Integration of co2 reduction with subsequent carbonylation: Towards extending chemical utilization of co2

Article abstract of DOI:10.1002/cssc.201800902

Currently, it still remains a challenge to amplify the spectrum of chemical fixation of CO₂, although enormous progress has been achieved in this field. In view of the widespread applications of CO in a myriad of industrial carbonylation processes, an alternative strategy is proposed in which CO₂ reduction to CO is combined with carbonylation with CO generated ex situ, which affords efficiently pharmaceutically and agrochemically attractive molecules. As such, CO₂ in this study was efficiently reduced by triphenysilane using CsF to CO in a sealed two-chamber reactor. Subsequently, palladium-catalyzed aminocar-bonylation, carbonylative Sonogashira coupling of aryl iodides, and rhodium(I)-mediated Pauson–Khand-type reaction proceeded smoothly to yield amides, alkynones, and bicyclic cy-clopentenones, respectively. Furthermore, the formed alkynones can further be successfully converted to a series of heterocycles, for example, pyrazoles, 3a-hydroxyisoxazolo[3,2-a]isoindol-8-(3aH)-one derivatives and pyrimidines in moderate yields. The striking features of this protocol include operational simplicity, high efficiency, and relatively broad application scope, which represents an alternative avenue for CO₂ transformation.

Full text of DOI:10.1002/cssc.201800902

Accepted Article
Title: Integration of CO2 Reduction with Subsequent Carbonylation:
Towards Extending Chemical Utilization of CO2
Authors: Xian-Dong Lang and Liang-Nian He
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10.1002/cssc.201800902
ChemSusChem
COMMUNICATION
Integration of CO2 Reduction with Subsequent Carbonylation:
Towards Extending Chemical Utilization of CO2
Xian-Dong Lang,[a] and Liang-Nian He*[a, b]
Currently, it still remains a challenge to amplify the spectrum of
chemical fixation of CO2, though enormous progresses have been
witnessed in this field. In view of the widespread applications of CO
in a myriad of industrial carbonylation processes, we proposed an
alternative strategy to integrate CO2 reduction to CO and
carbonylations with CO ex situ generated, efficiently affording
pharmaceutically and agrochemically attractive molecules. As such,
CO2 in this study was efficiently reduced by triphenysilane with CsF
range of carbonylative functionalization of alkenes, delivering
value-added molecules such as carboxylic acids,[11] esters,[12]
amines[13-14] and alcohols[15-19] efficiently. Recently, Ding and co-
workers firstly reported the exclusive synthesis of aldehydes via
rhodium-catalyzed one-pot hydroformylation of olefins with CO2,
poly(methyl-hydrosiloxane) (PMHS), and H2, and the
mechanistic investigations disclose that the presence of CO2
inhibites further reduction of the thus formed aldehydes.[20]
Furthermore, Skrydstrup and co-workers have elegantly
designed a connected two-chamber system (CO ware), in which
CO2 is efficiently reduced to CO using disilane as the reductant
under transition metal-free conditions, while the thus liberated
CO gas go through the metal promoted carbonylations to afford
the pharmaceutically relevant molecules[21] (Scheme 1). On the
other hand, some CO-releasing molecules (CORMs) including
Mo(CO)6,[22-23] formates,[24-25] silacarboxylic acids,[26-27] acid
chlorides,[28] N-formylsaccharin,[29-30] and chloroform[31] can
readily deliver CO upon its activation. Besides, some of them
can be recognized as the bridge molecules from CO2 to CO,
since they can be readily prepared from CO2.
to CO in
a
sealed two-chamber reactor; Subsequently, the
aminocarbonylation and carbonylative
palladium-catalyzed
Sonogashira coupling of aryl iodides, rhodium(I)-mediated Pauson-
Khand-type reaction proceeded smoothly to furnish the amides,
alkynones and bicyclic cyclopentenones, respectively. Furthermore,
the formed alkynones can further be successfully converted to a
series of heterocycles e.g. pyrazoles, 3a-hydroxyisoxazolo[3,2-
a]isoindol-8-(3aH)-one derivatives and pyrimidines in moderate
yields. The salient features of this protocol include operational
simplicity, high efficiency, relatively broad application scope, which
represents an alternative avenue for CO2 transformation.
