Direct Carboxylation of Aryl Tosylates by CO2 Catalyzed by in situ-Generated Ni0

Article abstract of DOI:10.1002/chem.201503926

A novel Ni⁰-catalyzed carboxylation of aryl tosylates with carbon dioxide has been achieved under moderate temperatures and atmospheric pressure. In this procedure, the active Ni⁰ species is generated in situ by simply mixing the Ni⁰ precatalyst [NiBr₂(bipy)] with an excess of manganese metal. This approach requires neither a glove-box nor the tedious preparation of sophisticated intermediate organometallic derivatives. This mild, convenient, and user-friendly process is successfully applied to the valorization of carbon dioxide and the synthesis of versatile reactants with broad tolerance of substituents.

Full text of DOI:10.1002/chem.201503926

DOI: 10.1002/chem.201503926
Full Paper
&
Nickel Catalysis
Direct Carboxylation of Aryl Tosylates by CO2 Catalyzed by In situ-
Generated Ni0
Fatima Rebih,[a] Manuel Andreini,[a] AurØlien Moncomble,[b] Anne Harrison-Marchand,[a]
Jacques Maddaluno,[a] and Muriel Durandetti*[a]
Abstract: A novel Ni0-catalyzed carboxylation of aryl tosy-
lates with carbon dioxide has been achieved under moder-
ate temperatures and atmospheric pressure. In this proce-
dure, the active Ni0 species is generated in situ by simply
mixing the Ni0 precatalyst [NiBr2(bipy)] with an excess of
manganese metal. This approach requires neither a glove-
box nor the tedious preparation of sophisticated intermedi-
ate organometallic derivatives. This mild, convenient, and
user-friendly process is successfully applied to the valoriza-
tion of carbon dioxide and the synthesis of versatile reac-
tants with broad tolerance of substituents.
Introduction
functionalized compounds by nickel-catalyzed cross-coupling
reactions, resorting to a methodology that allowed the in situ
generation of Ni0. This procedure relied on the reduction of
a very stable NiII complex, [NiBr2(bipy)], by Mn0 as a finely
grown metallic powder, in the presence of the reaction sub-
strates.[6a] After the oxidative addition of Ni0, the arylnickel in-
termediate proved to be reactive toward a-chloro esters,[6a]
leading to aryl propanoic esters in good yields, as well as
chloropyridines, affording arylpyridines[7] (Scheme 1). We later
Cross-coupling reactions play a leading role in modern syn-
thetic organic chemistry and palladium has proven to be an
outstandingly versatile catalyst for this type of reactions, as
recognized by the award of the 2010 Nobel Prize in chemistry
to Heck, Negishi, and Suzuki.[1] Owing to the scarcity and,
therefore, the high price of this noble metal, inexpensive alter-
native systems based on simple and effective nickel,[2] iron,[3]
and cobalt[4] salts are becoming commonplace. Although sev-
eral elegant studies relying on iron-based catalysts have been
reported,[3] nickel complexes seem, at the moment, more ver-
satile for performing direct carbon–carbon bond-forming reac-
tions. New nickel-based methods exhibit significant advantag-
es over highly reactive palladium complexes, such as air-stable
precatalysts and minimization of side reactions. However,
cross-coupling reactions involving nickel generally call for the
preliminary preparation of organometallic nucleophiles that
undergo transmetalation with nickel salts.[5] Therefore, the de-
velopment of direct procedures that allow CÀC bond forma-
tion while avoiding sensitive organometallic species remains
a challenge, especially when functionalized precursors are
used.[6] We previously reported a method that provided highly
Scheme 1. Synthesis of aryl propanoic esters and arylpyridines by nickel cat-
alysis.
showed that arylnickel intermediates are also reactive toward
alkynes, providing an efficient and stereoselective intramolecu-
lar access to various (hetero)aromatic compounds in good
yields.[8] The major advantage of this simple approach is that it
puts organonickel chemistry within reach of the entire organic
chemistry community.
[a] Dr. F. Rebih, Dr. M. Andreini, Dr. A. Harrison-Marchand, Dr. J. Maddaluno,
Dr. M. Durandetti
Laboratoire COBRA CNRS UMR 6014 & FR 3038, UniversitØ de Rouen
INSA de Rouen, 76821 Mt St Aignan Cedex (France)
E-mail: muriel.durandetti@univ-rouen.fr
To further improve this method, we report herein the re-
placement of aryl iodides or bromides by tosylates. These less
reactive substrates remain suitable for oxidative addition while
being cheaper than aryl halides and easily accessible from the
corresponding alcohols and phenols. Arylsulfonates have been
successfully used in palladium-catalyzed reactions,[9] such as
the Suzuki–Miyaura coupling, and are regarded as robust part-
ners that are particularly stable toward hydrolysis. However,
[b] Dr. A. Moncomble
Laboratoire de Spectrochimie Infrarouge et Raman (LASIR)
CNRS UMR 8516; UniversitØ de Lille, Sciences et Technologies
59655 Villeneuve d’Ascq Cedex (France)
Supporting information and ORCIDs from the authors for this article are
available on the WWW under http://dx.doi.org/10.1002/chem.201503926.
