Electroreductive Cobalt-Catalyzed Carboxylation: Cross-Electrophile Electrocoupling with Atmospheric CO2

Article abstract of DOI:10.1002/anie.202003218

The chemical use of CO₂ as an inexpensive, nontoxic C1 synthon is of utmost topical interest in the context of carbon capture and utilization (CCU). We present the merger of cobalt catalysis and electrochemical synthesis for mild catalytic carb

Full text of DOI:10.1002/anie.202003218

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Accepted Article
Title: Electro-Reductive Cobalt-Catalyzed Carboxylation: Cross-
Electrophile Electro-coupling with Atmospheric CO2
Authors: Nate W. J. Ang, Joao Carlos Agostinho de Oliveira, and Lutz
Ackermann
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Electro-Reductive Cobalt-Catalyzed Carboxylation: Cross-
Electrophile Electro-coupling with Atmospheric CO2
Nate W. J. Ang,[a] João C. A. Oliveira,[a] Lutz Ackermann*[a,b]
Abstract: The chemical use of CO2 as inexpensive, non-toxic C1
synthon is of utmost topical interest towards a carbon capture and
utilization (CCU) strategy. We present the merger of cobalt catalysis
and electrochemical synthesis for mild catalytic carboxylations of
allylic chlorides with CO2. Styrylacetic acid derivatives were obtained
with moderate to good yields and good functional group tolerance.
The thus-obtained products are useful as versatile synthons to γ-
arylbutyrolactones. Cyclic voltammetry and in-operando kinetic
analysis were performed to provide mechanistic insights into the
electrocatalytic carboxylation with CO2.
Recent advances for electro-carboxylation[14] include elegant
palladium-catalyzed reductive transformations of allyl esters to
useful carboxylic acids as reported by Mei (Scheme 1a).[15] Based
on precedence (Scheme 1)[16] including the work of Perichon,
where they reported an electrocarboxylation of cinammyl chloride
with the use of Hg pool cathode and Co(salen) complex.[16e]
Moreover, the effective usage of electrochemistry for the
reductive carboxylation, it is intriguing to unravel effective 3d-
metal catalysts for the carboxylation reactions that are
environmentally friendly. Herein, we report on a cobalt-catalyzed
carboxylation of allylic chlorides with CO2, featuring electricity as
the sole reducing agent to access styrylacetic acid derivatives
(Scheme 1b) as they are particularly useful as key synthons of
numerous γ-arylbutyrolactones, which are structural motifs found
in various natural products.[17]
The surge in the levels of carbon dioxide in the atmosphere
nowadays are caused mainly by the industrialisation of raw
material productions. A major component of greenhouse gases
CO2 attributes to the global climate change with the increase in
atmospheric temperature.[1] However, CO2 can be used as an
excellent C1 synthon/building block[2] for molecular syntheses and
one successful utilisation is the catalytic production of
polycarbonates and cyclic carbonates from epoxides.[3]
Carboxylation reactions are particularly desirable due to the
formation of kinetically stable C–C bonds.[4] Cross-electrophile
reactions have emerged as a powerful alternative for the
formation of C–C bonds explicitly from electrophiles, providing an
improvement in step-economy.[5] Since CO2 is thermodynamically
stable and kinetically inert with a high activation barrier, its use as
an inert electrophile mostly requires highly reactive nucleophiles,
such as high-energy Grignard reagents.[6] The use of metal
catalysts have favoured such transformations by lowering the
activation energy needed.[7] In the past, precious metals, such as
palladium and rhodium, dominated the field of carboxylation.[8]
However, recently, 3d-transition metals have gained major
Scheme 1. Cobalt-catalysed electro-assisted carboxylation.
