Integrative Photoreduction of CO2 with Subsequent Carbonylation: Photocatalysis for Reductive Functionalization of CO2

Article abstract of DOI:10.1002/cssc.201801621

Efficient conversion of CO₂ into fuels and chemicals with solar energy would be promising, but also faces great challenge. In this context, we describe the photoreductive functionalization of CO₂ to construct new C?C, C?N, and C?O bonds through the respective Pd-catalyzed Suzuki carbonylation, aminocarbonylation, and alkoxycarbonylation of aryl iodides with CO in situ generated through the photoreduction of CO₂. This protocol opens up an alternative avenue for CO₂ utilization by harnessing solar energy.

Full text of DOI:10.1002/cssc.201801621

Accepted Article
Title: Integrative Photoreduction of CO2 with Subsequent
Carbonylation: Photocatalysis for Reductive Functionalization of
CO2
Authors: Xing He, Yu Cao, Xian-Dong Lang, Ning Wang, and Liang-
Nian He
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To be cited as: ChemSusChem 10.1002/cssc.201801621
Link to VoR: http://dx.doi.org/10.1002/cssc.201801621
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Integrative Photoreduction of CO2 with Subsequent Carbonylation:
Photocatalysis for Reductive Functionalization of CO2
Xing He,[a] Yu Cao,[a] Xian-Dong Lang,[a] Ning Wang,[a] and Liang-Nian He*[a, b]
Abstract: Efficient conversion of CO2 into fuels and chemicals with
solar energy would be promising, but also faces great challenge. In
this context, we described a novel photoreductive functionalization of
CO2 strategy to construct new C-C, C-N and C-O bonds going
through the respective palladium-catalyzed Suzuki carbonylation,
aminocarbonylation and alkoxycarbonylation of aryl iodides with CO
in situ generated through the photoreduction of CO2. This protocol
opens up an alternative avenue for CO2 utilization by harnessing
solar energy.
chemical energy in the photoreduction process.[11c-e] Like
the old saying “killing two birds with one stone”, it is a
promising approach to obtain CO via the photoreduction of
CO2, which provides an alternative way to mitigate both
energy crisis and greenhouse effect. After the Halmann’s
pioneering work,[12] various excellent approaches have
been developed concerning the photocatalytic reduction of
CO2 to CO, photocatalysts include transition metal
complexes and semiconductors.[13] Nevertheless, there is a
gap between the photoreduction of CO2 to CO and further
valorization of the generated CO. In general, the
carbonylation with CO requires relatively high CO
concentration, but the CO evolved from the photoreduction
of CO2 usually cannot meet such prerequisite.
Although usually regarded as the major greenhouse gas,
CO2 also has drawn much attention since it is an abundant,
nontoxic, sustainable C1 source for the production of value-
added chemicals and fuels.[1] Among the methodologies for
CO2
transformation,
the
concept
of
reductive
functionalization of CO2 with amines and reductants to build
C-N bond is attractive.[2] As for CO2 reductive products, CO
is a versatile molecule and exploited as one of principal
industrial chemicals in modern chemical industry, providing
hydrocarbon liquids,[3] aldehydes,[4] acids, ketones, esters,
amide and other diverse carbonyl-containing compounds.[5]
Generally speaking, almost all of CO used in industry is
presently derived from fossil fuels. From the standpoint of
green and sustainable chemistry, it is appealing and
challenging to couple the “CO2 reduction to CO” with
subsequent carbonylation with the in situ formed CO.
However, there are a few works with respect to this strategy
as depicted in Scheme 1. In this context, the reduction step
includes reverse-water-gas-shift reaction (rWGSR),[6] Ru(II)-
mediated hydrogen transfer,[7] hydrosilylation,[8] oxygen
abstraction by disilane,[9] and electroreduction.[10]
Scheme 1. Representative reductive functionalization of CO2 via CO pathway.