With the growing recognition of low carbon economy and
sustainable development, much attention has been focused on
the chemical transformation of CO2, which bears attractive
characteristics such as low cost, nontoxicity, non-flammability,
easy accessibility and so on as a valuable C1 resource.[1-3]
Though recycling CO2 into chemicals, fuels and polymers has
been flourished, broadening the scope of conversion of CO2 still
remains a significant challenge due to its thermodynamic
stability and kinetic inertness.
Compared to CO2, CO has been universally recognized as
an industrially important gas in oxidative coupling to give diethyl
oxalate, Fischer-Tropsch process, Monsanto process, Reppe
reaction, and so on.[4-7] Furthermore, tremendous improvements
have also been achieved in the palladium-catalyzed
carbonylations of aryl halides with CO to furnish a variety of
carbonyl compounds such as aldehydes, amides, esters, etc.[8-10]
However, the high toxicity and gas pressure, along with gaseous
nature of CO remains a formidable obstacle in the activity of
both academia and industrial sectors. To circumvent such
problems and to extend the scope of CO2 utilization, CO2 has
been exploited as
a
CO precursor for conventional
Scheme 1. Integration of reduction of CO2 with carbonylation reaction.
carbonylations. For example, the CO formed through a reverse
water-gas shift reaction (rWGSR) can be consumed in situ in a
[a]
Dr. X.-D. Lang, Prof. L.-N. He
As part of our research endeavors on hydrogenation and
reductive functionalization of CO2,[32] along with the inspiration
by the readily decarbonylation of formates and the
thermodynamically favorable hydrosilylation of CO2 into silyl
formats[33], we speculated whether CO2 can be used directly with
hydrosilane to evolve CO with silyl formate as an intermediate,
for the carbonylative reactions. In this aspect, fluoride salts have
been demonstrated to be efficient catalyst for the hydrosilylation
of CO2 to silyl formate, due to the inherent high fluorophilicity of
the silicon atom.[34-35][43] Therefore, a common fluoride source e.g.
State Key Laboratory and Institute of Elemento-Organic Chemistry
College of Chemistry, Nankai University
Tianjin, 300071 (P. R. China)
E-mail: heln@nankai.edu.cn
Prof. L.-N. He
Collaborative Innovation Center of Chemical Science and Engineering
Nankai University, Tianjin, 300071 (P. R. China)
E-mail: heln@nankai.edu.cn
[b]
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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10.1002/cssc.201800902
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Table 1. Catalyst screening and reaction conditions optimization.[a]
KF was selected to evaluate the effect of the hydrosilane on the
reaction in a sealed two chamber reactor which is summarized
in Table 1, and the thus generated CO gas was trapped by the
Pd-catalyzed aminocarbonylation from p-iodoanisole and
cyclohexylamine at 80 °C for 24 h and quantified by the yield of
corresponding product 2a. To our surprise, the type of
hydrosilane has a substantial influence on the reaction, with
Ph3SiH gave up to 86% yield of N-cyclohexyl-4-
methoxybenzamide 2a with excellent chemoselectivity, and
other hydrosilanes such as PMHS, (EtO)3SiH, PhSiH3, Ph2SiH2,
Et3SiH and (CH3)2PhSiH did not provide satisfactory conversion
(entries 1-7). We deduced that the silyl formates readily form