We initiated our studies by optimizing the reaction conditions
(Table 1) on the envisioned electro-carboxylation. Different cobalt
salts were used as pre-catalysts with cinnamyl chloride 1a as the
substrate. In particular, Co(salen) did not perform well, even at a
higher loading of 10 mol % (entry 5). A simple Co(OAc)2 gave the
best result, alongside CoCl2 with a slight decrease in yield (see
Supporting Information). Control experiments verified the
important role of the electricity and cobalt pre-catalyst (entries 3-
4). The reaction was performed under constant current
electrolysis, the required amount of current to provide full
conversion of the starting material was found to be 10 mA for 6
hours with a Faradaic yield of 13%. Notably, no reaction was
observed without current. We found that polar aprotic solvents,
such as DMF and DMSO, performed well for the direct
carboxylation.[18] Alternative ligands were explored, including
bidentate nitrogen-containing ligands, such as bipyridine and
1,10-phenantroline, performed poorly (entries 6-7).[19] Instead,
cost-effective triphenylphosphine ligands gave the best results.
Different electrodes were next probed for both the cathode and
the anode (entries 9-12). The platinum cathode gave lower yield
as compared with nickel foam as the cathode choice. Even though
a few different anodes were tried, magnesium proved to be useful
momentum and are sought after due to their abundance and lower
9]
toxicities.[8b,
Notable examples of both precious and 3d-
transition metal include Satos’ studies on palladium-catalyzed
carboxylations of allylic alcohols, and cobalt-catalyzed allylic
C(sp3)–H carboxylation with CO2 respectively.[10] Yet, both
transformations used strong reducing agents, such as ZnEt2 and
AlMe3. Similarly, Mei and Martin independently realized a nickel-
catalyzed carboxylation of allylic alcohols using super-
stoichiometric amounts of manganese or zinc powder as the
reducing agent.[11] Electrocatalysis with 3d-metal catalysts[12] has
emerged as powerful tool for sustainable molecular syntheses.[13]
[a]
N. W. J. Ang, Dr. J. C. A. Oliveira, Prof. Dr. L. Ackermann
Institut für Organische und Biomolekulare Chemie
Georg-August-Universität Göttingen
Tammannstraße 2, 37077 Göttingen (Germany)
E-mail: Lutz.Ackermann@chemie.uni-goettingen.de
Homepage: http://www.ackermann.chemie.uni-goettingen.de/
[b]
Prof. Dr. L. Ackermann
Wöhler Research Institute for Sustainable Chemistry (WISCh)
Georg-August-Universität Göttingen
Tammannstraße 2, 37077 Göttingen (Germany)
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10.1002/anie.202003218
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COMMUNICATION
in decreasing the high overpotential for the carboxylation to occur.
Moreover, the reaction was also performed with chemical
reductants, such as manganese and zinc, but to no avail even at
elevated temperature (entries 13-14).[19]
only to a certain extent as 5-10% of the product were
dehalogenated giving rise to a small mixture of 2a in the product.
This was explicitly shown when para-iodo containing substrate
was tested and 40% of the dehalogenated product was isolated.
Under otherwise identical reaction conditions, the use of alkyl-
substituted and heterocyclic-substituted substrates provided as of
yet unsatisfactory results.[19]
Table 1. Optimization of cobalt-catalyzed electro-reductive carboxylation[a]
Entry
Deviation from standard conditions
Yield[b]
1
2
---
59% (1:1)
42% (1:1)
---
CCE = 5 mA
3
no current
4
without catalyst for 16 h
Co(salen) (5 mol %)
dppe instead of PPh3
bipyridine instead of PPh3
0.1 mol/L of 1a
Pt cathode
13% (1:1)
27% (1:1)
27% (1:1)
8% (1:2)
44% (1:1)
35% (1:1)
37% (1:1)
10% (1:1)
38% (1:1)
traces
5
6
7
8
9
10
11
12
13
14
15
16
Fe anode
Cu anode
Zn anode
Mn reductant, no electricity
Zn reductant, no electricity
T = 60 °C
---
42% (1:1)
58% (1:1)
CoCl(PPh3)3 3[c]
Scheme 2. Cobalt-catalysed electro-reductive carboxylation of cinnamyl
chlorides 1 with CO2. Regioselectivity 2/2’ given in parentheses, only major
products are shown. [a] A mixture with 5% dehalogenated product 2m.
