes for
the efficient synthesis of versatile anilines, as well as carbonyl compounds. With the cheap and durable graphite plates as electrodes,
and in
a simple undivided cell, this protocol is much more economical with the consumption of electricity.
Keywords: electrochemistry • C-C activation • amination • oxidation • rearrangements
Oxidative processes are ubiquitous in nature as well as in
fundamental transformations of chemical synthesis. Recently,
the oxidative C-N bond formation through C-H/C-C bond
cleavage is of great interest to chemists both in academia and
industry due to their importance of N-containing compounds
in materials and pharmaceuticals.1,2 Among these oxidative
processes, plenty of efficient common oxidants including hy-
pervalent iodine reagents, quinones, peroxides, and metal salts
were widely used.3 However, the stoichiometric loading of
these oxidants would cause separation problem and low atom-
economy.
Alternatively, electrochemistry has been convicted powerful
in chemicals synthesis,4-6 and some significant oxidative reac-
tions were achieved by electrochemical oxidation without any
external traditional oxidants. Recently, the breakthroughs in
electrochemical C-H aminations were remarkably achieved by
the consumption of only electricity (Scheme 1a).7-12 Yoshida
and co-workers pioneeringly disclosed an anodic oxidative C-
H amination of aromatic substrates with pyridine for the syn-
thesis of arylamines.7 Xu and co-workers developed an elegant
Scheme 1. Different Kinds of Oxidative C-N bond For-
mation
Kolbe reaction has been developed more than 150 years and
widely used for the electrochemical synthesis of alkanes via a
decarboxylative process,13 however, selective electrochemical
C-C bond cleavage to synthesize amines is less studied and
still a challenge, because the generated amine products are
easier oxidized than the parent materials, which would lead to
low chemical yield and current efficiency. In addition, it is
worthwhile to overcome the chemical bond selectivity for the
development of new C-C bond functionalizations. Herein, we
describe a novel electrochemical C-C amination of alkylarenes
via selective Csp2-Csp3 bond cleavage (Scheme 1b). The pro-
tocol not only produces arylamines and useful carbonyl com-
pounds simultaneously with high atom economy, but also cir-
cumvents the possible over-oxidation of resulting arylamines.
On account of trace-less and cheap electrochemical oxidation
taking place of toxic and expensive oxidant, this transfor-
mation becomes mild, green, sustainable and efficient. Nota-
intramolecular C-H amination
to afford polycyclic N-
heteroaromatic products via nitrogen-centered radicals.8 Lei’s
group developed a significant intermolecular dehydrogenative
C-H/N-H cross-coupling reaction.9 More recently, the combi-
nation of electrochemistry and transition-metal catalysis for C-
H amination of arenes was independently realized by the
groups of Lei,10 Ackermann11 and Mei.12 Although great pro-
gresses have been made in C-N bonds construction through
electrochemically oxidative C-H bonds cleavage, the electro-
chemically oxidative C-N bond formation through C-C bond
cleavage is still undeveloped.
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bly, with the cheap and durable graphite plates as electrodes, lytes such as Bu4NBF4 did not give better result (69%, entry
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and in a simple undivided cell, this reaction is much more
economical as well. In addition, the transition-metal catalyst
free condition eradicates the problem of metal residual in
products.
12).
Table 2. Electrochemical Oxidative C-C Bond Amination
of Alkylarenes.a
Table 1. Optimization of Reaction Conditions.a
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aReaction conditions: graphite plate anode and cathode ( 1.5 cm ×
1.5 cm × 0.1 cm, J = 8.9 mA/cm2), Me4NBF4 (0.11 M), solvent (9
mL), 25oC, argon. bYields determined by 1H-NMR analysis of the
crude reaction mixture using 1,1,2,2-tetrachloroethane as the in-
ternal standard. The yield of the isolated product is given within
the parentheses. cReaction temperature = 60oC. dRVC as elec-
trodes. eBu4NBF4 (0.06 M) as the electrolyte.
aStandard conditions: see entry 11, Table 1. Yields shown are
isolated yields. bBu4NPF6 (0.06 M) was used as electrolyte instead
c
of Me4NBF4, current density was 25 mA/cm2. Current density
was 30 mA/cm2.
Then we investigated the protocol using different alkyl ben-
zene substrates under the optimized reaction conditions (Table
2). Diarylmethanes showed good reactivity to afford the corre-
sponding products (1b-1g). The aromatic substrates with me-
thyl substitution at different position are competible with this
protocol (1b-1d). By the selective cleavage of Csp2-Csp3
bonds, varieties of diarylmethanes produced different substi-
tuted anilines. This transformation also worked well when
inert alkyl benzenes were employed as substrates. These sub-
strates afforded the desired N-alkylanilines in moderate to
good yields (1h-1o). Unfortunately, the current conditions are
not efficient to the substrates with strong electron-withdrawing
groups.
We previously developed oxidative nitrogenation reactions
of simple hydrocarbons with DDQ as the oxidant,14 which
suffers from its toxicity, high cost, and difficulty in the remov-
al of DDQH2 waste. Inspired by the above significant electro-
chemical C-H amination,7-12 we therefore tried to investigate
the possibility of the electrochemical C-C amination of al-
kylarenes. This chemistry started by chosing diphenylmethane
(1a) and 1-azidononane (2a) as the model compounds (Table
1). Interestingly, the electrochemical oxidation worked well
when graphite plate electrodes were employed as both anode
and cathode in the presence of tetramethylammonium tetra-
fluoroborate (Me4NBF4) as the electrolyte, which produced the
amination product 3a in 44-56% (entries 1-2, also see Table
S1 in the supporting information). The control experiment
without electric current did not afford the product 3a (entry 3).
The reaction using a mixture of 1, 2-dichloroethane (DCE) and
trifluoroacetic acid (TFA) as the solvent afforded 3a in 58%
yield (entry 4). The reactions in DCE or DCE/HOAc did not
work (entries 5-6). Although the substrate was consumed
completely under higher and lower current, the corresponding
yields were not improved (52%-48%, entries 7 and 8). No
desired product was detected when RVC electrodes were used
(entry 9). The yield improved to 84% when the substrate con-
centration was increased (entry 11). Meanwhile, other electro-
Interestingly, the chemistry provides a simple approach for
ring-opening reactions through selective oxidative C-C bond
cleavage at the preferred dibenzylic position. For examples,
the substrate dibenzosuberane (1p) was efficiently converted
into 3p in 71% yield, which also demonstrated the preferred
reactivity in dibenzylic position and the aldehyde by-product
of the leaving part of the substrates (Eq. 1). Moreover, 1e pro-
duced the aniline product 3e in 87% yield with the formation
of benzaldehyde 4e in 71% yield.
Furthermore, the results in Table 3 demonstrate that various
alkyl azides were also compatible in this transformation,
which make this reaction useful (Table 3). Both primary and
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secondary azides performed well under the standard
1
conditions (Table 3).
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Table 3. Substrate Scope of Different Alkyl Azides a
Figure 1. Cyclic voltammograms of 1a and 2a in 0.1 M
Me4NBF4/DCE:CF3COOH (2:1) using Pt disk working electrode
(ϕ 1 mm), Ag wire counter and Ag/AgNO3 (0.1 M in CH3CN)
reference electrode at 20 mV/s scan rate. (a) background. (b) 2a (1
mmol/L). (c) 1a (1 mmol/L). (d) 1a + 2a (1 mmol/L + 1 mmol/L).
aStandard conditions: see entry 11, Table 1. Yields shown are
isolated yields.
Scheme 2. Proposed Mechanism.
The results of cyclic voltammetry studies proved that alkyl
azide, 2a, is redox inactive and no obvious oxidative peak was
observed with the potential range of 0 to 3.0 V (Figure 1,
curve b), whereas, alkyl benzene 1a exhibits two obvious oxi-
dative peaks at 2.05 V and 2.39 V (vs Ag/AgNO3) (Figure 1,
curve c), which indicates that 1a is easier to be oxidized than
2a. In addition, the irreversible electrochemical behaviour of
1a discloses that the generated active species from anodic
oxidation of 1a are prone to undergo subsequent chemical
reaction(s) (EC process). This is further demonstrated from the
CVs of 1a in the presence of 2a. For example, the first peak
current of 1a decreased from 19.8 μA to 17.9 μA in the pres-
ence of 1 equiv of 2a.15 These results demonstrate that the
corresponding carbon cation formation with DDQ oxidation
could now be replaced by electrochemical oxidation.
On the basis of the cyclic voltammetry studies and the
related literature,16,17 we propose the mechanism of this C-C
bond amination process (Scheme 2). First, the substrate is
oxidized on the anode, thus generating radical cation A. The
initially generated radical cation deprotonates to give the
benzyl radical B, which further undergoes oxidation to form
the intermediate cation C. Then, the nucleophilic organic az-
ides18 attack cation C to produce the species D. Then the in-
termediate E is formed by the Schmidt-type rearrangement19
of intermediate D with the release of dinitrogen gas as the
driving force. Next, isomerization and hydrolysis produces N-
alkylanilines and benzaldehydes.
In summary, we have developed the first electrochemical
oxidative C-C amination. The reaction employs a pair of cheap
graphite plates as electrodes in an undivided cell without any
external catalyst or oxidants. Thus, by avoiding the exogenous
stoichiometric oxidants, the protocol is green, sustainable and
efficient, and also easy to operate. The anodic generation of
carbon cations and their subsequent reactions may be condu-
cive to develop novel electrochemical transformations.
ASSOCIATED CONTENT
AUTHOR INFORMATION
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Page 4 of 6
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Corresponding Author
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* E-mail: jiaoning@pku.edu.cn
* E-mail: zengcc@bjut.edu.cn
Notes
The authors declare no competing financial interest.
Supporting Information.
Experimental procedures, analytical data for products, NMR spec-
tra of products. The supporting information is available free of
charge via the Internet at http://pubs.acs.org.
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ACKNOWLEDGMENT
Financial support from the National Natural Science Foundation
of China (21632001, 81821004, 21772002), the National Basic
Research Program of China (973 Program) (No. 2015CB856600),
and the Drug Innovation Major Project (No. 2018ZX09711-001)
are greatly appreciated. We thank Xiaoxue Yang and Cheng
Zhang in this group for reproducing the results of 1o and 1h.
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