from the hydrosilanes and CO2, but release CO more difficult
than Ph3SiH. Notably, any side reaction such as double
carbonylation was not observed. We then switched our attention
to the dependence of 2a yield on the catalyst such as fluoride
and oxygen-containing bases owing to their dynamic interaction
with the silane to promote the reduction of CO2. The data in
Table 1, entry 8 illustrates that the reaction did not occur in the
absence of any catalyst and the starting material of
carbonylative reaction was recovered quantitatively, implying
that catalyst play a significant role in both the generation and the
decarbonylation of silyl formate HCOOSiPh3. Compared with KF,
CsF rendered a slight higher yield of 2a (entry 9 vs entry 5),
whereas TBAF (tetrabutylammonium fluoride) (1M solution in
Yield
2a
Hydrosilane
(mmol)
Entry
Catalyst
Solvent
T (oC)
t (h)
(%)[b]
1
2
3
4
5
6
PMHS (2)
(EtO)3SiH (2)
PhSiH3 (0.667)
Ph2SiH2 (1)
Ph3SiH (2)
KF
KF
KF
KF
KF
KF
DMF
DMF
DMF
DMF
DMF
DMF
130
130
130
130
130
130
24
24
24
24
24
24
12
18
15
24
86
4
Et3SiH (2)
(CH3)2PhSiH
(2)
7
KF
DMF
130
24
3
8
Ph3SiH (2)
Ph3SiH (2)
Ph3SiH (2)
Ph3SiH (2)
Ph3SiH (2)
Ph3SiH (2)
Ph3SiH (2)
Ph3SiH (2)
Ph3SiH (2)
Ph3SiH (2)
Ph3SiH (2)
Ph3SiH (2)
Ph3SiH (2)
Ph3SiH (2)
Ph3SiH (2)
Ph3SiH (2)
Ph3SiH (1.5)
Ph3SiH (1)
Ph3SiH (0.5)
Ph3SiH (2)
-
-
CsF
DMF
DMF
130
130
130
130
130
130
130
130
130
130
130
130
120
110
130
130
130
130
130
130
130
130
24
24
24
24
24
24
24
24
24
24
24
24
24
24
20
16
24
24
24
24
24
24
0
9
95
30
63
32
<1
34
51
11
10
<1
<1
74
59
87
73
65
37
22
<1
<1
<1
THF) displayed
a lower activity under otherwise identical
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27c
28d
29e
TBAF
NH4OAc
NaOAc
Na2CO3
CsF
DMF
conditions (entry 10 vs entry 5). For the catalyst with a fixed
anion, the catalytic activities followed the order of NH4OAc >
NaOAc, suggesting the pivotal role the cation played in the
solubility and catalytic performance (entries 11-12). For
comparison, Na2CO3 was tested to be inactive (entry 13).
DMF
DMF
DMF
The influence of reaction parameters including solvent,
temperature and reaction time on the reaction was then
investigated. Solvents with high polarity might be favorable for
the reaction (entries 9, 14-15 vs 16-19), and DMF was proved to
be an appropriate solvent. The poor yield in entry 19 may be
derived from the fact that THF inhibit the reaction evidently with
the lone pair in THF preventing the interaction between fluoride
and hydrosilane (entry 19). Subsequently, decreasing the
temperature from 130 oC to 110 oC caused lower yield of 2a,
whereas unchanged yield was obtained when enhance the
DMSO
NMP
CH3CN
toluene
dioxane
THF
CsF
CsF
CsF
CsF
CsF
o
temperature (entries 9, 20-21). Therefore, 130 C was selected
CsF
DMF
as the optimal temperature for further optimization of the
reaction times. A noticeable decrease in 2a yield was witnessed
when shortening the reaction times from 24 h to 16 h (entries 9,
22-23). Next, an evaluation of the amount of Ph3SiH in the step
of CO2 splitting into CO confirmed that 2 mmol Ph3SiH seems to
be most suitable (entries 9, 24-26). Subsequently, Pd(dba)2 was
confirmed to be the optimum catalyst for the carbonylation
reaction in this study through the investigation of various
palladium catalysts including Pd(OAc)2, PdCl2, Pd(PPh3)2Cl2,
Pd(PPh3)4, Pd/C and so on (for details, see Table S1 in
Supporting Information).
Blank runs were also conducted to demonstrate the
carbonyl fragment in 2a originates from CO2. Firstly, the
aminocarbonylation reaction in chamber B did not occur in the
absence of CO2 (entry 27). Besides, it has been reported that
DMF can also be employed as CO source at high
temperature.[36-37] To rule out the abovementioned possibility, the
reaction was performed just in the presence of DMF or in the
presence of both DMF and CsF, the starting material remain
intact after 24 h (entries 28-29), which further underscore the
significance of CO2 as a CO surrogate.
CsF
DMF
CsF
DMF
CsF
DMF
CsF
DMF
CsF
DMF
CsF
DMF
CsF
DMF
-
DMF
-
CsF
DMF
[a] Reaction conditions: chamber A was loaded with hydrosilane (0.5208
mmol), KF (0.0116 g, 10 mol%, 0.2 mmol), DMF (1.0 mL), and CO2 (approx.
20 mL, 0.892 mmol), 100 oC, 24 h; chamber B was loaded with Pd(dba)2 (5
mol%, 0.0229 g), PPh3 (10 mol%, 0.0131 g), p-iodoanisole (0.117 g, 0.50
mmol), cyclohexylamine (0.150 g, 1.5 mmol), Et3N (0.101 g, 1.0 mmol, 0.14
mL), dioxane (2.0 mL), 80 oC, 24 h. [b] GC yields were given using biphenyl as
the internal standard. [c] In the absence of CO2. [d] In the atmosphere of argon.
[e] In the atmosphere of argon.
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Afterwards, the catalytic protocol using connected two-
chamber reactor was then found to be applicable to the
aminocarbonylation of various aryl iodides with cyclohexylamine
as a fixed nucleophile, which is summarized in Scheme 2.
Various electron-withdrawing or electron-donating groups at the
phenyl ring such as F, Cl, OCH3, CH3 and tBu were well
tolerated to give the desired amides 2a-2j in excellent yields.
Moreover, 29% isolated yield of 2a was also obtained when
using 4-bromoanisole as the starting material, which is in
accordance with the general order of reactivity of aryl halide in
carbonylative reactions (aryl iodide > aryl bromide > aryl
chloride). Negligible difference was observed between the
activity of 2-iodofuran and 2-iodothiophene, and the same
happened to the activity of iodobenzene and 1-iodonaphthalene
(yield: 2k ≈ 2l, 2f ≈ 2m). To our delight, the catalytic system can
be extended to the synthesis of moclobemide 2p, an inhibitor of
the MAO-A isozyme, which is a pharmacological and therapeutic
useful molecule. Furthermore, aliphatic amines, such as
butylamine and benzyl amine provided good to excellent yields
of the corresponding product (2n-2o), whereas; secondary
amine, i.e. piperidine afforded lower yield of 2q. We then
switched our attention to the exploitation of benzylamines as
starting materials. 4-F, 4-Cl, 4-OCH3 substituted iodobenzene
showed almost the same activity compared with iodobenzene
when reacted with aniline (2s-2u). And high yields of 2v and 2w
(81% and 83%) were also obtained when p-chloroaniline and p-
anisidine were used as nucleophile, respectively.
Considering the abundant occurrence in a wide variety of
biologically active molecules and their pivotal role as key
synthetic intermediates,[40-42] the methodology was then applied
to the synthesis of α,β-alkynyl ketones, which is depicted in
Scheme 4. The carbonylative coupling reactions of iodobenzene
with various para-substituted phenylacetylenes was firstly
investigated. And the results showed that all the reactions
proceeded smoothly, with electron-donating groups substituted
ones at para position showing slightly higher reactivity. When
comes to the aliphatic alkynes, e.g. cyclopropylacetylene and 1-
hexyne, higher catalyst loading was required to obtain a satisfied
yield. Then the reaction scope was expanded to various
substituted aryl iodides with phenylacetylene as a fixed coupling
reagent. The results discovered that the electron-withdrawing or
electron-donating groups at the phenyl ring generally have little
influence on the reactivity, affording the corresponding products
3g-3k in 81-90% yields. 1-iodonaphthalene and 2-iodothiophene
were also proved to be suitable substrates under the optimized
conditions.
[a] Unless otherwise specified, all the reactions were performed with: chamber
A was loaded with Ph3SiH (0.5208g, 2 mmol), CsF (0.030 g, 10 mol%, 0.2
mmol), DMF (1.0 mL), and CO2 (approx. 20 mL, 0.892 mmol), 130 oC, 24 h;
chamber B was loaded with PdCl2 (5 mol%, 0.0045 g), Xantphos (10 mol%,
0.029 g), aryl iodides (0.50 mmol), alkyne (0.65 mmol), Et3N (0.101 g, 1.0
mmol, 0.14 mL), dioxane (2.0 mL), 80 oC, 24 h. [b] Isolated yields. [c] PdCl2
(7.5 mol%, 0.0067 g), Xantphos (15 mol%, 0.0435 g).
Scheme 4. CO gas-free carbonylative Sonogashira coupling reaction to
prepare α,β-alkynyl ketones.
N-containing heterocycles represent a synthetically useful
structural motif found in numerous biologically active molecules.
To further extend the application of current methodology, we
found that CO2 can also be successfully integrated into N-
containing heterocycles with the thus prepared alkynones as
important building blocks. For example, treatment of 3i and 3m
with hydrazine hydrate and phenylhydrazine provided
substituted pyrazoles 4i and 4m in high isolated yields through
dehydration and subsequent 1,4-addition process, respectively
(Scheme 5a-b). Furthermore, [3+2] annulation between 3a and
[a] Reactions were carried out with: chamber A was loaded with Ph3SiH
(0.5208g, 2 mmol), CsF (0.030 g, 10 mol%, 0.2 mmol), DMF (1.0 mL), and
CO2 (approx. 20 mL, 0.892 mmol), 130 oC, 24 h; chamber B was loaded with
Pd(dba)2 (5 mol%, 0.0229 g), PPh3 (10 mol%, 0.0131 g), aryl iodides (0.50
mmol), amines (1.5 mmol), Et3N (0.101 g, 1.0 mmol, 0.14 mL), dioxane (2.0
mL), 80 oC, 24 h. [b] Isolated yields.
Scheme 2. Scope of aminocarbonylations of various aryl iodides.
In addition, carbamate salts 1aa was proved to be excellent
CO2 and cyclohexylamine surrogate for the aminocarbonylation,
rending the reaction proceed smoothly under gas-free conditions
with negligible influence on 2a yield. The protocol is easily
handled, practical and high yielding as shown in Scheme 3.
NHPI
(N-hydroxyphthalimide)
provided
pharmaceutically
attractive
3a-hydroxyisoxazolo[3,2-a]isoindol-8-(3aH)-one
derivatives 4a in up to 89% yield, which is definitely confirmed
by X-ray analysis (Figure 1). Finally, the tandem reaction was
also extended to the preparation of pyrimidines via the
cyclization of 3a/3e with acetamidine hydrochloride (Scheme 5d).
All the above-mentioned results indicated that this methodology
is practical to valuable molecules preparation.
Recently, CO gas free version of Pauson-Khand reaction
has become
a
promising field for the construction of
cyclopentenones and their derivatives.[38-39] The combination of
Scheme 3. Synthesis of 2a under gas-free conditions.
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10.1002/cssc.201800902
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reduction of CO2 to CO and rhodium(I)-catalyzed Pauson-
Khand-type reaction was proved feasible, delivering the diester-
linked and oxygen-tethered products 4f and 4g in 36% and 41%
yields, respectively (Scheme 6).
hydrosilane as reductant and transition metal catalyzed
carbonylation in a connected two chamber reactor, providing
amides, alkynones and bicyclic cyclopentenones in nice yields.
Furthermore, the thus formed alkynones can also act as starting
materials for the synthesis of a series of heterocycles e.g.
pyrazoles,
3a-hydroxyisoxazolo[3,2-a]isoindol-8-(3aH)-one
derivatives and pyrimidines in moderate yields. This protocol is
practical, CO gas free, which amplifies the scope of CO2
transformation.
