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REVIEW

Received 10 Jul 2014 | Accepted 21 Nov 2014 | Published 20 Jan 2015 DOI: 10.1038/ncomms6933

Using carbon dioxide as a building block in organic


synthesis
Qiang Liu1, Lipeng Wu1, Ralf Jackstell1 & Matthias Beller1

Carbon dioxide exits in the atmosphere and is produced by the combustion of fossil fuels, the
fermentation of sugars and the respiration of all living organisms. An active goal in organic
synthesis is to take this carbon—trapped in a waste product—and re-use it to build useful
chemicals. Recent advances in organometallic chemistry and catalysis provide effective
means for the chemical transformation of CO2 and its incorporation into synthetic organic
molecules under mild conditions. Such a use of carbon dioxide as a renewable one-carbon
(C1) building block in organic synthesis could contribute to a more sustainable use of
resources.

A
more sensible resource management is the prerequisite for the sustainable development
of future generations. However, when dealing with the feedstock of the chemical
industry, the level of sustainability is still far from satisfactory. Until now, the vast
majority of carbon resources are based on crude oil, natural gas and coal. In addition to biomass,
CO2 offers the possibility to create a renewable carbon economy. Since pre-industrial times, the
amount of CO2 has steadily increased and nowadays CO2 is a component of greenhouse gases,
which are primarily responsible for the rise in atmospheric temperature and probably abnormal
changes in the global climate. This increase in CO2 concentration is largely due to the
combustion of fossil fuels, which are required to meet the world’s energy demand1. Obviously,
there is an urgent need to control CO2 emissions and develop efficient carbon capture systems.
Although the extensive use of carbon dioxide for chemical production cannot solve this problem
alone, CO2 is a useful one-carbon (C1) building block in organic synthesis due to its abundance,
availability, nontoxicity and recyclability. As a result, valorization of CO2 is currently receiving
considerable and ever increasing attention by the scientific community2–4. However, activation
and utilization of CO2 is still problematic due to the fact that it is the most oxidized form of
carbon, which is also thermodynamically stable and/or kinetically inert in certain desired
transformations. Consequently, most of the known studies used highly reactive substrates and/or
severe reaction conditions to activate CO2, limiting the application of such methods. In
particular, the catalytic coupling of CO2 with energy-rich substrates, such as epoxides and
aziridines, to generate polycarbonates/polycarbamates and/or cyclic carbonates/carbamates has
drawn significant attention over the past decades. To create C-C bonds with CO2, the use of
carbon nucleophiles is specifically limited to strong nucleophilic organolithiums and Grignard
reagents, as well as phenolates.

1 Leibniz-Institut
für Katalyse an der Universität Rostock, Albert-Einstein-Strasse 29a, 18059 Rostock, Germany. Correspondence should be addressed to M.B.
(email: matthias.beller@catalysis.de).

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REVIEW NATURE COMMUNICATIONS | DOI: 10.1038/ncomms6933

Along with the rapid development of organometallic chemistry One of the more successful processes for CO2 utilization for
and catalysis (see Box 1), various types of efficient CO2 material synthesis is the catalytic productions of cyclic carbonates
transformations in organic synthesis have been discovered in and polycarbonates from epoxides8, which has been
the past decades, greatly improving its efficiency and applicability. industrialized as well9. Nowadays, cyclic carbonates are widely
This review will describe the most recent advances made in the used as organic synthetic intermediates, aprotic polar solvents,
area of CO2 valorization—turning CO2 into a useful chemical precursors for biomedical applications and raw materials for
feedstock—under mild conditions. A special focus is given on the engineering plastics. Although this 100% atom economical
reaction modes for the CO2 activation and its application as C1 reaction has been commercialized for the synthesis of ethylene
building block in organic synthesis. While classical methods for and propylene carbonates for over 50 years10, recently a variety of
CO2 hydrogenation have been reviewed elsewhere and will not be highly selective and reactive catalysts were developed.
included here5–7, the following subjects will be addressed: (1) Representative systems are summarized in Fig. 2 (ref. 11).
novel transformations using carbon dioxide (briefly summarized Notably, in 1983, Inoue and co-workers described in their
in Fig. 1); (2) different reaction modes for CO2 activation (main seminal work that a (TPP)AlOMe complex can trap carbon
focus of this review); and (3) potential new applications of CO2 dioxide readily and reversibly at room temperature. The trapped
valorization. carbon dioxide is active enough to react with epoxide at ambient
conditions to afford the corresponding cyclic carbonates12. Since
then, various metalloprophyrin catalysts were studied in this
Activation modes for catalytic valorization of CO2
transformation. For example, in 2007, Jing et al.13 reported a
CO2 is the most stable form of oxidized carbon compounds.
Co(TPP)(OAc)/PTAT (phenyltrimethylammonium tribromide)
Nevertheless, it reacts easily with strong nucleophiles to form new
catalyst system to achieve this CO2 fixation at room temperature
C-C or C-H bonds. However, to use carbon dioxide in a more
and low pressure. More recently, Sakai et al. developed a highly
benign and practical manner, efficient transformations with less-
active bifunctional porphyrin catalyst, which combines an
activated substrates under mild conditions have to be developed.
organocatalytic group (quaternary ammonium bromide) and a
Obviously, reactions of CO2 that require a high-energy input are
metal ion (MgII). It shows a high turnover number
not benign because in general this energy leads also to formation
(TON ¼ 103,000) for the synthesis of cyclic carbonates from
of CO2.
CO2 and epoxides under solvent-free conditions14. Related salen-
based complexes represent another kind of effective catalysts for
Cooperative effects for CO2 activation. To achieve low-energy- the electrophilic addition of CO2 to epoxides. Already in 2001, air
demanding synthetic protocols using CO2 as C1 building block, stable and commercially available Cr(III) salen complexes were
efficient interactions with the specific substrate is required. In this presented to be highly efficient catalysts in the coupling of carbon
respect, cooperative activation of carbon dioxide with such sub- dioxide with epoxides at mild temperatures and pressures by the
strates often in the presence of a suitable catalyst is of funda- group of Nguyen15. While most of the work in this area made use
mental importance. Among the CO2 functionalization of pressurized carbon dioxide, Kleij and co-workers16 showed
methodologies, traditional examples that make use of cooperative that inexpensive and structurally simple Zn(salphen) catalysts can
effects are the catalytic valorization of energy-rich substrates (for be employed as efficient catalysts for the synthesis of cyclic
example, strong nucleophilic organometallic reagents, epoxides, carbonates from CO2 and terminal epoxides under mild
aziridines and so on). They provide a straightforward way for the conditions (2 bar CO2). Noteworthy, the group of North17
thermodynamic driving force. communicated the formation of cyclic carbonates even at 25 °C

Box 1 | Coordination modes of CO2 with transition metals.

A key issue for valorization of CO2 to valuable chemical intermediates and further on to consumer products relies on efficient catalysts. As a basis, an
insightful understanding of the detailed organometallic chemistry of CO2 is of great importance for the further design of the catalytic processes. In fact,
the chelating mode between transition metal centres and CO2 has been investigated intensively via stoichiometric experimental studies46,47.