Part of a Special Issue “Women in Chemistry” to celebrate International
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nickel catalysts,[10] and in particular [Ni(cod)2], have also been
known to activate arylsulfonates. In light of these data, it was
tempting to investigate the reactivity of tosylates in the pres-
ence of our in situ-generated Ni0 catalyst to perform the direct
carboxylation of s-arylnickels by CO2 (Scheme 2).
Table 1. Nickel-catalyzed synthesis of various carboxylic acid from aryl to-
sylates.[a]
Entry
Aryl tosylate
Coupling product[b]
Yield [%][c]
1
2
61
54
Scheme 2. Ni-catalyzed carboxylation of arylsulfonates.
3
4
5
56
57
51
Results and Discussion
The aryl tosylates were easily prepared in high yields (79–99%)
by treating substituted phenols with tosyl chloride. The reac-
tivity of the aryl tosylates toward Ni0 was first evaluated by
a test homocoupling reaction (2ArÀOTs!Ar2). The results
showed that our in situ Ni0 system successfully catalyzes this
dimerization.[11] With this firm proof of concept for the oxida-
tive addition of Ni0 into the CArÀOTs bond in hand, we focused
on the direct carboxylation of the same substrates with carbon
dioxide. This attractive electrophile is cheap and (overly) abun-
dant and is expected to provide aromatic carboxylic acids, de-
rivatives of which are known to be important and ubiquitous
products.[12] Many routes to selected structures have been de-
scribed, by oxidation of benzyl alcohols[13] or aryl aldehydes,[14]
by hydrolysis of nitriles,[15] or by reaction of aryl metals with
malonitriles,[16] CO,[17] or CO2.[18] Processes that use catalytic
amounts of metals have also been proposed for this latter
transformation,[19] as well as direct CÀH carboxylation.[20] Initial-
ly, the electrosynthesis of aryl carboxylate catalyzed by
nickel[21] or palladium[22] complexes was achieved by using
a sacrificial anode. Later on, Correa and Martín reported the
direct carboxylation of various aryl bromides through a Pd-cat-
alyzed method.[23] Recently, a purely chemical (i.e., non-electro-
chemical) process was achieved by Tsuji and co-workers, using
a [NiCl2(PPh3)2] precursor, which was reduced in situ by Mn
metal, in 1,3-dimethyl-2-imidazolidinone (DMI) as solvent.[24]
This process is efficient for the carboxylation of aryl or vinyl
chlorides, but only in the presence of NEt4I as additive (proba-
bly involving a Cl/I exchange).[25] More recently, Martín and co-
workers developed a [NiCl2(dppf)]-catalyzed carboxylation of
naphthyl pivalates in DMA [dppf=1,1’-bis(diphenylphosphino)-
ferrocene].[26] The process, running at 808C for 48 h, was limit-
ed to naphthyl derivatives, since other aryl pivalates only led
to traces of benzoic acids. Overall, direct carboxylation by un-
activated CO2 in a process that involves a cheap metal catalyst
and is applicable to a large variety of aryl substrates remains
a chemical and environmental challenge.
6
7
44
58
8
9
53
58
10
47
84
11[d]
12[d]
36
[a] Conditions (unless otherwise stated): aryl tosylate (1 mmol), manga-
nese metal (2 mmol), [NiBr2(bipy)] (0.1 mmol), DMF (5 mL), CO2 atmos-
phere[27] at 608C for 5–10 h; [b] all products gave satisfactory analytical
data, in good agreement with literature; [c] yields of isolated products,
based on initial aryl tosylates; [d] reaction is conducted at room tempera-
ture.