Scheme 7. Possible mechanism for the ex situ reduction of CO2 to CO and
subsequent carbonylative reaction.
Scheme 5. Transformations of alkynones into N-containing heterocycles.
Experimental Section
General procedure for the two chamber carbonylative
reactions
Take the synthesis of 2a under optimized conditions as an
example, in the CO producing chamber, Ph3SiH (0.5208 g, 2
mmol) and CsF (0.030 g, 10 mol%, 0.2 mmol) were added. Then
this chamber was connected with another chamber, namely CO
consuming chamber, which is charged with Pd(dba)2 (5 mol%,
0.0229 g), PPh3 (10 mol%, 0.0131 g), p-iodoanisole (0.117 g,
0.50 mmol). Subsequently, the whole setup was charged with
CO2 with Schlenk technique. Afterwards, DMF (1 mL) was
added to the CO producing chamber, and cyclohexylamine
(0.150 g, 1.5 mmol), Et3N (0.101 g, 1.0 mmol, 0.14 mL), dioxane
(2.0 mL) were added to another chamber. The two chambers
Fig. 1 The ORTEP diagram of compound 4a.
o
o
were conducted under 130 C and 80 C for 24 h, respectively.
After the reaction, 10 mg diphenyl was used as internal standard
for GC yield determination. To obtain pure products, 20 mL
water was added to the reaction mixture of CO consuming
chamber, extracted with ethyl acetate. Then the organic layers
were washed with saturated NaCl solution, dried with anhydrous
Na2SO4, column chromatography on silica gel (petroleum
ether/ethyl acetate = 3/1) was conducted. Similar procedure was
performed in the carbonylative Sonogashira coupling of aryl
iodides, rhodium(I)-catalyzed Pauson-Khand-type reaction. For
the characterization data of the products, see supporting
information.
Scheme 6. Application of the protocol to rhodium(I) catalyzed synthesis of
cyclopentenones.
A plausible mechanism for the reduction of CO2 to CO and
its consumption in a palladium-catalyzed aminocarbonylation is
illustrated in Scheme 7. The nucleophilic interaction between
fluoride anion and triphenylsilane leads to the hypervalent silicon
intermediate A, which makes the insertion of CO2 into the
polarized Si-H bond more easily to form the corresponding silyl
formate C.[43] C is thermosensitive to give CO gas and silanol.[44]
Then, a carbonylative reaction with CO ex situ generated occurs
to give the carbonyl compounds. Firstly, intermediate
D
generates via the oxidative addition of Pd(0) and iodobenzene.
Subsequently, the evolved CO gas from C inserts into Pd-C
bond in D to form the intermediate E. Subsequently, nucleophilic
attack by amine or alkyne in the presence of base produces the
amide and alkynone, respectively.
Acknowledgements
This work was financially supported by the National Program on
Key Research Project (2016YFA0602900), National Natural
Science Foundation of China (21472103, 21421001, 21672119),
In summary, we have demonstrated the feasibility of
combining the two process i.e. reduction of CO2 to CO using
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10.1002/cssc.201800902
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COMMUNICATION
the Natural Science Foundation of Tianjin Municipality
(16JCZDJC39900).
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Keywords: amides • carbon dioxide fixation • homogeneous
catalysis • reduction • synthetic methods
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10.1002/cssc.201800902
ChemSusChem
COMMUNICATION
COMMUNICATION
X.-D. Lang, L.-N. He*
Page No. – Page No.
Integration of CO2 Reduction with
Subsequent Carbonylation: Towards
Extending Chemical Utilization of CO2
Ex situ reduction of CO2 to CO for carbonylations: CO2 can be efficiently
reduced by triphenysilane to CO in a sealed two-chamber reactor, which subsequently
runs diverse carbonylation reactions to afford amides, alkynones and bicyclic
cyclopentenones. Furthermore, the thus formed alkynones can successfully be used as
scaffold for the synthesis of heterocycles e.g. pyrazoles and pyrimidine derivatives.
This article is protected by copyright. All rights reserved.