As shown above, CO2 has multiple reactive sites: the carbon atom is an electrophilic Lewis acid centre and the oxygen atoms act as weak nucleophilic
Lewis base. In its ground state, carbon dioxide possesses two equivalent C-O bonds that could both coordinate to a transition metal centre. As a result,
a series of transition metal CO2 complexes are known. If a metal centre reacts with one molecule of CO2, there are five different chelating modes
possible. More specifically, complex I with an M-C bond is sometimes termed as a metallacarboxylate. Electron-rich metal centres are more feasible to
form these types of complexes via electron transfer from metal centre to carbon atom. Adduct II (end-on type) seems less plausible due to the weak
interaction between the lone pair of only one oxygen atom and the metal centre. Meanwhile, complex III should be more stable, since CO2 acts as a
bidentate ligand with two oxygen atoms. In this case, a more electron-deficient metal centre is favoured for the electron transfer from oxygen atom to
transition metal. A combination of the above two mentioned electron transfer processed affords the three-membered metallacycle complex IV.
Moreover, the side-on-bonding p-complex V can also be formed in a similar spatial arrangement of atoms through the coordination of the C-O double
bond to the central metal.
On the basis of these different coordination and activation modes, well-designed transition metal complex catalysts are able to promote the reactivity
and also control the selectivity of CO2 fixation reactions in the organic synthesis. This promising research area still has many novelties to be discovered.

2 NATURE COMMUNICATIONS | 6:5933 | DOI: 10.1038/ncomms6933 | www.nature.com/naturecommunications


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NATURE COMMUNICATIONS | DOI: 10.1038/ncomms6933 REVIEW

Ts R2 R1
HOOC HO
N CO2R′
HOOC R
O
RCOOH ArCOOH RCOOH COOH
COOH R R3
3
R Ar
O O R
O R

X=Cl, Br, OPiv)


Ts R2 R1
N R

HSi(OMe)3
R-B or RZn

R′OH
Et2Zn
RX
Et2Zn

ArH
H2
Ar R R
R3 R3 R

Cheap and widely available Stable and less reactive

$: industrialized process
(M = M g , L i )

[H], R2NH

[H], RNH2
ONa
R

ROH

NH3
RM

NH NH O
O
OH
$

$
R R
COOH O H2N
HN O O RO R Me
HO O O N
RCOOH O O O O O HCONR2
N H2N O Me
O H O O RO
O
n
n

Figure 1 | Representative examples using CO2 as C1 building block in organic synthesis. Along with the rapid development of organometallic
chemistry and catalysis, various types of efficient CO2 transformations were have been discovered in the past decades. However, in general, the substrates’
scope and efficiency of these reactions are still limited due to the requirement of reactive agents for CO2 activation. As a result, only a few processes
have been industrialized until now (marked by $).

and 1 bar CO2 using bimetallic AlIII-salen complexes. More Apart from the utilization of energy-rich substrates (for
recently, the Kleij group18 presented an easily accessible amino example, epoxides), catalytic reductive formylation and methyla-
triphenolate complex based on AlIII metal centre. This complex is tion of amines represent important modern examples for
demonstrated to be a highly active and versatile catalyst for cooperative effects in the activation of CO2. Here the activation
organic carbonate formation. Remarkably, initial turnover energy for reductive deoxygenation of CO2 is significantly
frequencies as high as 36,000 per hour during the cycloaddition decreased by the coordination of amines to CO2 and the
of CO2 to epoxides were obtained with TONs exceeding 100,000. formation of N-C bonds (in a carbamate or urethane inter-
Except for the above-mentioned sophisticated metal complexes, mediate), which thus facilitates the reduction of CO2. Likely, the
simple onium salts can also acts as efficient catalysts. For instance, other advantage of amines is to increase CO2 concentration in the
a combination of ZnCl2 and [Bmim]Br reported by Xia’s group19 condensed phase28. These transformations represent diagonal
is a really practical, highly efficient and environmentally benign approaches to the chemical recycling of CO2, which combine
catalyst system for the chemical fixation of CO2 with epoxides. both reduction of CO2 and C-N bond formation processes
Finally, it is worth mentioning that Jiang, Han and (Fig. 3)29. More specifically, Cantat and co-workers reported an
co-workers20 in 2011 found that cellulose/KI was a very active, unprecedented organocatalytic synthesis of formamides from
selective and recyclable catalyst for this reaction without the CO2. Mechanistic studies uncovered the synergistic effect of the
assistance of any transition metal catalyst. organocatalyst TBD (triazabicyclodecene) and amine substrates
The direct polymerization of epoxides with CO2 to produce in the promotion of CO2 activation (Fig. 3, equation a)30. Shortly
polycarbonates has been accomplished too. In this respect, the afterwards, a highly active N-heterocyclic carbene organocatalyst
contributions from Coates and co-workers21,22 described very was designed by the same group for the formylation of N-H
active zinc b-diiminate catalysts for the synthesis of bonds in various amines and heterocycles under very mild
monodispersed, highly alternating carbon dioxide/epoxide conditions using CO2 and polymethylhydrosiloxane (PMHS;
copolymers with high molecular weight. In addition, the group Fig. 3, equation b)31.
of Williams23 demonstrated a zinc-based macrocyclic bimetallic Meanwhile, the methylation of amines via six-electron
catalyst for epoxide/CO2 copolymerization, which shows reduction of CO2 remains unknown until 2013. The market
remarkable activity at only 1 bar of CO2. Very recently, value of methylamines such as MeNH2, Me2NH and Me3N
iron  corrole complexes were synthesized by Nozaki and exceeds 4,000 Euro per ton. Therefore, the reductive methylation
co-workers24 to copolymerize epoxides with CO2, providing the of amines with CO2 can create additional value. In early 2013, our
first example of iron-catalysed PO (propylene oxide)/CO2 group developed a Ru catalyst system that was able to convert
and GPE (glycidyl phenyl ether)/CO2 copolymerization. The carbon dioxide and amines into various kinds of N-methylated
same group also demonstrated the stereoselective alternating products in the presence of hydrosilanes (PhSiH3). Notably,
copolymerization of cyclohexene oxide and CO2 with dimeric diverse functional groups were well tolerated under these
zinc complexes for the first time25. Besides, improved catalysts are conditions (Fig. 3, equation c)32. In the same year, Cantat
still desirable to better control the properties of the resulting et al.33 reported zinc catalysts able to perform the methylation of
materials26. Similarly, many efforts are also devoted to designing amines with CO2 and hydrosilanes at low pressure. Furthermore,
catalysts able to promote the reaction of CO2 with less-reactive the selective reduction of ureas was possible under similar
oxiranes, which could also provide novel materials27. reaction conditions. Although some silanes are considered to be

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O
O Cat.
CO2 O O
R R′
R R′
M = AlIII, X = OMe, Ar = Ph
Ar M = CrIII, X = Cl
Inoue et al., 1983
R3 R4 CO2 (8 bar), 100 °C,
M= CoIII,
X = OTs, Ar = Ph
(4-dimethylamino)pyridine
X CO2 (7 bar), 20 °C, PTAT
N N N N up to 916 TON
up to 930 TON, 93% yield
Ar M Ar M Nguyen et al., 2001
Jing et al., 2007
N N R1 O O R1 M = ZnII, R2 = t Bu
M = MgII, Ar = 3-O(CH2)6N+Bu3Br –-Ph X CO2 (2 bar), 25 °C, NBu4I
CO2 (17 bar), 120 °C
R2 R2 up to 86% yield
up to 103,000 TON, 83% yield
Kleij et al., 2011
Ar Sakai et al., 2012
Metalloporphyrin catalyst Salen catalyst

R1 R1

Cl
R2 R2 O
Cl O
N O O N O Al
Al O Al O Cl Cl
N N N
O O
R2 R2 CO2 (1 bar), 25 °C Cl CO2 (10 bar), 90 °C, NBu4I

NBu4 Br, up to 850 TON Up to 112,000 TON, 36,000 per hour TOF
Cl Kleij et al., 2013
North et al., 2010
R1 R1

Bimetallic aluminium(salen) catalyst Amino triphenolate aluminium catalyst

HO
OH
O HO
HO
ZnBr2 + N N Br – HO O O H
OH HO O n
CO2 (15 bar), 100 °C, KI CO2 (20 bar), 110 °C, KI
Up to 5,580 TON, 5,580 per hour TOF Up to 99% yield
Xia et al., 2004 Jiang and Han et al., 2011