[a] Undivided cell, 1a (0.25 mmol), cobalt(II) acetate (10 mol %), PPh3
(20 mol %), electrolyte (1.0 equiv), solvent (5.0 mL), 25 °C, 6 h, Mg foil electrode
(3.0 mm x 15 mm x 0.2 mm), Ni foam electrode (10 mm x 15 mm x 1.0 mm),
constant current electrolysis (CCE) at 10 mA. [b] Isolated yield. Regioselectivity
2a/2a’ given in parentheses. [c] 2 h reaction time.
To better understand the catalyst mode of action DFT calculations
were
carried
out
at
the
PW6B95-D4/def2-TZVPP+
SMD(DMF)//TPSS-D3(BJ)/def2-SVP level of theory (Figure 1).[19]
The isomerisation step of η3-allyl complex to η1-allyl complex
revealed to be not rate determining due to the low energy barrier
of 16.1 kcal mol-1 for product 2l. Given that the electrocatalysis of
the cross-electrophiles was performed at relatively high current
and high CO2 partial pressure, we direct our focus to the allylic C–
C bond formation. The latter is preferred for the chlorinated
substrate over the brominated substrate by 1.5 kcal mol-1.
Therefore, the DFT studies have shown to be in agreement with
the experimentally observed regioselectivity of the product 2l.
With the optimised reaction conditions in hand, we explored
the substrate scope of the cobaltaelectro-carboxylation reaction
(Scheme 2). Alkyl substituents in the ortho or para position of the
cinnamyl chlorides (1b-d) were well accepted to furnish the
products 2b-d. In addition, para-substituted phenyl containing 2e’
and polycyclic rings such as anthracene 2f’, gave moderate yield,
with higher branched selectivity. Electron-donating groups, such
as benzodioxole 2g’, thioether 2h’ and methoxy 2i, were well
tolerated for this reaction. The regioselectivity however differed as
2h’ favoured more towards the branched product, while substrate
2i gave higher preference for the linear product. Electron-
withdrawing substituents, such as trifluoromethyl 2j’, resulted in
good yield, with an improved regioselectivity for the branched
product. Halogen containing substrates 1k-m resulted in good
yields of the carboxylated products 2k-m, with fluoro 2k and
chloro 2l resulting in a higher selectivity for the linear product. The
product 2m’ gave an indication that the condition was tolerated
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10.1002/anie.202003218
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in the positive range.[25] These results postulated that the
oxidative addition of the substrate onto the active cobalt catalyst
is possibly not involved in the rate-determining step.
Stoichiometric reactions were also conducted with complex 3
without supply of electricity to rule out the possibility of in-situ
formed cobalt(III) being in the CO2 activation step. Thus, cathodic
reduction of cobalt(III) intermediate to cobalt(I) is required to
facilitate the carboxylated product.
A plausible catalytic cycle is proposed based on the obtained
results (Scheme 3).[26] Initially, coordination of the alkene 1a onto
the active cobalt(I) catalyst occurs. This, then, promotes the
cleavage of the adjacent allylic C–H bond resulting in an oxidative
addition of substrate 1a to form an η3-allyl-cobalt(III) intermediate
II. At this stage, the intermediate II could undergo rearrangement
to form η1-allyl-cobalt(III) intermediate III-A and III-B depending
on different ligand effects. For instance, heteroatom such as O-
atom containing ligands are known to promote tautomerization of
η3- to η1-allyl intermediates in related cobalt complexes.[10a] There
are two possible pathways from intermediates III, they can both
undergo cathodic reductions to give the corresponding low valent
η1-allyl-cobalt(I) species IV, which could be stabilized by an
alkenyl or aryl ligand.[27] This determines the regioselectivity of the
product which is highly dependent on the ligand being employed.
Here, the linear product is formed through C–C bond formation
with CO2 at the γ-position[28] to form the carboxylated product 2
and 2’.
Figure 1. Computed relative Gibbs free energies in kcal mol-1 for the a)
isomerisation of η3-allyl complex to η1-allyl, and b) allylic C–C bond formation at
the PW6B95-D4/def2-TZVPP+SMD(DMF)//TPSS-D3(BJ)/def2-SVP level of
theory. Hydrogen in the computed transition state structures were omitted for
clarity.
In order to understand the mechanism of this cobaltaelectro-
catalyzed carboxylation reaction with CO2, we sought to
investigate the mode of action. First, we elucidated the kinetic
profile (Figure 2a) of the standard reaction condition together with
the different simple cobalt salts as pre-catalyst for comparison in
terms of the rate of reaction. An in-operando infra-red
spectroscopy (IR) method was adopted in this case. To our delight,
simple Co(OAc)2 and the halide salts performed in a superior
fashion (Figure 2b) since higher catalytic loading of Co(salen) was
tried, but did not improve the yield.[20] Second, the pre-formed
reduced cobalt(I) intermediate was of interest as this might
indicate whether it is involved in the rate-determining step of this
particular system. One such low valent cobalt(I) intermediate has
been reported in the past for its use on amination reaction of
unactivated aryl iodides[21] and among others for C–H activation
reactions.[22]
100
a)
80
-1
peak at 755 cm
peak at 685 cm
-1
60
40
20
0
0
1
2
3
4
5
6
t / h
0,5
0,4
0,3
0,2
0,1
0,0
b)
A
B
C
D
E
F
Detailed mechanistic studies performed by means of cyclic
voltammetry revealed that simple cobalt(II) complexes did not
interact with the allylic chloride 1a (Figure 3a). The reduction
potential of the parent cinnamyl chloride 1a was shown to be
irreversible at E = −1.90 V vs. SCE. Interestingly, the cobalt(I)
complex 3 showed one irreversible reduction peak at E = −1.82 V
vs. SCE (Figure 3b) which could correspond to the reduction of
cobalt(I) to cobalt(0).[23] However, the addition of substrate 1a,
resulted in an oxidative addition of the substrate onto the cobalt(I)
complex 3 to give a cobalt(III) intermediate. This could be seen as
there are two reduction peaks and they could be plausibly
assigned as E = −1.70 V vs. SCE for the reduction of cobalt(II) to
cobalt(I) and E = −1.95 V vs. SCE for the reduction of cobalt(I) to
cobalt(0) (Figure 3b).[24] The reduction of cobalt(III) to cobalt(II)
was not observed as they have a much higher potential, usually
A: Co(OAc)
2
B: CoBr
2
C: CoCl
2
D: Co(salen)
E: Co(acac)2
F: CoI
2
0
1
2
3
4
t / h
Figure 2. a) Kinetic profile with 3D surface plot. b) Comparison of various cobalt
catalyst.
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Acknowledgements
blank in CO2
a)
1a in CO2
50
0
Generous support by the DFG (Gottfried-Wilhelm-Leibniz award
to LA) is gratefully acknowledged.
Co(OAc)2 + PPh3
Co(OAc)2 + PPh3 + 1a
-50
Conflict of interest
The authors declare no conflict of interest.
-100
-150
Keywords: cobalt • carboxylation • reductive • coupling •
electrocatalysis
-3,2 -3,0 -2,8 -2,6 -2,4 -2,2 -2,0 -1,8 -1,6 -1,4 -1,2
Potential (V vs. SCE)
b)
20
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In summary, we have developed an effective cobalt
phosphine catalyst for the cross-electrophile electro-coupling of
allylic chlorides with ambient, being devoid of harsh chemical
reductants. In-operando IR spectroscopy and cyclic voltammetry
provided detailed insights into the reaction mechanism.
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COMMUNICATION
Nate W. J. Ang, João C. A. Oliveira, Lutz
Ackermann*
Page No. – Page No.
Electro-Reductive Cobalt-Catalyzed
Carboxylation: Cross-Electrophile
Electro-Coupling with Atmospheric
CO2
Text for Table of Contents
Cobalta-electrocarboxylation: An allied co-operation between cobalt catalysis and
electrochemical synthesis enabled the mild catalytic carboxylation of allylic chlorides with
atmospheric CO2.
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