608C under one atmosphere of CO2,[27] into the expected acids
with uniform conditions, regardless of the substituent. It is
noteworthy that the corresponding aryl iodides reacted even
at room temperature (Table 1, entry 11). Whereas Martín’s con-
ditions were not applicable to conventional benzene motifs,[26]
our method converts the aryl tosylates in moderate to good
chemical yields, even for substrates with electron-donating or
-withdrawing substituents. In all cases, biaryls (10–30%) were
formed as by-products arising from homocoupling of the aryl
tosylates.[11] Finally, the versatility of the process was demon-
strated by using phenyl tosylates bearing sensitive functional
groups, such as nitrile, ester, or ketone (Table 1, entries 7–8,
11). These substrates are clearly incompatible with Grignard or
organolithium reagents. Complementarily to the method of
We first attempted the direct formation of benzoic acids
from a range of aryl tosylates, using the [NiBr2(bipy)]/Mn0
system, which avoids the preparation of an organometallic
species and performs well in the absence of any additive
(Table 1). The aryl tosylates were transformed efficiently, at
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Tsuji, which does not apply to ortho-substituted aromatics,[24]
our system transforms, in the absence of any iodinated addi-
tive, sterically hindered substrates into the corresponding car-
boxylic acids under the same catalytic conditions (Table 1, en-
tries 6, 8, and 10). In these cases, lower yields were obtained,
probably due to steric effects.
away and the original voltammogram of [NiBr2(bipy)] is re-
stored. This clearly shows that the catalytic cycle begins in
a similar way to that with aryl halides, that is, in the first step
the low-valent nickel complex generated at the cathode at
À1.05 V/SCE reacts with PhOTs to give the [PhNiIIX] intermedi-
ate (X=OTs), which is further reduced into [PhNiI] at a slightly
lower potential. The value of the kinetic constant k0 of the oxi-
dative addition was determined using the method described
Notably, 2-methyl-1-tosyl-naphtyl, an o,o’-disubstituted tosy-
late, could be converted into the expected acid, albeit in mod-
erate yield (Table 1, entry 10). In addition, the access to a para-
cyclophane derivative, [2.2]PC, was shown to be possible from
a [2.2]PC bromoester prepared according to a literature proce-
dure.[28] Our methodology led, after hydrolysis, to the carboxyl-
ic derivative in 36% yield, whereas the addition product was
obtained in only 15% yield when the halogen-metal exchange
was performed with nBuLi. This reaction was completely ineffi-
cient with magnesium.
by Nicholson and Shain,[30] which is based on the measurement
[PhOTs]
of the (iox/ired
)
ratio at a given PhOTs excess, as compared
to the system in the absence of PhOTs ((iox/ired)0).[31] The rate
constant is thus estimated as k0 =5.7Æ0.6 molÀ1 LsÀ1. Thus, Ni0
inserts more slowly into the CÀO bond of phenyl tosylate than
into the CÀBr bond of aryl bromides (k0 =69 molÀ1 LsÀ1 for
PhBr, and 14 molÀ1 LsÀ1 for o-tolylBr).[29b] Finally, this value is
very close to that obtained with ortho-electron-donor-substi-
tuted aryl bromides (k0 =6.7 molÀ1 LsÀ1 for o-bromoanisole).
Next, the electrochemical behavior of the s-arylnickel com-
plex in saturated CO2 atmosphere was studied. A preliminary
bubbling of CO2 into the same solution of [NiBr2(bipy)] and
PhOTs resulted in the modified cyclic voltammogram displayed
in Figure 1, curve c. The two reduction waves of the s-arylnick-
el at À1.2 and À1.4 V/SCE disappeared, whereas a new one at
À1.35 V/SCE appeared, whatever the scan rate of potentials. To
assign this peak, the electrochemical behavior of [NiBr2(bipy)]
To gain insight into the catalytic mechanism, we carried out
a series of electrochemical experiments. These studies were ini-
tiated by determining the kinetic constant for the oxidative ad-
dition of electrogenerated Ni0 with aryl tosylate. The cyclic
voltammogram of [NiBr2(bipy)] in DMF containing tetrabuty-
lammonium tetrafluoroborate as supporting electrolyte is pre-
sented in Figure 1.
alone under
(Figure 2).