Onium salts catalyst Cellulose catalyst

O Cat. O O
CO2
R n
R O

C6F5
X Ph
X
N N Ph
R R
Zn N
N N H O
Zn tBu t Bu Zn Zn
O O
N N C6F5 Fe C6F5 Et NH
Zn O
R R N N N N Ph
X Ph
X = OAc
2
O
CO2 (7 bar), 50 °C, TON = 354 CO2 (1 bar), 100 °C, TON = 527 CO2 (20 bar), 60 °C, TOF = 1,004 CO2 (30 bar), 40 °C, 74%ee
Mn = 25.5 × 10–3, Mw /Mn = 1.1 Mn = 7,360, Mw /Mn = 1.2 Mn = 29,000, Mw/Mn = 1.3 Mn = 12,000, Mw/Mn = 1.3
Coates et al., 2003 Williams et al., 2009 Nozaki et al., 2013 Nozaki et al., 2003

Zinc β-diiminate catalyst Dimetallic zinc catalyst Iron-corrole catalyst Dimeric zinc catalyst

Figure 2 | Established catalysts and reaction conditions for the catalytic productions of cyclic carbonate and polycarbonate from oxiranes using CO2
as the feedstock. Examples include metalloporphyrin, salen, metal-corrole, dimetallic as well as metal-free catalysts.

waste products of the silicone industry, all these methodologies systems shortly afterwards to convert amines into methylamines
are limited by the accessibility of the hydrosilanes and an in the presence of CO2 and H2. On one hand, Klankermayer and
additional workup step to remove siloxane by-products. co-workers34 presented the use of a molecularly defined
Obviously, catalytic methylations using CO2 and H2 represent a ruthenium complex [Ru(triphos)(tmm)] together with readily
greener method with H2O as the only by-product. In this respect, available organic acids as co-catalysts to afford the methylation of
two research groups independently reported similar catalytic aryl amines in good yields (Fig. 3, equation d). Meanwhile, the

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NATURE COMMUNICATIONS | DOI: 10.1038/ncomms6933 REVIEW

O
R1 R1 O
5 mol% TBD R1 5mol% IPr
N H + CO2 + PhSiH3 N H + siloxanes N H + CO2 + PMHS R1
THF, 24 h, 100 °C THF, 24 h, RT N H + siloxanes
R2 R2
R2 R2
24 –100%, 7 examples 6–99%, 26 examples
N
N i Pr
N i Pr
N + N O N N
N N TBD IPr
R1 N N
H H + (EtO)3SiH + N H H
H H i Pr i Pr

O O O R2
C
N Si(OEt)3
R1 R2 Cantat et al., 2012 Cantat et al., 2012

Ar
R CH3
2 mol% [RuCl2(dmso)4] N H [Ru(triphos)(tmm)]
R1 R1 CH3 + CO2 + H2 N or
4 mol% nBuPAd2 R or Ar N
HNTf2, THF, 150 °C CH3 Ar CH3
N H or RNH2 + CO2 N CH3 or
N
R2 PhSiH3, toluene, 100 °C R2 R CH3 ArNH2
27–94%, 12 examples

R1 63–99%, 25 examples Ph2P


Ph2P PPh2 PPh2
N H O Triphos Ru [Ru(triphos)(tmm)]
R1 P
R2 R1 R2 PPh2
N H + CO2 [R1R2NCO2– +H2NR1R2] N N
Ph2
Klankermayer et al., 2013
R2 –H2O
R2 R2 1 mol% Ru(acac)3
R1 1 mol% triphos
[Ru]/[H] –H2O H CH3
[Ru]/[H] 1.5 mol% MSA or LiCl
N H R–NH2 + CO2 + H2 N or
THF, 140 °C, 24 h R CH3 N
R2 R CH3
R1 O R1
[Ru]/[H] 40–99%, 35 examples
N N CH3
R2 –H2O O R CH3
H R2 [Ru] [Ru]/H2 R CH3 N
R–NH2 + CO2 R N
H2 N H H
H CH3
Beller et al., 2013 Beller et al., 2013

Figure 3 | Catalytic reductive formylation and methylation of amines with CO2 as C1 source. (a,b) Organocatalytic formylation of amines with
CO2 using silanes as the reductants. (c) Ru-catalysed methylation of amines with CO2 using silanes as the reductants. (d,e) Ru-catalysed methylation
of amines with CO2 using H2 as the reductant.

group of Beller demonstrated the efficient N-methylation of both diynes in the presence of catalytic amounts of Ni(0) and specific
aromatic and aliphatic amines using CO2/H2 as the methylation carbene ligands (Fig. 4, equation c). In the same year, the group of
reagent. Applying an in situ combination of Ru(acac)3, triphos Mori42,43 developed a nickel-catalysed regio- and stereoselective
and either acid additives or LiCl, the desired methylated amines ring-closing carboxylation of bis-1,3-dienes, which proceeds via
were obtained with high efficiency. Notably, selective insertion of CO2 into a bis-p-allylnickel intermediate followed by
monomethylation of primary amines as well as the methylation a transmetalation process of the resulting cyclic nickel carboxylate
of more challenging aliphatic amines proceeded smoothly under with a sensitive dialkylzinc reagent (Fig. 4, equation d). Except for
these conditions (Fig. 3, equation e)35. Interestingly, Shi et al.36 nickel-catalysed cyclization reactions, the Pd-catalysed
described in 2014 heterogeneous copper catalysts for the telomerization of 1,3-butadiene with CO2 is one of the first
same transformation with CO2 and H2. In general, formamides successful examples of the catalytic formation of a new C-C bond
are the common reaction intermediates for the above-mentioned between CO2 and an organic compound. Thirty years ago, Behr
methylation reactions. Again, this indicates the advantageous et al. found that the cyclization product is selectively produced
activation effect of amine substrates for the CO2 reduction step. employing Pd(acac)3 and PiPr3 as the catalyst. The resulting
d-lactone is formed via an allylic palladium carboxylate complex
as a key intermediate (Fig. 4, equation e)44. Generally, the CO2
CO2 fixation via oxidative cyclometallation. Pioneered by the transformations via oxidative cyclometallation pathways are
synthesis and isolation of Aresta’s complex [Ni(CO2)(PCy3)2] in restricted to substrates with extensive p systems (for example,
1975 (ref. 37), the development of low-valent metal (nickel or dienes and diynes). Interestingly, in 2008, the group of
palladium) complexes that mediate the oxidative couplings of Dong discovered that Aresta’s complex catalysed the
CO2 with various unsaturated hydrocarbons provides a facile cross-coupling of organozinc reagents with CO2. By replacing
approach to overcome the obstacles of CO2 fixation. While it nickel catalysts with palladium, the latter complexes were found
permitted the use of CO2 under atmospheric pressure, to be catalytically active as well for the reaction of aryl
stoichiometric amounts of metal were necessary to generate zinc bromides (Fig. 4, equation f). The proposed mechanism
various metallacycle complexes via the oxidative cyclometallation consisted of an oxidative addition of Ni(0) to CO2 to generate
of Ni(0) complexes with CO2 and olefins or alkynes (Fig. 4, Aresta’s complex; transmetalation with the organozinc reagent
equations a and b)38,39. The nickel-mediated stoichiometric and reductive elimination affording the corresponding zinc
fixation of carbon dioxide with alkenes40 has been known for over carboxylate that was finally hydrolysed by acidic workup
20 years largely due to the works from Hoberg and co-workers. (Fig. 4, equation g)45.
However, the limited substrate scope and/or relatively harsh
conditions still remain concerns for this CO2 activation strategy.
Meanwhile, only a few catalytic systems based on this strategy Carboxylation reactions via CO2 insertion into C-M bonds.
have been developed. In 2002, Louie et al.41 communicated an The formation of a thermodynamically and kinetically stable C-C
efficient nickel-catalysed [2 þ 2 þ 2] cycloaddition of CO2 and bond is the most desirable form of CO2 fixation. Since carbon

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Ni(0), DBU Ni(0), TMEDA N O


+ CO2 O + CO2
(DBU)2Ni O Ni O
N
R3
5 mol% Ni(cod)2 O
R1 R3 R1
10 mol% IPr
+ CO2
R2 60 °C, 2 h R2 O
R4 1 atm
R4
O
75 – 92%, 9 examples Louie et al., 2002 Cy3P C
Ni
Cy3P O
1. 10 mol% Ni(acac)2 CO2Me
20 mol% PPh3 H
Aresta complex
4. 5 eq. R2Zn, 0 °C
X + CO2
2. CH2N2,Et2O X
1 atm R
H
56 – 94%, 8 examples Mori et al., 2002

0.06 mol% Pd(acac)2


0.18 mol% Pi Pr3 L Pd
+ CO2
O
MeCN, 90 °C
O O O
Intermediate δ-lactone
40% yield, 96% selectivity Behr et al.,1983
10 mol% Pd(OAc)2
20 mol% PCy3 5 mol% [Ni(PCy3)2]2(N2)
Ar ZnBr Ar COOH R ZnBr R COOH
THF, 0 °C,1 atm CO2 Toluene, 0 °C,1 atm CO2

HCl
O Cy3P CO2ZnBr
CO2 Cy3P C R ZnBr
Ni(0)(PCy3)2 Ni RCO2ZnBr
Ni
Cy3P O Cy3P R –Ni(0)(PCy3)2

73–97%, 20 examples Dong et al., 2008

Figure 4 | Catalytic CO2 fixation via oxidative cyclometallation with low-valent Ni and Pd complexes. (a,b) The generation of metallacycle
complexes via the oxidative cyclometallation of Ni(0) complexes with CO2 and unsaturated bonds. (c) Ni-catalysed [2 þ 2 þ 2] cycloaddition of
CO2 and diynes. (e) Pd-catalysed telomerization of 1,3-butadiene with CO2. (f,g) Aresta’s complex catalysed the carboxylation of organozinc reagents
with CO2.

dioxide is an inert electrophile, highly reactive organolithium and Pioneered by the work of Iwasawa et al. in 2006 (Table 1, entry
Grignard reagents are typically utilized as strong nucleophiles to 1) the catalytic carboxylation of organoboron reagents with CO2
react with CO2 directly to construct C-C bonds and furnish in the presence of Rh53, Cu54–57 and Ag (Table 1, entry 4)58
valuable carboxylic acids and their derivatives. In fact, the current catalysts has been developed. These coupling reagents exhibit
industrial synthesis of salicylic acid derivatives is a prime example milder nucleophilicity, better stability to air and moisture as well
for this type of reaction. In general, nitrogen or oxygen nucleo- as higher compatibility with sensitive functional groups. Among
philes exhibit much better reactivity than carbon nucleophiles for these results, the combination of IPrCu-NHC complex and
CO2 activation. As a result, catalytic C-C bond formation using alkoxide base (M0 OR0 ) developed by the group of Hou55,57 since
CO2 as C1 building block with less-reactive substrates has been 2008 was found to be the most active catalyst system for the
and constitutes still a major challenging task for organic synthesis carboxylation of aryl-, alkenyl- and also alkylboronic acid
and catalysis research46. This goal can be achieved with the aid of derivatives (Table 1, entries 3 and 6). A general synthesis of
transition metal catalysts that lower the activation energy and various carboxylic acids with CO2 was accomplished, and a wide
thus considerably increase the reaction rate for the C-C bond- range of functional groups were well tolerated. On the basis of
forming step. Particularly, the CO2 insertion reactions into stoichiometric experiments (taken the reactions of ArBPin, for
various C-M bonds to form carboxylato complex via the example, as shown in Fig. 5a), a general mechanism for such
formation of a new C-C bond are well known47. Moreover, reactions was also proposed: the metathesis reaction between
transition metal complexes can react with less-nucleophilic [(IPr)CuCl] and alkoxide generates the corresponding alkoxide
organometallic reagents, for example, organoboron compounds, complex [(IPr)Cu(OR0 )], which could coordinate with
as well as organohalides, unsaturated bonds even activated C-H organoboron reagents (R-BX2) through interaction between the
bonds to form C-M bonds efficiently, similar to their alkoxy group and the boron atom. Subsequent transmetalation to
performance in the classic cross-coupling reactions48. the copper atom generates the organocopper complex [(IPr)CuR].
Furthermore, the CO2 insertion intermediate (RCOO-M) might Then, CO2 insertion into the C-Cu bond yields the carboxylate
be quenched in a suitable way to regenerate the catalytically active [(IPr)Cu(OCOR)], which on metathesis with alkoxide base
species. This provides numerous possibilities for catalytic M0 OR0 regenerates [(IPr)Cu(OR0 )] and releases the carboxylate
carboxylation reactions with all the above-mentioned salt RCO2M0 . Finally, the latter yields the carboxylic acid RCO2H
substrates49–52. Representative examples for such processes are via hydrolysis. Some key reaction intermediates, such as the
listed in Table 1 including a summary of substrates, catalyst copper(I) alkoxide complexes [(IPr)Cu-(OR0 )], organocopper
precursors, ligands, additives as well as other conditions. In species [(IPr)CuR] and the carboxylate copper intermediates
addition, a comparison of the postulated mechanisms for [(IPr)Cu(OCOR)], were successfully isolated and structurally
carboxylation and hydro(bora)carboxylation reactions are characterized, which were also confirmed to be catalytically active
presented in Fig. 5. species in these transformations.

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Table 1 | A summary of carboxylation reactions of C-B, C-X and C-H bonds with CO2: catalytic systems and reaction conditions.

Entry R X Catalyst precursor/ligand Additive Condition Ref.


1 Aryl, alkenyl B(OR0 )2 3 mol% [Rh(OH)(cod)]2/7 mol% dppp 3 equiv. CsF 1,4-dioxane, 60 °C 53
2 Aryl, alkenyl B(OR0 )2 5 mol% CuI/6 mol% bisoxazoline 3 equiv. CsF DMF, 60 °C 54
3 Aryl, alkenyl B(OR0 )2 1 mol% [(IPr)CuCl] 1 equiv. tBuOK THF, 70 °C 55
4 Aryl, alkenyl B(OR0 )2 10 mol% AgOAc/10 mol% PPh3 2 equiv. tBuOK THF, 70 °C 58
5 Alkyl B(OR0 )2 10 mol% CuOAc/1,10-Phen 1 equiv. tBuOK Toluene, 100 °C 56
6 Alkyl B(OR0 )2 3 mol% [(IPr)CuCl] 1.05 equiv. MeOLi THF, 70 °C 57
7 Akynyl H 10 mol% Cu(diPhPhen)(PPh3)2NO3 1.2 equiv. Cs2CO3 DMF, 35–50 °C 62
8 Akynyl H 5 mol% P(NHC)0.5(NHC-Cu)0.5 1.2 equiv. Cs2CO3 DMF, RT 61
9 Akynyl H 1 mol% AgI 1.5 equiv. Cs2CO3 DMF, 50 °C 59
10 Akynyl H None 1.2 equiv. Cs2CO3 DMF, 120 °C 60
11 Aryl H (pKa(C- 1.5 mol% [(IPr)AuOH] 1.05 equiv. KOH THF, RT 65
H)o30.3)
12 Aryl H (pKa(C- 3 mol% [(IPr)CuOH] 1.1 equiv. CsOH THF, 40 °C 66
H)o27.3)
13 Aryl H (pKa(C- 5 mol% [(IPr)CuCl] 1.1 equiv. tBuOK THF, 80 °C 63
H)o32.5)
14 Aryl H (pKa(C- None 1.2 equiv. Cs2CO3 DMF, 125 °C 64
H)o27.3)
15 Aryl Br 5 mol% Pd(OAc)2/10 mol% tBu-XPhos 2 equiv. Et2Zn DMA, 40 °C 69
16 Aryl, alkenyl Cl 5 mol% NiCl2(PPh3)2/10 mol% PPh3/10 mol% 2 equiv. Mn DMI, 25 °C 70
Et4NI
17 Benzyl Cl 10 mol%NiCl2  glyme/PCp3  HBF4 5 equiv. Zn, 2 equiv. DMA, RT 71
MgCl2
18 Aryl or OPiv 7 mol% NiCl2(dppf)/10 mol% NiCl2(PMe3) 1 or 2 equiv. Mn DMA, RT or DMF, 72
benzyl 80 °C
COD, cyclooctadiene; DMA, dimethylacetamide; DMF, dimethylformamide; DMI, 1,3-dimethyl-2-imidazolidinone; dppp, 1,3-bis(diphenylphosphino)propane; equiv., equivalent; THF, tetrahydrofuran.

Apart from organoboron reagents, acidic C-H bonds can also with Pd(OAc)2 along with coordination of the second molecule of
undergo deprotonative metallation with specific transition metal substrate. Subsequently, the alkenyl palladium(II) species
complexes to form C-M bonds with the assistance of strong bases. undergoes nucleophilic carboxylation to afford a palladium
Accordingly, the catalytic carboxylation of terminal alkynes carboxylate intermediate, which reacts with 2-hydroxystyrene
(Table 1, entries 7–10)59–62 and electron-deficient and base to give lactone with regeneration of the cyclometalated
(hetero)arenes (Table 1, entries 11–14)63–66 (pKa(C-H)o32.5) intermediate. The same group also reported another approach for
is achieved through the following CO2 insertion and metathesis of the direct carboxylation reaction of aromatic C-H bonds: namely,
metal carboxylate intermediates with base. Except the active the Rh(I)-catalysed carboxylation of aromatic compounds via
copper and gold N-heterocyclic carbene complexes, chelation-assisted ortho-metalation (Fig. 5d)68. The key
Cu(diPhPhen)(PPh3)2NO3 (Table 1, entry 7) and AgI (Table 1, intermediate is proposed to be the methylrhodium(I) complex F,
entry 9) were also demonstrated to be the effectual catalysts for which undergoes chelation-assisted oxidative addition with a
the carboxylation of terminal alkynes by the group of Goossen62 suitable C-H bond to afford rhodium(III) complex G, followed by
and Lu59, respectively. Interestingly, at higher temperature reductive elimination of methane to give the nucleophilic
(4120 °C), the Cs2CO3-mediated carboxylation of heteroarenes arylrhodium(I) complex H. Consequently, nucleophilic
(Table 1, entry 14)64 and terminal alkynes (Table 1, entry 10)60 carboxylation of intermediate H affords rhodium carboxylate I,
with CO2 were reported by Hu and Zhang’s groups which undergoes transmetalation with a methylaluminium reagent
independently as well. to give aluminium carboxylate J and regenerate the active
Later on, the group of Iwasawa showed the formation of C-M methylrhodium(I) complex F.
bonds by a directing group-assisted C-H activation process, which The oxidative addition of organo(pseudo)halides with low-
was used for subsequent carboxylation reactions with CO2. In fact, valent transition metals constitutes another way to form C-M
treatment of 2-hydroxystyrenes bearing a hydroxy group as the bonds. In this respect, in 2009, Martin and co-workers69
chelating group with catalytic amount of Pd(OAc)2 in the presence presented a palladium-catalysed direct carboxylation of aryl
of Cs2CO3 and CO2 afforded the corresponding coumarins via bromides with CO2 (Table 1, entry 15). In contrast to the
carboxylation/condensation (Fig. 5c)67. It is proposed that first the reactions vide supra, this is the first example for carboxylation
six-membered alkenyl palladium intermediate is generated by reactions of electrophiles instead of nucleophiles. Therefore,
chelation-assisted alkenyl C-H bond cleavage of 2-hydroxystyrene additional reductant (here Et2Zn) is needed to regenerate the

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NiCl2·L2 R1
PhCH(R1)COOH
Zn X
[(IPr)CuCl]/KOt Bu H+
R–BPin + CO2 R COOH ZnCl2
[H+] 1/2 (PhCH(R1)COO)2Zn
Ni(0)L2
[(IPr)CuCl] 1/2 Zn A

KOOC OMe KOt Bu THF, RT BPin OMe

[(IPr)Cu(Ot Bu)] R1 R1 R1
KOt Bu 92% yield +L L
O L L
THF, RT Ni Ni X
Ni –L L
O L
O E X
B C
(IPr)Cu O
1 atm CO2
(IPr)Cu OMe R1
L 1/2 Zn
THF, –78 °C to RT
92% yield 91% yield Ni
OMe 1/2 ZnX2
L
Hou et al., 2008 CO2 D Martin et al., 2013

O
R OH Pd(OAc)2/Cs2CO3 ArCOOH [LnRhI-Cl]
+ CO2 O R
H+ MeAlX2
ArCOOAlX2
J [LnRhI-Me] N
MeAlX2 F
R
R
R
CO2 O
OH O Cs Pd O N
Pd(OAc)2 Cs Pd O
Cs2CO3 O O N
O
R O RhILn RhIII(H)(Me)Ln
I
G
R
O –CsHCO3, CsOH N

O R R OH RhILn
CO2 H CH4

Iwasawa et al., 2013 Iwasawa et al., 2011

Figure 5 | Possible reaction mechanisms for typical carboxylation reactions with CO2. (a) Reaction mechanism for Cu-catalysed carboxylation reactions
of organoboron compounds. (b) Reaction mechanism for Ni-catalysed carboxylation reactions of benzyl halides. (c,d) Directing group-assisted
carboxylation of C-H bonds.

catalytically active low-valent Pd(0) species. After Martin’s work, reported a novel Ni-catalysed carboxylation of aryl esters with
Tsuji and co-workers found that less-expensive nickel catalysts less-activated C-O bonds (Table 1, entry 18)72. This new protocol
are active in carboxylation of aryl chlorides and vinyl chlorides. deals with the development of a synergistic activation of CO2 and
Notably, these reactions proceed under 1 atm CO2 pressure at a rather challenging activation of inert C(sp2)  O and
room temperature (Table 1, entry 16)70. The Ni(I) species was C(sp3)  O bonds derived from simple and cheap alcohols. In
involved in the catalytic cycle with the aid of the Mn/Et4NI general, all these modern transformations have to be compared
system as an efficient reducing agent. Although the carboxylation with the classic carboxylation of Grignard reagents. The main
of aryl bromides and chlorides with CO2 provides a advantage of these recent methodologies can be the tolerance of
straightforward synthetic route to functionalized benzoic acids, functional groups, and thus the possibility to synthesize complex
these protocols cannot be utilized to access aliphatic electrophiles, carboxylic acid derivatives. On the other hand, the major
for example, for the synthesis of biologically active phenylacetic drawback of all carboxylation reactions of electrophiles is the
acid derivatives. Hence, it was interesting when Martin’s group necessity to use (over)stoichiometric amounts of metals as
reported in 2013 the first catalytic carboxylation of primary, reducing agents. Obviously, hydrogen would be a much more
secondary and tertiary benzyl halides utilizing CO2. Their favourable reductant for such processes; however, no efficient
protocol provides an opportunity to prepare phenylacetic acids regeneration of the active low-valent metal complexes have been
from commercially available and cheap starting materials realized yet.
(Table 1, entry 17)71. The proposed catalytic cycle starts with Significant advancements were made in the catalytic CO2
an initial reduction of the Ni(II) pre-catalyst by Zn followed by hydrocarboxylation of unsaturated C-C bonds too. For example,
oxidative addition to the corresponding alkyl halides, thus in 2008, Iwasawa and co-workers reported the hydrocarboxyla-
delivering Z3- and Z1-bound nickel complexes B and C in a tion of allenes and 1,3-dienes with a silyl pincer-type palladium
rapid equilibrium. Generation of the reduced Ni(I) species D by complex. The reactions were carried out at room temperature
Zn and CO2 insertion affords the carboxylate nickel intermediate under 1 atm CO2 and enabled the facile and regioselective
E. Further treatment with Zn regenerates the active Ni(0)L2 A synthesis of b,g-unsaturated carboxylic acids73. The reaction is
species and provides zinc carboxylate, which on hydrolysis believed to start with generation of a silyl pincer-type palladium
delivers the final product (Fig. 5b). Very recently, the same group hydride complex via transmetalation of AlEt3 to (PSiP)PdOTf

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followed by b-hydride elimination. Hydrometalation of 1,1- hydride species. It reacted with an alkyne substrate smoothly to
disubstituted allenes preferentially afford the less-congested afford the corresponding copper alkenyl complex, which on CO2
s-allylpalladium intermediate, which then undergoes insertion affords the copper carboxylato complex. d-bond
nucleophilic addition to CO2 at the g-position of the palladium metathesis of this species with hydrosilane regenerated
regioselectively to give the carboxylate palladium complex. [Cl2IPrCuH] and provided the corresponding silyl ester. In
Finally, a transmetalation/b-hydride elimination sequence analogy to hydrocarboxylations, catalytic boracarboxylations of
regenerates the catalytically active palladium hydride species alkynes with diborane and CO2 using an N-heterocyclic carbene
and releases the carboxylation product as its Al salt (Fig. 6a). copper catalyst were recognized by Hou in 2012 (ref. 77). The
Meanwhile, the first direct hydrocarboxylation of alkenes reaction of [(NHC)Cu(OR)] with B2(pin)2 instantly gave the
occurred in similar manner. Rovis and co-workers74 developed borylcopper complex [(NHC)CuB(pin)]. Its subsequent reaction
a Ni-catalysed hydrocarboxylation of styrenes using Et2Zn as the with internal alkyne afforded a b-boryl alkenyl complex, which
hydride donor with CO2 (Fig. 6b). The suggested mechanism undergoes the following CO2 insertion and metathesis processes
involved a nickel hydride complex as active catalyst. Afterwards, a to furnish the final product (Fig. 6d).
highly regio- and stereoselective three-component Ni-catalysed
syn-hydrocarboxylation of alkynes with Et2Zn and CO2 using
Ni(cod)2 as catalyst and CsF as additive was presented by Ma and Carbonylation reactions using CO2 as CO surrogates.
co-workers75. Although these three examples demonstrate Compared with all above strategies to directly use CO2 as C1
interesting carboxylation reactions, strong and extremely air- building block in chemical synthesis, the in situ generation of CO
sensitive reducing agents are indispensable. This problem is from CO2 is clearly underdeveloped. Nevertheless, this strategy
partially avoided in the copper-catalysed hydrocarboxylation of represents a particularly promising tool for more practical
alkynes with CO2 using hydrosilanes as milder reducing agent applications. We are convinced that such CO2 valorization
realized by Tsuji and co-workers (Fig. 6c)76. The fundamental approach will open up new opportunities to realize industrially
catalytic steps in their hydrocarboxylation were examined by important carbonylation reactions. Advantageously, here CO2 is
stoichiometric reactions. Treatment of the catalyst precursor used as a sustainable carbonyl source instead of hazardous CO.
[Cl2IPrCuF] with silane led to the catalytically active copper For more than 60 years, carbonylation reactions using CO

10 mol% Ni(acac)2
20 mol% Cs2CO3 COOH
1 mol% (PSiP)PdOTf Ar + CO2 H
2.5 eq. Et2Zn, THF, 23 °C Ar
1.5 eq. AlEt3 H+ COOH
Ph • CO2
1 bar CO2, DMF, RT Ph Ar NiLn
88%
(PSiP)PdOTf
Ar H
AlEt3
H+
[(PSiP)PdH]
Et2Zn CO2NiLn
Pd(PSiP) COOPd(PSiP) COOAlEt2 H–NiLn
ZnX H
Ar
Ph CO2 Ph AlEt3 Ph
Ar
OTf
Et2Zn
Ph2P Pd PPh2
Et–NiLn
Si (PSiP)PdOTf
Me CO2ZnEt H+ CO2H
H H
Ar Ar
Iwasawa et al., 2008 Rovis et al., 2008

O Li +
5 mol% [Cl2IPrCuF] H CO2H 5 mol% [(SIMes)CuCl] O O
R R′ + CO2 R R′ + B2(pin)2 + CO2 B–
2 eq. HSi(OEt)3, hexane, 70 °C 1.1 eq. LiOt Bu O
R R′
THF, 80 °C, 14 h R R′
[Cl2IPrCuF]
T.M
HSi(OEt)3
H+
H CO2Si(OEt)3 R R′
Cl Cl
Ph Ph (IPr)Cu B(Pin)
R i Pr i Pr [(IPr)Cu-B(Pin)]
R′
HSi(OEt)3 N N Hexane, RT, 92% Ph Ph
i Pr i Pr
Cu Benzene,
B2(pin)2 CO2
H [Cl2IPrCuH] RT, 1 h, 95%
Cl Cl
Cl Cl +
i Pr i Pr
i Pr i Pr LiOt Bu, THF, RT, quant. (PrI)Cu
N N
N N [(IPr)Cu-Ot Bu]
i Pr i Pr O O O
Cu i Pr i Pr –B
Cu O
O O
H O Li +
R O O Ph Ph
H B–
R R′ O
R′ Tsuji et al., 2011 Ph Ph Hou et al., 2012

Figure 6 | Selected examples for hydro(bora)carboxylation reactions of alkenes and alkynes with CO2. Examples include (a) allenes, (b) styrenes and
(c,d) internal alkynes.

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represent major technology for the production of value-added development of next-generation CO2 utilization. Apart from
bulk and fine chemicals from easily available feedstocks. As an CO2 reduction with hydrogen and alcohols, Skrydstrup and co-
example, over 10 million tons of oxo-products are produced every workers shortly afterwards reported the successful identification
year from alkenes via hydroformylation and related tandem of an efficient conversion of CO2 to CO performed at room
reactions78. Besides, methyl propionate, a key intermediate for temperature with catalytic caesium fluoride in the presence of a
methyl methacrylate (annual demand is currently about 3 million disilane, which can be coupled to Pd-catalysed amino- and
tons), is in part produced by palladium-catalysed alkoxycarbonylations with aryl bromides and iodides86.
methoxycarbonylation of ethylene79. So far, all these processes Inspired by nature’s efficiency in converting carbon dioxide
make use of CO, which is also difficult to transport on a bulk into carbohydrates and other organic matter through photo-
scale. Notably, the physical properties of carbon monoxide synthesis, chemists have also explored opportunities to directly
(especially its toxicity) impede its wider use in academia too. In reduce CO2 to CO by photocatalytic means. Since CO2 does not
this respect, carbonylations with CO2 offer a more safe and absorb either visible or ultraviolet radiation in the wavelengths of
accessible tool for synthetic organic chemists. The general 200–700 nm, this process requires a suitable photocatalyst to
strategy to use carbon dioxide as a carbonyl source is based on absorb ultraviolet–visible radiation and transfer it to CO2.
the in situ reduction of CO2 to CO, which then can be used in Photosensitizers (PSs) that meet this criterion often include a
subsequent carbonylation reactions. It is long known that metal centre, as the d-orbital splitting in organometallic species
combination of carbon dioxide and H2 at high temperature often falls within the energy range of far-ultraviolet and visible
(4300 °C) allows for so-called reverse water gas shift (RWGS) light. The reduction process begins with excitation of the PS. This
reaction, in which a mixture of carbon monoxide, carbon dioxide, causes the transfer of an electron from the metal centre into the
hydrogen and water is formed. On the basis of their previous coordinated ligands. This movement is termed as metal-to-ligand
studies on the RWGS process, Tominaga and Sasaki et al.80 charge transfer process. Back-electron transfer from the ligands to
reported in 2000 the first ruthenium-catalysed hydroformylation/ the metal after the charge transfer is prevented by including an
reduction of alkenes with CO2 using Ru3(CO)12 as catalyst in the electron-donating species to quench the exciting state of the
presence of LiCl as additive. It is surprising that this seminal work photocatalyst, thus forming the one-electron-reduced (OER)
of Tominaga et al. has attracted only minor attention, probably intermediate for further CO2 reduction processes87.
due to the still drastic conditions and the efficiency of the Initial work by Lehn and co-workers in the 1980s led the
reaction. For example, unwanted alkene hydrogenation side development of first photocatalytic CO2 reductions. Here, CoCl2
reactions occurred. Recently, our group improved this process by was used as the catalytic site for CO2 reduction with
the application of a specific bulky phosphite ligand (Fig. 7a)81. [Ru(bpy)3]Cl2 as PS (Fig. 7d)88. However, CoCl2 has very low
Applying the optimized catalytic system, the yields of alcohols, selectivity towards the reduction of CO2 to CO, resulting from the
the chemoselectivity of the process and especially the TON of the reduction of water in the aqueous media to produce H2 that is the
catalyst was significantly improved compared with the known main product in this system. The TON of (CO þ H2) is only 32
ligand-free catalysis system. In the above-mentioned based on [Ru(bpy)3]Cl2. The efficiency of these photocatalytic
carbonylation reactions via RWSG reaction, water is always processes is also characterized by its quantum yield ^, which is
produced as a side product and is not involved in the following defined as the number of times a CO2 molecule is transformed
alkene carbonylation reactions. Remarkably, the group of per photon absorbed by the PS. However, this system reached a
Leitner82 reported a rhodium-catalysed hydrocarboxylation of quantum yield of only 1.2%. Despite the low selectivity and
alkenes with CO2 and H2 to produce carboxylic acids, in which efficiency of this reaction, the simultaneous reduction of CO2 and
in situ-formed H2O was utilized as the nucleophile in this H2O produces in fact syngas, which is of interest for large-scale
transformation (Fig. 7b). industrial processes. Moreover, it represents an early step in the
Although H2 can act as an efficient reducing reagent for CO2 development of chemical systems capable of artificial
reduction, in many cases the following carbonylation reaction photosynthesis and solar energy conversion. Later, the same
does not tolerate H2 due to the hydrogenation of the substrate. As research group found that rhenium-based complexes
a result, the development of other benign CO2 reductions to [Re(bipy)(CO)3X] (X ¼ Cl, Br) acting as both PS and catalyst
generate CO is highly desired for the valorization of CO2. are more efficient and represent more selective catalysts for CO2
Combining our long-term experience in alcohol dehydrogena- reduction89. The process has very high CO/H2, selectivity,
tion83 and carbon dioxide reduction reactions5,84, very recently generating only CO, and affords a quantum yield of up to 14%.
efficient reforming processes of alcohols and CO2 were developed. It is indicated that the dissociation of the ligand X  from the
This allows for catalytic alkoxycarbonylation reactions using CO2 unstable 19-electron OER is a key step in this photocatalytic
as the C1 source in the presence of a ruthenium/[Bmim]Cl reduction of CO2 (ref. 90). In addition, Fujita and co-workers
catalyst system. Key to success was an unprecedented in situ identified the binuclear [Re-C(O)O-Re] moiety as a key
formation of CO from CO2 (Fig. 7c)85. In contrast to previously intermediate of the two-electron reduction process from CO2 to
reported hydrocarboxylation reactions of alkenes with CO2, CO (ref. 91). In 2008, based on their insightful mechanistic study,
similar carboxylated products are obtained, but the presence of the most efficient photocatalytic system was successfully
stoichiometric amounts of strong and expensive reductants like developed by the group of Ishitani using a mixed catalysts’
Et2Zn and silanes is avoided. The following reaction steps are system with fac-[Re(bpy)(CO)3(CH3CN)] þ and fac-[Re-4,40 -
proposed: initially, CO2 is reduced to CO (path I) or alkyl (MeO)2bpy(CO)3P(OEt)3] þ affording the optimized quantum
formates (path II) through transfer hydrogenation with alcohols. yield for CO formation was 0.59 (ref. 92).
Path I is proposed to be the major reaction pathway for this Despite the improved activity of rhenium polypyridine
transformation based on the control experiments. Meanwhile, the complexes for CO2 reduction, a major problem with these
alcohol undergoes dehydrogenation to form the corresponding photocatalysts is the lack of an extended absorption into the
carbonyl compound (path III). Interestingly, a minor amount of visible region. To solve this problem, Ishitani and Bian and co-
the CO comes from further decarbonylation reactions of the workers presented the use of covalently linked heteronuclear Ru
alcohol as shown by isotope-labelling experiments. It is estimated and Re multimetallic complexes in the photocatalytic reduction of
that this novel methodology is applicable to other carbonylation CO2 (refs 93,94). Enhancement of the photocatalytic response to
reactions as well and will contribute substantially to the light in the visible region was achieved by specifically designed

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H2 as the reductant :
Ru3(CO)12 (0.5 mol%),
L* (Ru:L* 1:1.1) R R
R + CO2/H2 + + R
CH2OH CHO
LiCl (25 mol%), NMP,
(R = nC H )
6 13
(60 bar, 1:1) 130 °C, 24 h

L* 76% (51:49) 1% 15%


MeO
No ligand 33% (51:49) 6% 22%
O
P O
O L* (Beller et al., 2014) TONRu(0.05 mol%) 200

MeO L* No ligand (Tominaga et al., 2000) TONRu <20

[{RhCl(CO)2}2] (2.4 mol%)


PPh3 (24 mol%)
p-TsOH (18 mol%)
R + CO2/H2 + R
COOH
50 mol% CH3I
(R = nC6H13) (70 bar, 6:1) 74%
AcOH, 180 °C, 16 h
Leitner et al., 2013

ROH as the reductant :


N
Ru3(CO)12(1 mol%) Cl–
R′ [Bmim]Cl (2 equiv.) R′
+ CO2 + ROH N
R
(40 bar) 160 °C, 20 h R
COOR nBu
36 examples, 41%–95% yield [Bmim]Cl
Path I (major)
R OH + CO2 CO Beller et al., 2014
–RH

Path II R OH R′
(Minor)

R′ –H2
HCOOCH2R COOCH2R RCHO R OH
R′
Path II (minor) Path III (minor)

Photocatalytic approach :

hν PS RS– CO2

PS: [Ru(bipy)3]Cl2

RS: Co(II) species

D: R3N
PS*
PS–
Lehn et al., 1982
RS CO
D OC CO
D+ OC
Re N
Cl
N
N
Re OH
N N
N N N COCO Re N N
Ru Re OH
CO N N N N CO
N N OH N Cl CO
Ru Re CO
N OC Cl OH N N OH N Cl
OC
Re N N
N OC
Ru N N

TON (CO2) 170 190 240


HPW12O402–
Pt(0)
+ H2 5– O
H+ VI
3[PW 12O40]
3– H+ 5 [PWV VI
2W 10O40]
O O
M+
5– ReIbpy(CO)3X
CO2 + H+5[PWV2WVI10O40] CO + H2O + H+3[PWVI12O40]3– O O
Light

Light
CO2 + H2 CO + H2O
Catalyst N N
Re NCCH
OC 3
Neumann et al., 2011 OC CO

Figure 7 | Catalytic production of CO from CO2 reduction and its application in carbonylation reactions. (a,b) H2 as the reductant. (c) Alcohol as the
reductant. (d–f) Photocatalytic approach.

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supramolecular complexes, and their high photocatalytic activities Carboxylation reactions via CO2 insertion into C-M bonds in
were attributed to intramolecular electron transfer from the OER combination with classical coupling reactions are intensively
Ru species to the Re moiety. The binuclear complex Ru–Re, studied in the past 10 years. Although this strategy furnished a
trinuclear complex RuRe2 and tetranuclear complex RuRe3 all series of interesting transformations, the requirement of stoichio-
furnished higher TON of CO (Fig. 7e). Despite recent improve- metric amounts of strong bases, sensitive metal reagents or
ments95, it should be noted that, in the above-mentioned expensive hydrosilanes are evident drawbacks that need to be
photochemical CO2 reduction, common sacrificial donors such overcome. The key point to solve such problems in the future will
as triethylamine (TEA), triethanolamine (TEOA) and 1-benzyl- be the invention of new routes to quench metal carboxylate
1,4-dihydronicotinamide (BNAH) have to be used. From a complex (RCOOM) with less-nucleophilic agents to afford the
practical point of view, it is noteworthy that in 2011 Neumann final product and regenerate the original catalytically active species.
and co-workers96 developed a photoreduction of CO2 to CO with Finally, it is worth noting that the catalytic in situ generation of
H2 catalysed by a rhenium(I) phenanthroline-polyoxometalate CO from CO2 and its recent applications in sequential carbonyla-
hybrid complex. In this study, previously used sacrificial electron tion reactions is a more favourable strategy for CO2 valorization. It
donors were replaced by H2. The working catalysis system is provides the use of safe and abundant CO2 instead of CO as
summarized in Fig. 7f. On one hand, a polyoxometalate oxidizes carbonyl source. Here the improvement of (regio)selectivities and
H2 to two protons and two electrons in the presence of Pt(0). On to use milder reaction conditions represent important targets. So
the other hand, the reduced form of the polyoxometalate reacts far, most catalysts in such reactions are ruthenium-based
with CO2 with the assistance of a chromophoric rhenium(I) complexes. Encouraged by the recently developed highly regiose-
complex and visible light to produce CO and H2O. As a result, the lective ruthenium-catalysed hydroformylation reaction98,99, in the
overall reaction is a photocatalytic RWGS reaction, which is of future more efforts should be donated to solve the regioselectivity
interest for both industry and academia for its further potential problem with suitable ligands and/or additives. Last but not the
application in carbonylation reaction with CO2. least, similar to other catalysis processes, the discovery of non-
noble metal-catalysed reactions, for example, iron catalysts, is an
essential issue in this field. Although related photocatalytic
Future perspectives
Today’s chemical production as well as academic organic approaches proceed under very mild conditions, the TON is too
low currently. Probably, cascade reaction sequences that make use
synthesis relies mainly on the use of fossil-based carbon sources.
In contrast, the increased valorization of CO2 as a recyclable and of carbonylation processes to consume the in situ-generated CO
will drive the overall reaction more efficiently.
abundant C1 building block would allow for the development of a
sustainable chemical industry. In this respect, the development of
benign transformations of carbon dioxide is a highly attractive Towards artificial photosynthesis. Photosynthesis basically
object for synthetic chemistry. Clearly, in the past decades, several supplies the carbon source for all organic compounds on Earth. It
effective activation modes for catalytic CO2 fixation and a series is an ideal green process for the conversion of light energy into
of novel transformations have been disclosed. chemical energy, which makes use of CO2 (Fig. 8, equation a).
Inspired by the nature’s strategy, the development of sustainable
and straightforward catalytic C-C bond-forming reactions of CO2
Issues need to be resolved. Despite the impressive progress, the in industrially relevant target molecules will be the ‘crown jewel’
efficiency of most reactions is far from satisfying. Hence, only of organic synthesis and catalysis research in the future. We
recent new processes utilizing CO2 as the C1 source have been expect several dream reactions towards artificial photosynthesis
industrialized. In most methodology-driven work, there remain (CO2 reduction under very mild conditions) and beyond will
important issues that need to be addressed in the future, for become true in the coming years. For example, sodium acrylate is
example, less utilization of very reactive/sensitive reagents, an industrially important acrylate, with a global market volume of
extending substrate scope, milder reaction conditions, improved about 4 million tons and is commonly used as a monomer in the
chemo- and regioselectivity. Due its inherent inertness, not sur- production of superabsorber polymers. Thus, the direct synthesis
prisingly, reactions of carbon dioxide under mild conditions need a of acrylic acid from CO2 and ethylene represents an economically
thermodynamic driving force, for example, energy-rich coupling attractive but also most challenging dream reaction. Until now, a
partners. The copolymerization of epoxides with CO2 to produce TON of only 10 (Ni catalyst and NaOtBu as base) has been
polycarbonates is an elegant example for this strategy and permits realized; nevertheless, the possibility of this reaction was clearly
efficient CO2 valorization. Alternative copolymerizations with demonstrated (Fig. 8, equation b)100. Ethylene glycol is another
easily available chemical feedstocks, such as olefins, are highly important raw material in the manufacture of polyester fibres and
desired too. In this respect, the recent report from Nozaki’s group polyethylene terephthalate resins used in bottling. The direct
of a copolymerization of CO2 and 1,3-butadiene is interesting. This
work provides a straightforward approach towards the production
of novel polymeric materials from CO2 (ref. 97). 6 CO2 + 6 H2O
Cat.
C6H12O6 + 6 O2
Another promising field might be the use of carbon dioxide as hν
methylation agent. For example, ruthenium-catalysed methylation
Cat.
of amines with CO2 and H2 to afford valuable products has very CO2 + CO2H
recently been achieved. However, the current catalyst loading is Cat. Cat.
2 CO2 OH
still too high for large-scale production. Hence, the development of HO2C CO2H HO + 2 H2O
H2 H2
more efficient catalyst systems and non-noble metal-based catalysts
for this and related transformations constitutes a demanding goal. 3 H2 + Cat.
CO2 + CH3 + 2 H2O
Most of the CO2-fixation reactions, which proceed via
oxidative cyclometallation pathway, are restricted to extensive p
systems (dienes and diynes) as substrates and the use of zinc Figure 8 | Dream reactions towards artificial photosynthesis. (a)
reagents to cleave the metallacycle intermediates. Consequently, Photosynthesis reaction process. (b) Direct synthesis of acrylic acid from
utilization of other simple alkene or alkyne substrates and milder ethylene and CO2. (c) Ethylene glycol synthesis via reductive coupling of
nucleophiles is highly desired to further improve this strategy. CO2. (d) Reductive methylation of benzene using H2 and CO2.

12 NATURE COMMUNICATIONS | 6:5933 | DOI: 10.1038/ncomms6933 | www.nature.com/naturecommunications


& 2015 Macmillan Publishers Limited. All rights reserved.
NATURE COMMUNICATIONS | DOI: 10.1038/ncomms6933 REVIEW

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97. Nakano, R., Ito, S. & Nozaki, K. Copolymerization of carbon dioxide and Acknowledgements
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