Solar energy is the largest energy resource on the earth
and serves as cornerstone for survival and development of
all living creature through the natural photosynthesis.[11a, b]
In this aspect, solar energy is regarded as an ideal energy
to address the thermodynamic issue facing in CO2
Among the carbonylations, the carbonylative Suzuki
reaction[14] has drawn increasing attention and emerged as
one of the most useful tools in organic synthesis.[5, 15] Rapid
development of carbonylative Suzuki reaction has been
witnessed with regard to CO source, and several CO
surrogates such as Mo(CO)6,[16] acyl chloride,[17] formic
acid,[18] chloroform,[19] N,N-dimethylformamide,[20] and N-
formylsaccharin[21] have already been applied in the
carbonylative Suzuki reaction. From the viewpoint of atom
economy, the above-mentioned CO surrogates are far from
satisfactory, and the ideal CO surrogate could be CO2 in
this vein. Recently, Skrydstrup et al. have successfully
performed a series of the palladium-catalyzed carbonylation
reactions for the synthesis of pharmaceuticals, being
coupled with electroreduction of CO2 to CO through the
two-chamber technology they elegantly designed.[10]
conversion.
Mimicking
natural
photosynthesis,
photoreduction of CO2 has gained considerable attention
due to solar energy being a clean and inexhaustible energy
source. Simultaneously, solar energy is accumulated as
[a]
[b]
Xing He, Yu Cao, Dr. Xian-Dong Lang, Ning Wang, Prof. Dr. Liang-
Nian He
State Key Laboratory of Elemento-Organic Chemistry, College of
Chemistry, Nankai University
Tianjin, 300071 (P. R. China)
E-mail: heln@nankai.edu.cn
Prof. Liang-Nian He
Considering the promising value of photoreduction of
CO2 and carbonylation reaction, we envisioned that it is
plausible to implement a carbonylative Suzuki reaction by
employing the CO evolved from photochemical reduction of
CO2. Herein, we would like to report a Pd-catalyzed
Collaborative Innovation Center of Chemical Science and
Engineering, Nankai University, Tianjin, 300071 (P. R. China)
E-mail: heln@nankai.edu.cn
Supporting information for this article is given via a link at the end of
the document.
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10.1002/cssc.201801621
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COMMUNICATION
carbonylative Suzuki reaction using CO from CO2
photoreduction to construct “C-C” bond, to further extend
= 370 nm).[13c]. Subsequently, control experiment showed that
both light and CO2 are prerequisite to running this kind of
photoreductive functionalization (entries 7, 8). In addition, the
influence of organic base on CO2 photoreduction was studied by
using different bases (Table S1), which demonstrates the
superiority of TEOA in fixing CO2 into the photocatalyst for CO
formation.[22e, f]
this
strategy,
the
aminocarbonylation
and
alkoxycarbonylation with the formation of “C-N” and “C-O”
bonds (Scheme 2) were also studied respectively.
Table 1: Influence of CO2 pressure on the carbonylative Suzuki reaction.[a]
Entry
1[c]
2
Pressure (MPa)
Yield[b] 3aa (%)
Yield[b] 4aa (%)
Conv.[b]
92
0.1
2.0
0.3
0.2
0.1
0.2
0.2
-
89
16
54
79
40
36
-
3
Scheme 2. Photocatalytic reduction of CO2 to CO coupled with carbonylation.
1
65
3
3
9
78
Among the various kinds of CO2 photochemical reduction
catalysts,[13] Re(bpy)(CO)3Cl (bpy = 2,2’-bipyridine) was chosen
as CO2 photoreduction catalyst, which has the advantages of
easy fabrication, high selectivity towards CO production, and
simultaneously acting as photosensitizer and catalyst.[22] A 500
W high pressure mercury arc lamp (main peak wavelength 365
nm) was used as light source, a connected two-autoclave
system was exploited as experimental setup (Figure S1). The
reaction between iodobenzene (1a) and phenylboronic acid (2a)
was selected as the model reaction to validate our hypothesis
(for details see the general procedure in Supporting Information).
At the beginning, a carbonylative Suzuki reaction using a
mixture of CO2/CO (4:1) was carried out in the absence of
photoreduction of CO2 (Table 1, entry 1). The outcome proves
that it is feasible to implement the reaction by using a mixture of
CO2/CO. Indeed, 16% yield of benzophenone 3aa was
successfully obtained under 2.0 MPa of CO2 (entry 2). This
result demonstrated the feasibility of our hypothesis and
encouraged us to further optimize the reaction conditions. Firstly,
the influence of CO2 pressure on the reaction was investigated
as summarized in Table 1. Considering 2.0 MPa of CO2 was too
much to dilute the produced CO, we decreased the CO2
pressure, thus 3aa yield increased accordingly (entries 3, 4 vs.
2). As a result, 0.2 MPa of CO2 gave the best result, the amount
of the generated CO in this gas mixture accounted for 6.3%
(Figure S2), which was determined by gas chromatograph FULI
9790 equipped with a thermal conductivity detector (TCD). While
further decreased CO2 pressure to 0.1 MPa had a negative
effect (entry 5). This is understandable that appropriate pressure
is required to take up the generated CO from the photocatalysis
reactor to the carbonylation one; on the other hand, too much
CO2 acts as a diluting agent and thus has detrimental effect on
the carbonylation. Therefore, the additional gaseous CO2 plays a
dual role in acting as the starting material in the first
photoreduction and CO carrier for the carbonylation. Compared
with Xe lamp, the mercury lamp was a better choice (entry 4 vs.
6) due to more suitable light absorption for Re(bpy)(CO)3Cl (abs
4
92
5
17
57
6[d]
7[e]
8[g]
30
84
86 (83)[f]
84
99
-
99
[a] Photoreduction conditions: Re(bpy)(CO)3Cl (12.1 mg, 0.026 mmol), NEt4Cl
(99.4 mg, 0.6 mmol), 15 mL DMA-TEOA (5:1) (bubbled with CO2), 500 W high
pressure mercury arc lamp, 10 h. Carbonylative Suzuki conditions: 1a (20.4
mg, 0.1 mmol), 2a (13.4 mg, 0.11 mmol), K2CO3 (41.5 mg, 0.3 mmol),
PdCl2(PPh3)2 (2.1 mg, 3 mol%), anisole (1 mL), 12 h. [b] Determined by GC,
1,3,5-methoxybenzene as internal standard. [c] Without photoreduction of
CO2, a mixture of CO2/CO (4:1) was used. [d] Xe lamp (400-780 nm). [e]
Without light. [f] Isolated yield. [g] Without CO2.
Afterwards, palladium catalyst and phosphine ligand
were optimized. Among palladium catalysts, PdCl2(PPh3)2
showed better activity than several other palladium
compounds (entries 1-7, Table 2). The role of phosphine
ligand was simultaneously proved by the increased yield of
3aa and reduced the by-product 4aa yield (entry 1 vs. 7).
This is because the phosphine ligand plays a crucial role in
the Pd-catalyzed carbonylation by changing the steric
hindrance including coordination angle and electronic
properties of the metal complex.[24] Confusingly, the yield of
3aa and conversion of 1a were even worse when the
loading of PdCl2(PPh3)2 was increased to 10 mol% (entry 8).
Mixing PdCl2 with PPh3 displayed similar result to
PdCl2(PPh3)2 (entry 7 vs. 9). A higher reaction temperature
led to an increased yield of 4aa (entry 10 vs. 9). It may be
reasoned that, the active species ArCO-Pd-I is unstable at
high temperature with removal of the CO moiety,[25]
facilitating the generation of direct coupling product 4aa. To
our delight, both yield of 3aa and selectivity were
satisfactory when the reaction time was prolonged to 18 h
(entry 11). Among the phosphine ligands, PCy3
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(tricyclohexyl phosphine) performed better than the other
three phosphine ligands, but was inferior to PPh3 (entries
12-15). The cone angle[26] of the phosphine ligands may
account for such reactivity difference, the cone angle of
On the other hand, steric effect was examined through the
introduction of a methyl group at different positions of the aryl
iodide respectively (3ca, 3ia and 3ja). As a result, a substituent
at the meta-position of the aryl iodide had negligible on the yield
(3ca vs. 3ia), while a substituent at the ortho-position had
remarkable impact on the yield (3ca vs. 3ja). Arylboronic acids
with the introduction of electron-withdrawing substituents at the
o
o
PCy3 (170 ) is bigger than that of PPh3 (145 ).[26, 27] The
unique character of cone angle of PPh3 is beneficial to the
CO fixation (namely, CO insertion) in the presence of
23, 24]
PdCl2,[14,
making the formation of the acylpalladium
para-position could offer
a
good yield of the desired
species ArCO-Pd-I easier. To verify this hypothesis, Sphos
(2-dicyclohexylphosphino-2’,6’-dimethoxy-1,1’-biphenyl)
was selected as phosphine ligand for the carbonylative
benzophenones 3ad and 3ae. Whereas, arylboronic acids
featuring with electron donating group (-Me, -OMe) at the para-
position gave moderate yields of carbonylated products 3ab and
3ac. Furthermore, 4-hydroxyphenylboronic acid with a strong
electron donating group at the para-position afforded the 4-
benzoylphenol (3af) in low yield. The ortho-position substituent
in arylboronic acids had influence on the reaction outcome, and
the larger steric effect resulted in the lower yield (3ah vs. 3ai).
o
[27]
Suzuki reaction, whose cone angle (217
)
is much
bigger than PPh3. As expected, the yield of the desired
product was poor (entry 15).
Table 2: Screening of the reaction conditions.[a]
Yield[b]
3aa (%)
Yield[b]
4aa (%)
Entry
Cat.([Pd])
Ligand
Conv.[b]
1
2
PdCl2
Pd(OAc)2
Pd2(dba)3
PdCl2(CH3CN)2
Pd(PPh3)4
Pd/C
-
53
53
50
36
59
49
79
16
79
80
95
27
53
66
7
20
24
8
74
83
82
60
90
83
92
70
85
99
99
97
73
87
74
-
3
-
4
-
-
18
27
22
9
5
6
-
7
PdCl2(PPh3)2
PdCl2(PPh3)2
PdCl2
-
8[c]
9
-
35
6
PPh3
PPh3
PPh3
Xantphos
dppm
PCy3
Sphos
10[d]
11[e]
12[e]
13[e]
14[e]
15[e]
PdCl2
19
4
PdCl2
PdCl2
6
PdCl2
5
Scheme 3. Substrate scope. Photoreduction conditions: Re(bpy)(CO)3Cl (12.1
mg, 0.026 mmol), NEt4Cl (99.4 mg, 0.6 mmol), 15 mL DMA-TEOA (5:1)
(bubbled with CO2), 0.2 MPa CO2, 500 W high pressure mercury arc lamp, 10
h. Carbonylative Suzuki conditions: 1 (0.1 mmol), 2 (0.11 mmol), K2CO3 (41.5
mg, 0.3 mmol), PdCl2 (0.6 mg, 3 mol%), PPh3 (1.6 mg, 6 mol%), anisole (1
mL), 18 h. Yields were determined by GC, 1,3,5-methoxybenzene as internal
standard, isolated yields were given in parenthesis.
PdCl2
9
PdCl2
5
[a] Photoreduction conditions: Re(bpy)(CO)3Cl (12.1 mg, 0.026 mmol),
NEt4Cl (99.4 mg, 0.6 mmol), 15 mL DMA-TEOA (5:1) (bubbled with CO2),
0.2 MPa CO2, 500 W high pressure mercury arc lamp, 10 h. Carbonylative
Suzuki conditions: 1a (20.4 mg, 0.1 mmol), 2a (13.4 mg, 0.11 mmol), K2CO3
(41.5 mg, 0.3 mmol), [Pd] (3 mol%), ligand (6 mol%), anisole (1 mL), 12 h.
[b] Determined by GC, 1,3,5-methoxybenzene as internal standard. [c] 10
mol% loading of PdCl2(PPh3)2. [d] 90 oC. [e] 18 h.
Apart from the aforementioned fundamental studies, our
attention diverted to the practical application of this method.
Fenofibrate, namely Lipanthyl, is one kind of hypolipidemic
agents to regulate the lipoprotein cholesterol, total
cholesterol, triglycerides for patients.[28] The successful
synthesis of Fenofibrate with a good yield under the
selected conditions (Scheme 4) proves the feasibility of this
protocol and further broadens the scope of CO2
transformation.
