Cobalt(II)-Catalyzed Electrooxidative C-H Amination of Arenes with Alkylamines

Article abstract of DOI:10.1021/jacs.7b13049

An environmentally friendly electrochemical protocol about cobalt-catalyzed C-H amination of arenes has been developed, which offers a simple way to access synthetically useful arylamines. In divided cells, a wide variety of arenes and alkylamines are exa

Full text of DOI:10.1021/jacs.7b13049

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Cobalt(II)-Catalyzed Electrooxidative C
-H Amination of Arenes with Alkylamines
Xinlong Gao, Pan Wang, Li Zeng, Shan Tang, and Aiwen Lei
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.7b13049 • Publication Date (Web): 09 Mar 2018
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Cobalt(II)-Catalyzed Electroo
Alkylamines
Amination of Arenes with
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Xinlong Gao,†, ‡ Pan Wang,†, ‡ Li Zeng,† Shan Tang† and Aiwen Lei*,†
† The Institute for Advanced Studies (IAS), College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072,
P. R. China
Supporting Information Placeholder
ABSTRACT: An environmentally friendly electrochemical pro-
tocol about cobalt-catalyzed C-H amination of arenes has been de-
veloped, which offers a simple way to access synthetically useful
arylamines. In divided cells, a wide variety of arenes and alkyla-
mines are examined to afford C-N formation products without us-
ing external oxidants, which avoids the formation of undesired by-
products and exhibits high atom economy. Importantly, the reac-
tion can also be extended to gram level with moderate efficiency.
KIE experiment indicates that C−H bond cleavage might not be in-
volved during the rate-limiting step.
Figure 1. Electrochemical Cobalt-Catalyzed C-H Amination.
Table 1. Effect of the Reaction Parameters.a
Transition-metal-catalyzed C-H functionalization has been rec-
ognized as one of powerful strategies to construct C-C and C-X
(X=N, O, P, S etc.) bonds.1 Compared with some noble metals, co-
balt exhibited various advantages in low cost and toxicity, unique
catalytic reactivity.2 In recent years, cobalt-catalyzed C-H alkoxy-
lation,3 amination4 and arylation5 have been widely reported. How-
ever, high consumption of material and severe metal residue were
inevitable since a large excess of silver and manganese salts were
needed for the dehydrogenative process.6 Therefore, it is highly de-
sirable to seek for a more efficient oxidant-free Co-catalytic sys-
tem.
Entry
1
Variation from standard conditions
none
Yield (%)
74
2
CoCl2·6H2O
67
3
Co(acac)2
14
The development of efficient and environmentally friendly
methods is an important topic in organic synthesis. As an ideal al-
ternative to chemical oxidants, electrochemical anodic oxidation
can serve as an environmentally friendly synthetic tool in organic
chemistry.7 Under electrolytic conditions, substrates could be oxi-
dized at anode directly8 or indirectly.9 Nevertheless, most metal
catalysts are prone to be reduced at cathode and lose catalytic reac-
tivity. For this reason, continuous efforts have been devoted to de-
veloping transition-metal-catalyzed electrooxidative C-H function-
alization under divided cell.10 In 2007, Jutand and co-workers
firstly reported Pd-catalyzed electrooxidative C(sp2)-H alkenyla-
tion.10a Subsequently, Kakiuchi and co-workers developed Cu-cat-
alyzed electrooxidative C(sp3)-H chlorination.10e Overall, transi-
tion-metal-catalyzed electrooxidative C-H functionalization was
mainly limited to Pd-catalyzed reactions.11 Therefore, it would
make sense to develop cheaper transition-metal-catalyzed elec-
trooxidative C-H functionalization. Herein, we demonstrated co-
balt-catalyzed electrooxidative C-H amination between arylamides
and alkylamines under divided electrolytic conditions (Fig. 1). The
replacement of oxidants with electricity made organic reactions
proceed efficiently.
4
NaOAc at anode
HOPiv at anode
67
5
46
6
DMF instead of MeCN
CF3CH2OH instead of MeCN
H2O instead of MeOH
5 mA, 6 h
54
7
n.d.
68
8
9
68
10
11
12
13
15 mA, 2 h
68
undivided cell
n.d.
n.d.
n.d.
without Co(OAc)2·4H2O
no electric current
a Reaction conditions: 1a (0.25 mmol), 2a (2.0 equiv.), Co(OAc)2·4H2O (20
mol%), NaOPiv·H2O (1.0 equiv.), nBu4NBF4 (2.0 equiv.), MeCN (10.0 mL)
[anode], and NaOPiv·H2O (2.0 equiv.), HOPiv (8.0 equiv.), MeOH (10.0
mL) [cathode] in H-type divided cell with carbon cloth anode (15 mm×15
mm×0.36 mm), nickel plate cathode (15 mm×15 mm×1.0 mm) and a AMI-
7001-30 membrane, constant current = 10.0 mA (janode = 4.4 mA/cm2), ni-
trogen balloon, 65 ºC, 3 h (4.5 F). Isolated yields are shown.
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Initially, we chose N-(quinolin-8-yl)thiophene-2-carboxamide
at cathode (Table 1, entry 8). Keeping constant electric quantity,
increasing or decreasing electric current resulted in lower yields
(Table 1, entries 9 and 10). In addition, this reaction couldn’t occur
under undivided cell (Table 1, entry 11). Finally, the control exper-
iment indicated that both Co(OAc)2·4H2O and electricity were es-
sential for this reaction (Table 1, entries 12 and 13).
(1a) and morpholine (2a) as standard substrates. After unremitting
efforts, under constant-current electrolysis at 10 mA for 3 h, 74 %
isolated yield of the desired product (3aa) could be obtained in the
presence of 20 mol% Co(OAc)2·4H2O and 1 equiv. NaOPiv·H2O
in MeCN at 65 ºC (Table 1, entry 1). Replacing Co(OAc)2·4H2O
by CoCl2·6H2O or Co(acac)2 would lead to the decreased yields
(Table 1, entries 2 and 3). While we attempted to use NaOAc or
HOPiv as additive at anode, lower yields would be obtained in this
transformation (Table 1, entries 4 and 5). Then we investigated the
effect of different solvents, MeCN exhibited the best transformati-
on compared with DMF and CF3CH2OH (Table 1, entries 6 and 7).
The yield would decrease slightly when replacing MeOH by H2O
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With the optimized protocols in hand, the substrate scope of am-
ides was screened next (Scheme 1). Firstly, we explored the reacti
vity of various aromatic amides. Thiophene-2-carboxamide, furan-
2-carboxamide, benzothiophene-2-carboxamide and naphthalene-
1-carboxamide were compatible in the reaction (3aa-3ca, 3pa), 8-
aminoquinolinebenzamide could afford 61 % yield (3da). Ben-
zamide possessing para or ortho methyl could furnish the desired
product in moderate yield (3ea and 3fa). As for the benzamide pos-
sessing meta methyl, exclusive product could be obtained in lower
yield at the less hindered ortho position (3ga). To our delight, other
electron-neutral substituents, such as fluoride, chloride and bro-
mide group, as well as phenyl group, could also be tolerated and
gave desirable yields (3ha-3ka). Benzamide bearing electron-rich
groups, such as methoxyl, showed moderate efficiency in the trans-
formation (3la). Moreover, benzamide possessing electron-
withdawing groups participated in the reaction smoothly, obtained
in acceptable yields (3ma-3oa).
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Scheme 1. Substrate Scope of Amides.a
Scheme 2. Substrate Scope of Alkylamines.a
a Reaction conditions: 1a (0.25 mmol), 2a (2.0 equiv.), Co(OAc)2·4H2O (20
mol%), NaOPiv·H2O (1.0 equiv.), nBu4NBF4 (2.0 equiv.), MeCN (10.0 mL)
[anode], and NaOPiv·H2O (2.0 equiv.), HOPiv (8.0 equiv.), MeOH (10.0
mL) [cathode] in H-type divided cell with carbon cloth anode (15 mm×15
mm×0.36 mm), nickel plate cathode (15 mm×15 mm×1.0 mm) and a AMI-
7001-30 membrane, constant current = 10 mA (janode = 4.4 mA/cm2), nitro-
gen balloon (1 atm.), 65 ºC, 3.0 h (4.5 F). Isolated yields are shown. b Con-
stant current = 12 mA (janode = 4.4 mA/cm2), 3.5 h (6.3 F). c The yield was
determined by 1H NMR spectroscopy with CH2Br2 as the internal standard.
After investigating the scope of amides, we explored varieties of
a Reaction conditions: 1a (0.25 mmol), 2a (2.0 equiv.), Co(OAc)2·4H2O (20
mol%), NaOPiv·H2O (1.0 equiv.), nBu4NBF4 (2.0 equiv.), MeCN (10.0 mL)
[anode], and NaOPiv·H2O (2.0 equiv.), HOPiv (8.0 equiv.), MeOH (10.0
mL) [cathode] in H-type divided cell with carbon cloth anode (15 mm×15
mm×0.36 mm), nickel plate cathode (15 mm×15 mm×1.0 mm) and a AMI-
7001-30 membrane, constant current = 10 mA (janode = 4.4 mA/cm2), nitro-
gen balloon (1 atm.), 65 ºC, 3.5 h (5.2 F). Isolated yields are shown. b Con-
stant current = 10 mA (janode = 4.4 mA/cm2), 3.0 h (4.5 F).
alkylamines under optimized conditions (Scheme 2). Some cyclic
alkylamines could participate in the reaction, such as piperidine,
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thiomorpholine and 1,2,3,4-tetrahydroisoquinoline; afforded me-
occurring in the electrolysis (Fig. 2). In blank experiment, current
density was close to nought. After addition of Co(OAc)2·4H2O,
current density was big at first and then experienced the fast decay
to reach relatively steady state. This result indicated that the current
decay arose from consumption of Co(II).
dium yields (3ab-3ad). When piperidine or piperazine was substi-
tuted with some electron-withdrawing groups, desired products
would be obtained in moderate to good yields (3ae-3ag). It was ob-
served that hydroxyl could also be tolerated in this transformation
(3ah); no by-product was observed by C-H/O-H coupling. Unfor-
tunately, when we investigated different chain amines, only N-
methylbenzylamine could give desired product in inferior yield
(3ai); other chain amines, such as diethylamine and dibutylamine,
would afford homo-coupling product of thiophene-2-carboxamide.
Primary alkylamines were not suitable for this transformations,
which might result from the coordination to Co(II) and over-oxida-
tion of primary alkylamines.
The scalability of electrochemical cobalt-catalyzed C-H amina-
tion was evaluated in a 5.0 mmol scale (Scheme 3). The reaction
between 1a and 2a furnished the desired product in 59 % yield,
which shows great potential of this electrochemical cobalt-cata-
lyzed C-H/N-H cross-coupling.
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2
3
4
5
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7
8
0.35
[Co]
Blank
0.30
0.25
0.20
0.15
0.10
0.05
0.00
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0
400
800
1200
1600
Time (S)
Scheme 3. Gram Scale Experiment.
Figure 2. Chronoamperometry Curves
Based on the experimental results and literature reports,5b,6c,6d,13
we attempted to propose two plausible mechanism. Path I: Co(II)
was oxidized to Co(III) at anode; then Co(III) coordinated to N-
(quinolin-8-yl)benzamide to get Co(III)-complex B. Path II: In the
presence of base, Co(II) coordinated to N-(quinolin-8-yl)ben-
zamide to get Co(II)-complex A before electrolysis. This Co(II)-
complex A was oxidized at anode to furnish Co(III)-complex B. In
the presence of base, C-H activation took place and Co(III)-
complex B was attacked by morpholine to form Co(III)-complex
C, followed by reductive elimination of Co(III)-complex C to re-
lease the desired product and Co(I) species. Co(I) species was re-
oxidized to Co(II) at anode to complete the whole catalytic cycle of
Co.
To gain some insights into this reaction mechanism, we carried
out kinetic isotope effect experiment and cyclic voltammetry ex-
periment. Firstly, we demonstrated intermolecular competition ex-
periment between 1d and [D5]-1d (Scheme 4, a), the ratio of C-H
bond amination products 3da and [D4]-3da is 1.13:1. The intramo-
lecular competition experiment has been demonstrated in this trans-
formation (Scheme 4, b). Reaction of the monodeuterated substrate
1d led to an 63:37 ratio of product isotopologues (KIE= 1.70).
These results indicated that C−H bond cleavage might not be in-
volved during the rate-limiting step.
Scheme 5. Proposed Mechanism.
Scheme 4. Kinetic Isotope Effect Experiment.
In conclusion, we have developed cobalt-catalyzed electrooxida-
tive C-H amination of arenes in divided cells. Various functional
groups are tolerated in this transformation. Compared with previ-
ous cobalt-catalyzed C-H functionalization, no external oxidants
are needed; lower temperature and good scalability are also bene-
Furthermore, we carried out cyclic voltammetry experiment (see
ESI, Fig: S1). The naught potential E012 of Co(OAc)2·4H2O was
1.269 V. Then we added 1e and Co(OAc)2·4H2O together; the
naught potential E0 turned to 1.460 V. Finally, we performed chron-
oamperometry to proof the hypothesis for the oxidation of Co(II)
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ASSOCIATED CONTENT
Supporting Information
The experimental procedure, characterization data, and copies of
1H and 13C NMR spectra. This material is available free of charge
via the Internet at http://pubs.acs.org.
9
AUTHOR INFORMATION
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Corresponding Author
*E-mail: aiwenlei@whu.edu.cn.
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Author Contributions
‡Xinlong Gao and Pan Wang contributed equally.
Notes
The authors declare no competing financial interests.
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ACKNOWLEDGMENT
This work was supported by the National Natural Science Founda-
tion of China (21390400, 21520102003, 21272180, 21302148), the
Hubei Province Natural Science Foundation of China
(2013CFA081), the Research Fund for the Doctoral Program of
Higher Education of China (20120141130002), and the Ministry of
Science and Technology of China (2012YQ120060). The Program
of Introducing Talents of Discipline to Universities of China (111
Program) is also appreciated.
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