a saturated CO2 atmosphere was studied
Figure 1. Cyclic voltammogram in DMF+0.1m NBu4BF4, at a gold-disk mi-
croelectrode (0.25 mm diameter) at v=0.2 VsÀ1 at room temperature:
a) 10À2 m [NiBr2(bipy)]; b) 10À2 m [NiBr2(bipy)] in the presence of 5”10À2
m
PhOTs ; c) 10À2 m [NiBr2(bipy)] in the presence of 5”10À2 m PhOTs in CO2 at-
mosphere.[27]
Figure 2. Cyclic voltammogram in DMF + 0.1m NBu4BF4, at a gold-disk mi-
croelectrode (0.25 mm diameter) at v=0.2 V. sÀ1 and at room temperature:
(a) 10À2 m [NiBr2(bipy)]; (b) 10À2 m [NiBr2(bipy)] in CO2 atmosphere.[27]
We propose that the catalytic cycle involved in this reaction
begins similarly to that which operates in the dimerization of
aryl halides.[29] Indeed, the voltammogram obtained for phenyl
tosylate (PhOTs) in the presence of [NiBr2(bipy)] (Figure 1) is
very close to that obtained for C6H5Br.[29b] That the NiII/Ni0
system slightly shifts towards positive potentials (Ep =À1.0 V/
SCE vs. À1.05 V/SCE for [NiBr2(bipy)] alone; SCE=saturated cal-
omel electrode) indicates that a chemical reaction takes place
right after the electrochemical reduction. The peak height is
unchanged, while two new peaks appear at À1.2 and À1.4 V/
SCE, respectively. Concurrently, during the reverse scan, the Ni0
re-oxidation peak at À0.9 V/SCE disappears. At higher scan
rates, the peak at À1.2 V/SCE then that at À1.4 V/SCE fade
Whereas the first two-electron reduction wave at À1.05 V/
SCE remains unchanged, a similar peak at À1.35 V/SCE appears
along with a large peak at around À1.7 V/SCE. The latter does
not correspond to the direct reduction of free CO2, which
takes place at À2.2 V.[32a,b] Nickel-coordinated carbon dioxide
complexes are well known,[32] and previous results on [Ni(bi-
py)3](BF4)2 reported by Perichon and co-workers[32b] suggested
that the peak at À1.7 V/SCE could be assigned to the reduc-
tion of [Ni0(bipy)(CO2)] into [Ni0(bipy)(CO2)]À. In contrast, the
peak at À1.35 V/SCE has never been observed. We postulate
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that this corresponds to the reduction of the 2,2’-bipyridine
ligand coordinated to Ni0ÀCO2, as the intensity is comparable
to that of the peak at at À1.9 V/SCE (reduction of [Ni0(bipy)] to
[Ni0(bipy)]·À) under argon atmosphere. This observation eluci-
dates Figure 1, curve c, since the disappearance of the reduc-
tion signals of [PhNiX] in the presence of CO2 suggests that
a rapid chemical reaction occurs between the s-arylnickel and
this electrophile.
At this stage, it is not possible to rule out the reduction of
[PhNiX] before the chemical reaction with CO2, as the reduc-
tion wave of this latter is very close to the one corresponding
to the NiII salt (À1.20 and À1.05 V/SCE, respectively). In agree-
ment with previously described Ni-catalyzed reductive carboxy-
lation protocols,[24,26,33] we can tentatively propose a catalytic
cycle based on the arylnickel(II) generated after the oxidative
addition of Ni0 to ArOTs (Scheme 3). The other possibility in-
Figure 3. Optimized structures for [PhNiII(bipy)(h2-CO2)] (a) and
[PhNiI(bipy)(h2-CO2)] (b). For the sake of clarity, the tosylate in (a) is not fea-
tured, except for the oxygen bound to Ni. C black; H white; O red; N blue;
Ni green.
with and without tosylate.[34] This entity has a Gibbs free en-
thalpy value that is 28.2 kcalmolÀ1 below that of its NiII coun-
terpart. The structural parameters (in the absence of tosylate)
of this optimized complex (Figure 3b) are the following: NiÀO
212.4 pm, NiÀC 202.8 pm, CÀO 123.3 pm; O-C-O 143.58. These
values compare well with those obtained in a previous study
by Sakaki and co-workers.[33b]
These computational data suggest that the Ni complex, in
its two oxidation states, can bind and activate CO2. Thus, if we
cannot, at this stage, discriminate between the two pathways,
it appears that the proposed mechanisms both involve realistic
intermediates. The route based on NiI seems easier with re-
gards to energy, but the absence of an intermediate h1 coordi-
nation could militate against this mechanism. Obtaining the
missing clues to elucidate the mechanism of this reaction
probably requires the coupling of electrochemistry and UV
spectroscopy plus an exhaustive DFT study of the catalytic
cycle. We plan to pursue these aims soon.
Scheme 3. One of the proposed catalytic cycles for the carboxylation pro-
cess.
volves the reduction of [ArNiII(bipy)] to [ArNiI(bipy)] before re-
acting with CO2, leading finally to [Ar(CO2)NiI(bipy)]. Once
formed, the transmetalation of the nickel carboxylate with
MnII, produced during the generation of Ni0, would release NiII
or NiI, which could be reduced again by Mn0.