With the optimal conditions in hand, we turned to test the
general applicability of this protocol with a series of different aryl
iodides and aryl boronic acids (Scheme 3). The aryl iodides
featuring with electron-donating group (-OMe, -Me and -Ph) and
electron-withdrawing substituent (-F) at the para-position, were
prone to deliver the carbonylation products in nice yields (3ba,
3ca, 3da, 3ea). 4-iodophenol bearing a free hydroxyl group
could offer the corresponding biarylketone (3ha) with moderate
yield (48%), proving functional group tolerance of this protocol.
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To prove the origin of CO, a reaction was conducted using
13CO2, and the 13C-labeled product 3aa was obtained as shown
in Figure 1. This result clearly demonstrated that CO was
derived from CO2. Based on the previous reports,[22-24, 31] and
this study, the proposed mechanism for consolidation of CO2
photoreduction with subsequent carbonylation reaction is
Scheme 4. The synthesis of Fenofibrate via the carbonylative Suzuki reaction
with CO in situ produced from photocatalytic reduction of CO2.
proposed as shown in Scheme 6. Initially, the active Pd(0)
31a-e]
specie (A) forms in situ.[24b,
Then, oxidative addition of
iodobenzene to the Pd(0) specie offers the intermediate Pd(II)
(B). The acylpalladium intermediate (C) is formed after the
coordination and insertion of CO, which is in situ generated
Inspired by success in the biaryl-ketone synthesis, we
would like further to expand the scope of this photoreductive
functionalization of CO2 strategy. As we know, amides and
esters represent two other important kinds of carbonyl-
containing compounds widely used in the synthesis of natural
products, pharmaceuticals, polymers and organic materials,[29]
which can be prepared through the aminocarbonylation and
alkoxycarbonylation of aryl halides respectively.[30] As depicted in
Scheme 5, this method also worked well for the Pd-catalyzed
aminocarbonylation and alkoxycarbonylation of iodobenzene.
Therefore, this photocatalysis protocol offers an alternative
access to the amides and esters, and represents examples for
extending the reductive functionalization of CO2 from the
formation of common “C-N” bond[2] to “C-C”, “C-N” and “C-O”
through the photoreduction of CO2, followed by
a
transmetalation reaction. Finally, the carbonyl-containing product
(D) is released through the reductive elimination process.
In summary, we have developed a photocatalytic protocol for
reductive functionalization of CO2 with subsequent carbonylation
to afford biaryl ketone, amide and ester in good to excellent
yields through the palladium-catalyzed carbonylation of aryl
iodides with CO in situ produced from the photoreduction of CO2.
Therefore, this work fills the gap between the photoreduction of
CO2 and the valorization of the obtained reductive products, thus
enriches the reductive functionalization of CO2 via photocatalysis,
resulting in formation of new “C-C”, “C-N” and “C-O” bonds,
respectively.
bonds
.
Scheme 5. Palladium-catalyzed aminocarbonylation and alkoxycarbonylation
of iodobenzene with CO produced from the photoredution of CO2.
Scheme 6. Proposed mechanism for the Pd-catalyzed carbonylation using CO
generated from photoreduction of CO2.
Acknowledgements
This work was financially supported by National Key Research
and Development Program (2016YFA0602900), National
Natural Science Foundation of China (21421001, 21672119),
Natural Science Foundation of Tianjin (16JCZDJC39900).
Keywords: carbon dioxide fixation • carbonylation • cross-
coupling • photocatalysis • reduction
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Entry for the Table of Contents (Please choose one layout)
Layout 1:
COMMUNICATION
Photoreductive functionalization of
CO2 combines the reduction of CO2 to
CO with subsequent carbonylation to
afford value-added chemicals via new
C-C/C-N/C-O bond formation. This
work constitutes a great step toward
the incorporation of solar energy in the
production of chemicals through CO2
valorization.
Xing He, Yu Cao, Xian-Dong Lang, Ning
Wang, Liang-Nian He*
Page No. – Page No.
Integrative Photoreduction of CO2
with Subsequent Carbonylation:
Photocatalysis for Reductive
Functionalization of CO2
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