Conclusion
In conclusion, we have developed a novel, mild, and user-
friendly nickel-catalyzed method for the reductive carboxyla-
tion of aromatic tosylates. The process described herein pro-
ceeds with stable substrates (ArOTs) that are easily prepared
from inexpensive and commercially available phenols or naph-
thols, a catalytic amount (10 mol%) of the robust complex
[NiBr2(bipy)], and gaseous CO2 at atmospheric pressure. The
mechanism of this reaction was examined through an electro-
chemical analysis that provided valuable clues on the likely for-
mation of s-arylnickel intermediates. A complementary theo-
retical DFT analysis suggests that the complexation and inser-
tion of CO2 into the s-arylnickel intermediate is likely. This effi-
To go beyond the electrochemical investigation and test
whether these two routes were realistic, we undertook a theo-
retical analysis of the key steps of the catalytic cycle. We first
undertook a DFT-based study of the [ArNiII(bipy)(CO2)] species.
For the sake of simplicity, Ar was taken as phenyl during the
whole computational study. Two local minima were found for
[PhNiII(bipy)(CO2)], corresponding to the two coordination
modes of carbon dioxide. If the h1 mode appears to be slightly
favored (dDrG8=8.9 kcalmolÀ1), it leaves the CO2 molecule in-
activated (linear). However, the h1 complex converts easily into
the h2 mode, affording a structure in which the carbon dioxide
is now activated (Figure 3a). In this complex, the NiÀO and NiÀ cient carboxylation using standard quality CO2, a gas regarded
C bond lengths are 203.3 pm and 204.3 pm, respectively. Also,
the CÀO bond of CO2 is lengthened to 120.2 pm (from
115.7 pm in free CO2) and the O-C-O bond angle bends to
158.28.
The same structural optimization was next carried out for
[PhNiI(bipy)(CO2)]. No local minimum could be found for the h1
coordination while a h2 complex could be characterized, both
both as a threatening waste and a challenging substrate to val-
orize, is particularly noteworthy from the perspective of the
production of value-added carboxylic acids. The direct and cat-
alytic conversion of CO2 into commodity chemicals is of prime
importance in tackling the major contemporary challenge: cli-
mate change related to the overwhelming emissions of CO2 by
human activities during the early anthropocene.[35]
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Experimental Section and Computational
Details
Keywords: carbon dioxide · carboxylation · CÀC coupling ·
homogeneous catalysis · nickel
General considerations: DMF was stored under argon. The catalyst
precursor [NiBr2(bipy)] was prepared separately according to a liter-
ature procedure.[36] The CO2 atmosphere was obtained as follows:
dry ice was introduced into an isolated round-bottom flask in an
anhydrous atmosphere, delivering CO2 gas, which was dried over
P2O5 or SiO2, before bubbling through the reaction mixture. GC
analysis was carried out by using a 24 m HP-methyl silicon capillary
column. Mass spectra were recorded with a quadrupolar MS instru-
ment coupled to a gas chromatograph. Elemental analyses were
performed by the Laboratoire de Microanalyse Organique (C.N.R.S.,
IRCOF, Rouen). Column chromatography was performed on stan-
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benzoic acid: To a solution of aryl tosylate (1 mmol, 1 equiv) in an-
hydrous DMF (5 mL) under a CO2 atmosphere at 608C was added
manganese (2 mmol, 2 equiv) followed by [NiBr2(bipy)] (0.1 mmol,
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Computational details: Computations were carried out by using
Gaussian 09 software.[37] Energy values were obtained by applying
density functional theory (DFT), using the PBE0 global hybrid func-
tional.[38] The unrestricted formalism was used in every cases to
compare rigorously energetic quantities. Structural optimizations
were carried out using standard algorithms and the nature of sta-
tionary points was checked by subsequent vibrational analysis. The
solvent (DMF) was taken into account in an implicit manner, using
the PCM model as implemented in Gaussian 09.[39] For optimiza-
tions and energetic comparisons, all atoms in ligands were repre-
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Acknowledgements
The authors would like to thank the European Regional Devel-
opment Fund (ERDF), the Conventions Industrielles de Forma-
tion pour la Recherche (CIFRE), the Region Haute-Normandie,
and the Arkema group, who funded this study. We acknowl-
edge Labex SynOrg (ANR-11-LABX-0029) for its financial contri-
bution to our research projects and the ANR project Saturnix
(2008-CESA-020) for a post-doctoral fellowship to MA. We
thank Dr. Jie Guang for proofreading this manuscript.
Chem. Eur. J. 2016, 22, 3758 – 3763
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ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim