ExcellentCO2ConversionCookbook

Chem. Rev.
2007, 107, 2365−2387 2365
Transformation of Carbon Dioxide

Toshiyasu Sakakura,* Jun-Chul Choi, and Hiroyuki Yasuda
National Institute of Advanced Industrial Science and Technology (AIST), AIST Central 5, 1-1-1 Higashi, Tsukuba, Ibaraki 305-8565, Japan
Received December 19, 2006
Contents Scheme 1. CO2 as a Green Carbon Resource
1. Introduction 2365
2. Direct Synthesis of Dimethyl Carbonate from 2367
Methanol and CO2
2.1. Outlines 2367
2.2. Organic Dehydrating Agents and 2367
Homogeneous Catalysts
2.3. Reaction Mechanism 2368
2.4. Heterogeneous Catalysis 2369
2.5. Inorganic Dehydrating Agents 2369 the biggest obstacle for establishing industrial processes
2.6. Other Topics 2370 based on CO2 as a raw material is its low energy level. In
3. Dimethyl Carbonate Synthesis via Cyclic 2370 other words, a large energy input is required to transform
Carbonates CO2. There are four main methodologies to transform CO2
4. Synthesis of Cyclic Carbonates 2371 into useful chemicals:
4.1. Cyclic Carbonate Synthesis Outline 2371 (i) To use high-energy starting materials such as hydrogen,
4.2. Catalysts for the Cycloaddition of CO2 with 2371 unsaturated compounds, small-membered ring compounds,
Oxiranes and organometallics.
4.3. Reaction Mechanism 2373 (ii) To choose oxidized low-energy synthetic targets such
4.4. Asymmetric Synthesis 2374 as organic carbonates.
4.5. Outlook 2374 (iii) To shift the equilibrium to the product side by
5. Alternating Polymerization of Oxiranes and CO2 2374 removing a particular compound.
5.1. Reaction Outlines 2374 (iv) To supply physical energy such as light or electricity.
Selecting appropriate reactions can lead to a negative
5.2. Catalyst 2376
Gibbs free energy of the reaction (Scheme 2).
5.3. Asymmetric Polymerization 2377
5.4. Immobilized Catalysts 2377 Scheme 2. Organic Synthesis Using CO2
6. Synthesis of Urea and Urethane Derivatives 2378
7. Synthesis of Carboxylic Acid 2379
8. Synthesis of Esters and Lactones 2380
9. Synthesis of Isocyanates 2382
10. Hydrogenation and Hydroformylation, and Alcohol 2382
Homologation
11. Electrochemical Reaction 2383
12. Prospects of CO2 Transformation323 2383
13. Abbreviations 2383
14. References 2383
1. Introduction
Utilizing renewable resources is a prerequisite for a
sustainable society. One easily available renewable carbon
resource is carbon dioxide (CO2), which has the advantages
of being nontoxic, abundant, and economical (Scheme 1).1-21
CO2 is also attractive as an environmentally friendly chemical A lot of research has been conducted on reactions using
reagent and is especially useful as a phosgene substitute. CO2 as a raw material, as shown in Scheme 3, e.g. CO2
However, few industrial processes utilize CO2 as a raw reductions under photoirradiation, or under electrolytic
material. Because CO2 is the most oxidized state of carbon, conditions, or production of synthesis gas by reforming
natural gas with CO2. However, many of these reactions
* To whom correspondence should be addressed. Telephone and fax: +81- produce rather simple molecules such as carbon monoxide
29-861-4719. E-mail: [email protected]. and formic acid. This review article mainly address synthetic
10.1021/cr068357u CCC: $65.00 © 2007 American Chemical Society
Published on Web 06/13/2007
2366 Chemical Reviews, 2007, Vol. 107, No. 6 Sakakura et al.
Toshiyasu Sakakura received his B.S., M.S., and Ph.D. in Organic Hiroyuki Yasuda was born in 1964 in Tokyo, Japan. He received his Ph.D.
Chemistry from the University of Tokyo under the supervision of Professors in 1994 from the University of Tokyo under the supervision of Professor
T. Mukaiyama and K. Narasaka. He now is affiliated with the National Makoto Misono. He began his research career at the National Institute of
Institute of Advanced Industrial Science and Technology (AIST), which is Materials and Chemical Research in AIST in 1995, and he joined the
one of the largest national research institutes in Japan, and also has a research group of Professor Sakakura in 2000. In 2001, he received the
position as a professor at the University of Tsukuba. He is author of Noguchi Memorial Award for Encouragement of Research and Develop-
about 100 patents and 100 scientific papers. Dr. Sakakura’s research ment from The Japan Petroleum Institute. He is presently a leader of the
goal is the development of efficient synthetic reactions by homogeneous Molecular Catalysis Group at the Research Institute for Innovation in
catalysis, especially utilization of fundamental molecules such as carbon Sustainable Chemistry in AIST. His current research interests include
dioxide, hydrocarbons, and water. He is also interested in combining development of chemical processes utilizing CO2 and design of organic−
homogeneous catalysis with photolysis, supercritical fluids, and micro- inorganic hybrid catalysts.
reactors. He received the CSJ Award for Young Chemists from the Japan
Chemical Society for the catalytic C−H bond activation by the rhodium Scheme 3. Scope of the Current Review
trimethylphosphine complex.
Scheme 4. Typical Transformations of Carbon Dioxide
Jun-Chul Choi was born in 1968 in Korea and studied Chemistry at

Kangnung University and obtained his M.Sc. degree in 1994. Then, he
moved to Japan and received his Ph.D. in 1998 under the supervision of
Professor Kohtaro Osakada at Tokyo Institute of Technology. He joined
the research group of Professor Sakakura at the National Institute of
Advanced Industrial Science and Technology (AIST) as a JST postdoctoral
fellow in 1998. He currently holds a permanent position as a senior
researcher in the same group at AIST. His research interest is focused
on CO2 conversion and C−H bond activation by metal complexes.
in similar manners to produce compounds with a carboxyl
technologies for organic compounds that contain equal to or carboxylate group. These reactions conveniently produce
or more than three carbon atoms and use CO2 as a raw carbonic and carbamic acids (Scheme 4). Further reactions
material. Most of the references have been published after of these species with electrophiles lead to the formation of
1992. organic carbonates and carbamates. On the other hand,
A widely accepted idea is that CO2 is so thermodynami- reactions of low valent metal complexes (mainly nickel(0)
cally and kinetically stable that it is rarely used to its fullest and palladium(0)) with CO2 and unsaturated compounds lead
potential. However, due to the electron deficiency of the to the formation of five-membered metallalactones (Scheme
carbonyl carbons, CO2 has a strong affinity toward nucleo- 4).22 Because the valence of the metal increases by two, this
philes and electron-donating reagents. In other words, CO2 type of reaction is called an “oxidative cycloaddition”. Hence,
is an “anhydrous carbonic acid”, which rapidly reacts with reactions involving CO2 can be categorized into two pat-
basic compounds. For example, organometallic reagents such terns: (1) formation of a carboxyl group through nucleophilic
as Grignard reagents readily react with CO2 even at a low attack (pattern a) and (2) generation of a five-membered ring
temperature. Water, alkoxides, and amines also add to CO2 through oxidative cycloaddition (pattern b) (Scheme 4).
Transformation of Carbon Dioxide Chemical Reviews, 2007, Vol. 107, No. 6 2367
Scheme 5. Transformations of Carbon Dioxide as aprotic polar solvents. Furthermore, the excellent proper-
ties of DMC as a fuel additive have attracted much
attention.25 Moreover, linear carbonates are important alkyl-
ating agents, as are alkyl halides or dialkyl sulfates, and
carbonylating agents, as is phosgene or carbon monoxide.10,26
This section illustrates synthetic methods of linear carbonates,
especially dimethyl carbonate (DMC), starting from CO2. It
should be noted that cyclic carbonates can be easily
synthesized by reacting CO2 and epoxides, which is described
in section 4.
Currently, the largest future application of organic carbon-
ates is as a substitute for phosgene in the syntheses of
polycarbonates24 and polyurethanes.27 Polycarbonates are the
most extensively used engineering plastics, and the current
annual production of polycarbonates amounts to two million
tons worldwide. In addition, the amount produced increases
between 5 and 10% annually. On the other hand, 80-90%
of polycarbonates are currently being synthesized through
the phosgene process; an interfacial polymerization of
phosgene and bisphenol A using methylene chloride and
water as the solvents.
The major drawbacks of the phosgene processes (Scheme
7) are (i) the high toxicity of phosgene, which is controlled
by the international treaty concerning chemical weapons, and
(ii) the disposal of the coproduced hydrogen chloride.
Moreover, substituting phosgene with CO2 would drastically
reduce environmental concerns (Scheme 8),4,28 as the byprod-
uct is merely water.
Scheme 7. Dialkyl Carbonate Synthesis with Phosgene
Scheme 8. Dialkyl Carbonate Synthesis with CO2
Scheme 5 summarizes examples of organic synthesis

starting from CO2. The outlook of each reaction utilizing
CO2 as a chemical reagent is discussed hereinafter. However, the equilibrium for forming linear carbonates
from alcohols and CO2 (Scheme 8) is located on the left-
2. Direct Synthesis of Dimethyl Carbonate from hand side of the equation (the starting materials side). In
Methanol and CO2 order to avoid this thermodynamic limitation, it is necessary
to remove water from the right-hand side using an adequate
2.1. Outlines drying agent or to increase the CO2 concentration by
pressurizing CO2.
Organic carbonates are roughly categorized into cyclic and
linear carbonates.23 Because both compounds have three 2.2. Organic Dehydrating Agents and
oxygens in each molecule, they are relatively suitable from Homogeneous Catalysts
a thermodynamic point of view as synthetic targets starting
from CO2. Four industrially important organic carbonates Dehydration may be the most powerful methodology to
are ethylene carbonate (EC), propylene carbonate (PC), shift the reaction depicted in Scheme 8 to the carbonate side.
dimethyl carbonate (DMC), and diphenyl carbonate (DPC). However, it is difficult to dehydrate a reaction mixture with
EC, DMC, and DPC are useful intermediates for manufac- a large amount of alcohol, such as methanol, at a high
turing polycarbonates through a non-phosgene process temperature under a high CO2 pressure. Indeed, employing
(Scheme 6).24,25 In addition, EC, PC, and DMC are employed typical drying agents such as sodium sulfate, magnesium
as electrolytes in lithium ion batteries and are widely used sulfate, dicyclohexyl carbodiimide, trimethyl phosphate, and
molecular sieves has a negligible effect on the amount of
Scheme 6. Four-Step Process for Polycarbonate product formed.29-31 Although the synthesis of DMC by
consuming an equimolar amount of a phosphorus-containing
dehydrating agent has been reported, it is impractical from
an industrial viewpoint.32
In order to avoid problems associated with dehydration, a
new methodology where first water is removed from the
alcohol and then the dehydrated derivatives of the alcohol
react with CO2 has been proposed (Scheme 9). In these cases,
dehydrating the reaction mixture is unnecessary. Acyclic and
Scheme 9. Synthesis of Dialkyl Carbonate from CO2
cyclic ethers, ketals, and orthoesters are potential substrates. (iv) Catalyst: The addition of halides to tin alkoxides
[We have formally included orthoesters in the dehydrated accelerates the orthoester reaction, but adding halides
derivatives of alcohols, but it is difficult to synthesize interferes with the ketal reactions.
orthoesters by the dehydrative condensation of alcohols and (v) Recycling the dehydrating agents: Upon hydrolysis,
esters.] The reactivity of the substrates increases in the order orthoesters and ketals are converted to esters and ketones,
of route a to d in Scheme 9. For example, epoxides or cyclic respectively. Regeneration of ketals from ketones is easily
ethers easily react with CO2 to give five-membered ring achieved through a dehydrative condensation with alcohols
carbonates such as ethylene carbonate in high yields (route (Scheme 12).40 DMC production and dehydration are inde-
d). Details of the reaction conditions, including catalysts, are pendently conducted at the different places.
discussed in section 4. On the other hand, linear ethers do
not have ring strain and are much less reactive compared to Scheme 12. Recycling of Ketal as a Dehydrating Agent
epoxides. Although the CO2 insertion to dimethyl ether has
been reported, the details are unknown (route a).33
The dehydrating characteristics of orthoesters and ketals
(Schemes 10 and 11) have been well examined for the dialkyl
Scheme 10. Dehydration by Orthoester
Because acetone appears to be the most convenient

carbonyl compound for the ketal process with regards to cost
Scheme 11. Dehydration by Ketal and availability, 2,2-dimethoxypropane is a promising can-
didate for the ketal. However, a wide range of ketones such
as cyclohexanone and diethyl ketone can also be used.
Among tin alkoxides [BunSn(OMe)4-n, n ) 0-3], Bu2Sn-
carbonate synthesis. If Schemes 8 and 10 are combined, then (OMe)2 exhibits the best catalytic activity. Dibutyltin oxide
water can be canceled out, which yields a new equation that [(Bu2SnO)n] also works as a convenient precursor of the
is independent of alcohol (route c, Scheme 9). Indeed, the active species because it is stable under air and is easier to
reaction of orthoesters proceeds in the presence of a metal handle than Bu2Sn(OMe)2. Moreover, adding a very small
complex such as Bu2Sn(OMe)2 in high yields without adding amount of an acidic cocatalyst greatly improves the produc-
alcohol.34 However, the yields are highly dependent on the tivity (STY) (Scheme 13).41 It is hypothesized that the
CO2 pressure and reach a maximum around the critical cocatalyst accelerates ketal hydrolysis (Vide infra), but details
pressure of CO2. The reaction of orthoesters and CO2 is also of the reaction mechanism are unknown.
promoted by several types of catalysts, including alkali metal
halides and immobilized ammonium salts.35,36 The demerits Scheme 13. DMC Synthesis with Dimethyl Ketal
of the orthoester method are obvious: (i) expensive starting
material, (ii) coproduction of esters, and (iii) difficulty in
regenerating orthoesters from esters.
By combining Schemes 8 and 11, water can also be
canceled out (route b, Scheme 9). Interestingly, the reaction
between ketals and CO2 does not proceed in the absence of
alcohols.37-39 The reaction of orthoesters and the reaction
of ketals seem to have different mechanisms and show
largely different properties, which are described in items (i)
Other than tin compounds, combinations involving tita-
to (v).
nium alkoxides and polyether ligands (e.g., crown ethers or
(i) Alcohol: Orthoesters do not need alcohol to react with
polyethylene glycols) show relatively high catalytic activi-
CO2, but ketals absolutely must have it.
ties.42 Furthermore, cobalt,43 nickel,44 and niobium45 com-
(ii) Pressure: Orthoesters have an optimal pressure to
plexes catalyze the reaction in Scheme 8.
produce the highest carbonate yield, while higher pressure
gives higher yields for the reaction of ketals.
(iii) Byproducts: The major byproduct in the orthoester
2.3. Reaction Mechanism
reaction is dialkyl ethers, while the byproducts in the ketal The direct formation of methyl bicarbonate [MeO(CdO)-
reaction are enol ethers, and dialkyl ethers are not produced. OH] from CO2 and methanol is negligible.46 However, CO2
Scheme 14. Synthesis of Dialkyl Carbonate from CO2 yield decreases to nearly half. As for step C, regeneration
of Bu2Sn(OMe)2 from (Bu2SnO)n and methanol under similar
temperatures and pressures as those for the catalytic DMC
formation has been examined. The resulting complex is a
stanoxane-type tetranuclear complex {[Bu2(MeO)SnOSn-
(MeO)Bu2]2} that has a nearly equal catalytic activity to that
of Bu2Sn(OMe)2 based on the tin atom.56 Similar observa-
tions have been reported.57,58
2.4. Heterogeneous Catalysis

Solid acid-base catalysts such as zirconia catalyze DMC
formation from methanol and CO2.59,60 The reaction mech-
anism has been investigated by measuring of the infrared
spectra.61,62 DMC is produced through the following steps.
(i) Dissociative adsorption of methanol to form methoxide
species. (ii) CO2 insertion resulting in the formation of
monomethyl carbonate, an important intermediate in the
DMC synthesis. (iii) The transfer of a methyl group from
adsorbed methanol to the monomethyl carbonate to form
DMC. Every step proceeds more rapidly on monoclinic
reacts with alcohols in the presence of metal complexes to zirconia compared with tetragonal zirconia. The observed
give linear carbonates (Scheme 8).37,38,47 The most intensively patterns are attributed to the higher Bronsted basicity of
studied complexes for this purpose are tin alkoxides. The hydroxyl groups, and Lewis acid/base pairs present on the
formation of a methyl carbonato complex through a reaction surface of zirconia. Interestingly, titania does not display
of tin methoxide with CO2 was reported in 1967.48,49 The catalytic activity.63 Modifying zirconia by ceria and acidic
formation of DMC upon thermolysis of methyl (carbonato) compounds such as phosphoric acid promotes catalytic
tin was first reported in 1975, but the yield was very low; activity.64-66 Heteropoly acids supported on zirconia are also
only 10% based on tin.50 Another group later reported similar active for the DMC formation from methanol and CO2.67 In
results.51 However, due to the unfavorable equilibrium for addition to zirconium-based catalysts, vanadium-based cata-
the reaction in Scheme 8, the reaction performance is lysts such as H3PO4/V2O568 and Cu-Ni/V2O5-SiO269 have
unsatisfactory. In fact, the yield of DMC based on methanol been applied to gas-phase reactions. Most of the heteroge-
charged was only 1-2%, indicating that the turnover number neously catalyzed reactions seem less productive compared
of the tin complex [e.g., Bu2Sn(OMe)2] is less than one and to the homogeneous reaction using ketals (e.g., Scheme 13).
that the reaction is stoichiometric rather than catalytic.
Scheme 14 shows a plausible catalytic cycle based on a 2.5. Inorganic Dehydrating Agents30,70
mononuclear or a multinuclear metal alkoxide as active
species. As for steps A and B, the tin alkoxide and the tin If the catalytic cycle depicted in Scheme 14 is correct,
carbonato complexes have been isolated. The molecular then the role of ketals is to dehydrate. Then DMC synthesis
structures by a single-crystal X-ray diffraction method have should proceed using inorganic dehydrating agents such as
also been successfully determined. (See Figure 1 for the zeolites. Using inorganic dehydrating agents should have the
structure of [Me2Sn(OMe)(OCO2Me)]2.) CO2 insertion into following merits compared to using organic ones: (i) easy
the tin-oxygen bond readily proceeds even at room tem- separation by filtration from the reaction mixture and (ii)
perature.47,52 CO2 insertion into the metal-oxygen bond of facile recycling of the dehydrating agent by drying.
other metal alkoxides has also been reported.45,53-55 However, the addition of inorganic dehydrating agents
In step B, thermolysis of the carbonato complex yields such as zeolite or MgSO4 to the tin alkoxide system or to
DMC in 60% in the presence of methanol and CO2. The the ZrO2 system does not improve the DMC yield (Vide
reaction without adding methanol also gives DMC, but the supra).29,30 This is probably because the capability of
dehydration is low at high reaction temperatures. For
improving the DMC yield, a reaction process separating the
reaction part (high temperature) from the dehydrating part
(room temperature), and circulating the reaction mixture
Scheme 15. DMC Synthesis Using an Inorganic Dehydrating

Agent
Figure 1. Molecular structure of [Me2Sn(OMe)(OCO2Me)]2.

Scheme 16. DMC Synthesis in the Presence of Methyl

Iodide
Figure 2. Time dependence of dimethyl carbonate synthesis from

CO2 and methanol. Reaction conditions: autoclave with internal
recycle, dibutyltin dimethoxide (2.0 mmol), methanol (100 mmol), Scheme 17. DMC Formation from K2CO3
molecular sieve 3A (15 g), carbon dioxide (total pressure 300 atm),
180 °C. Yields are based on methanol.
between these two parts, has been designed; molecular sieves

3A are packed in the dehydrating tube (Scheme 15). In the are equal to or less than one. In addition, the reaction of
absence of the dehydrating part, the yield of DMC is CD3OD with CH3I produced CD3(CO3)CH3, while CD3(CO3)-
saturated at a very early stage, showing the thermodynamic CD3 was not observed. Judging from these results, CH3I is
limitation. On the other hand, in the presence of the not merely a catalyst but is one of the reactants. In other
dehydrating part, the DMC yield increases as the reaction words, step b is not fast enough. Because inorganic carbon-
time proceeds and eventually achieves nearly a 50% yield ates such as K2CO3 are used as a base in these reactions, it
based on methanol charged (Figure 2). In addition, in the is possible that the CO3 moiety in DMC comes from K2CO3
presence of the dehydrating part, the DMC yield increases (Scheme 17). Microwave irradiation significantly accelerates
in proportion to the catalyst amount and the reaction pressure. the reaction.77
DMC formation is very selective, and byproducts such as
dimethyl ether are not observed. 3. Dimethyl Carbonate Synthesis via Cyclic
Carbonates
2.6. Other Topics The reaction of CO2 with epoxides to yield alkylene
Employing a separation membrane is a promising meth- carbonates followed by in situ ester exchange with a large
odology in order to remove the water on the right-hand side excess of methanol can form dimethyl carbonate. The merits
of Scheme 8. In fact, dimethyl carbonate synthesis from of this process are as follows. (1) Unlike the direct reaction
methanol and CO2 has been investigated using water separa- of methanol and CO2 (Scheme 8), a high yield can be
tion membranes such as mesoporous silica, polyimide silica, achieved in this reaction because dehydration is unnecessary.
and polyimide-titania hybrid membranes,71 although the (2) If the coproduced 1,2-diols are recycled, the total reaction
effect of the membranes on the DMC yield is obscure. is regarded as the DMC synthesis from methanol and CO2.
Dimethyl carbonate synthesis by reacting CO2 and metha- The demerits of the process are (1) coproduction of 1,2-
nol in the presence of methyl iodide has been proposed.72-76 diols, (2) side reactions such as ring opening of epoxides by
Scheme 16 shows a possible catalytic cycle. However, in alcohols, and (3) the requirement for a large excess of alcohol
most of these reports, the turnover numbers based on CH3I to achieve high conversions due to the unfavorable ester
Table 1. Dimethyl Carbonate Synthesis from Epoxides, Methanol, and CO2
epoxidea MeOH catalyst PCO2 temp time yield

year (mmol) (mmol) (g) (bar) (°C) (h) (%) ref
2001 PO (25) 200 MgO (0.5) 80 150 15 14 78
2003 EO (45) 562 KI (0.2)/K2CO3 (0.2) 150 140 2 73 79
2003 PO (21) 200 Mg[smectite] (0.5) 80 150 15 34 80
2004 PEPO (1) 40 DBU (0.008) 150 150 24 97 81
2004 PO (1000) 4000 5 wt % [K2CO3-KCl/MgO] (-) 25 160 5 46 82
2004 EO (10) 40 [K2CO3-KI/ZnO] (0.25) 165 150 4 69 83
2005 PO (828) 1234 KOH/molecular sieves 4A (5) 30 (rt) 180 6 17 84
2006 SO (5) 200 Bu4NBr (0.04)/Bu3N (0.02) 150 150 8 84 85
a For the abbreviations, see section 13 of this article.
exchange between methanol and alkylene carbonates. Table Scheme 22. Synthesis of a Cyclic Carbonate from a
1 summarizes typical catalytic systems for this reaction. Propargyl Carbonate
Suitable catalysts need to activate both step a and step b,
and in general, basic compounds seem appropriate.78-85
Recently, it has been reported that an Fe-Zn double metal
cyanide, prepared from ZnCl2 and K4Fe(CN)6, is a highly
active heterogeneous catalyst for the synthesis of a range of
dialkyl carbonates in high yields by transesterification of
propylene carbonate with alcohols.86 The catalyst can be
recycled without significant loss in activity.
4. Synthesis of Cyclic Carbonates 4.2. Catalysts for the Cycloaddition of CO2 with
4.1. Cyclic Carbonate Synthesis Outline Oxiranes
Oxiranes and oxetanes undergo cycloaddition with CO2 A typical process of CO2 cycloaddition with oxiranes uses
to give five- and six-membered ring carbonates (Scheme the produced carbonate as a solvent in the presence of an
18).11,87,88 Similar to linear dialkyl carbonates, cyclic carbon- onium salt such as tetraethyl ammonium bromide as a
ates are useful as intermediates for polycarbonates, electro- catalyst.11 In addition to onium salts, the reaction proceeds
lytes in lithium ion batteries, or green solvents. The in the presence of a wide range of catalysts, including metal
production of five-membered cyclic carbonates from CO2 halides.96 Although the catalytic activity at lower tempera-
has been industrialized since the 1950s.11 Although oxirane tures is not very high, KI seems to be one of the best catalysts
cycloaddition is rather selective, alternating copolymerization in recent industrial processes. This is probably because
of oxiranes with CO2 and homopolymerization of oxiranes potassium iodide is more economical and more durable
also proceed as explained in the next section. As another compared to quaternary ammonium salts and it is highly
type of the five-membered carbonate synthesis starting from soluble in cyclic carbonates. Supporting halide salts on solid
CO2, Nb-catalyzed oxidative carboxylation of olefins has supports such as ZnO, SiO2, carbon, and zeolite results in
been reported (Scheme 19).89 On the other hand, the high catalytic activities.97-100
dehydrative reaction of 1,2-diols to give cyclic carbonates Tables 2-4 summarize recently proposed homogeneous
is catalyzed by CeO2-ZrO2 or Bu2SnO (Scheme 20).90-92 catalysts for the cyclic carbonate synthesis from oxiranes
An iron- or copper-catalyzed reaction of a cyclic ketal with and CO2: metal complexes (Table 2), onium salts (Table
CO2 has also been proposed (Scheme 21).93 The reaction of 3), and others (Table 4). One requirement for industrial
propargyl carbonate with phenol proceeds in the presence homogeneous catalysts is not to produce solids during the
of a palladium catalyst, which leads to phenoxy-substituted catalyst separation stage by evaporating the product after
cyclic carbonates via CO2 evolution (Scheme 22).94,95 cycloaddition.
Scheme 18. Synthesis of a Cyclic Carbonate from an Among metal complexes, salen complexes of alumi-
Oxirane num,101-104 chromium,105,106 cobalt,107,108 zinc,107 and tin109
exhibit high catalytic activities. Aluminum complexes of
phthalocyanines or porphyrins are also highly active.110-114
Utilizing ionic liquids in organic synthesis has attracted
increasing attention.115 Cyclic carbonate synthesis using ionic
liquids (i.e., imidazolium salts) as catalysts,116-118 or by
combining ionic liquids and metal salts, has been re-
ported.119-123 In addition, a reaction in liquid quaternary
Scheme 19. Synthesis of a Cyclic Carbonate from an Olefin ammonium salts, e.g., Bu4NBr, has been proposed.124
Furthermore, various metal complexes of nickel,125 ruthe-
nium,126 zinc,127 copper,128 manganese,128,129 and so on have
been reported to be active (Table 4). Combining with organic
compounds such as crown ethers, onium salts, and phos-
phines has significantly improved the catalytic activities of
Scheme 20. Synthesis of a Cyclic Carbonate from a Diol metal halides.130-134 Cobalt- or manganese-substituted poly-
oxometalates have been proposed as catalysts with non-halide
counter-anions.135 These polyoxometalates work as homo-
geneous catalysts. Fully organic catalysts based on phenols
and amines have also been investigated.136,137
Scheme 21. Synthesis of a Cyclic Carbonate from a Cyclic Many papers claim low reaction temperatures and advertise
Ketal high catalytic activities. However, this is not very meaningful
from a practical viewpoint because cycloaddition (Scheme
18) is highly exothermic and effective heat removal is
fundamental to save energy. In order to recover the reaction
heat as steam, a reaction temperature around 150 °C would
be desirable. Reaction temperatures below 100 °C result in
low heat exchange efficiencies and produce nearly useless
warm water.
Table 2. Cyclic Carbonate Synthesis Catalyzed by Salen and Phthalocyanine Complexes
amount of PCO2 temp time TOFa

expoxide catalyst cat. (mol %) solvent (bar) (°C) (h) TON (h-1) ref
PO 1a/[Bu4NBr] 0.13 6 25 8 504 63.0 102
PO 1a/[Bu4NI] 0.13 6 35 8 674 84.2 102
PO 1a/[18-crown-6-KI] 0.13 6 25 8 463 57.9 102
EO 1a/[Bu4NI] 0.02 160 110 1 2360 2360 104
PO 1b/[18-crown-6-KI] 0.13 6 25 8 498 62.3 101
PO 1c/[(4-dimethylamino)pyridine] 0.075 CH2Cl2 8 100 1 916 916 105
PO 1d/2[Et3N] 0.1 CH2Cl2 35 100 2 913 456.5 107
PO 1e/2[Et3N] 0.1 CH2Cl2 35 100 2 856 428 107
PO 1f/4.5[N-methylimidazole] 0.1 >61 140 1.2 961 801 113
a
TOF: estimated from the literature.
Table 3. Cyclic Carbonate Synthesis Catalyzed by Onium Salts

expoxide catalyst cat. (mol %) (bar) (°C) (h) TON (h-1) ref
PO 2a 2.5 25 110 6 40 6.7 116
PO 2b 1.7 140 100 0.08 516 6192 118
PO ZnBr2 + 6 equiv 2c 0.018 15 100 1 5580 5580 121
SO ZnBr2 + 4 equiv 2d 1.1 140 80 1 84 84 123
PO 2e 0.05 35 100 1 1846 1846 119
EO 2f 0.02 35 100 1 3588 3588 119
PO 2g 0.2 35 100 1 500 500 120
PO 2h 0.5 7 120 1 194 194 122
a
Table 4. Various Homogeneous Catalysts for Cyclic Carbonate Synthesis

epoxide catalyst cat. (mol %) solvent (bar) (°C) (h) TON (h-1) ref
PO Ni(PPh3)2Cl2/2[PPh3]/4[Bu4NBr]/20[Zn] 0.028 25 (rt) 120 1 3544 3544 125
PO Cp(CO)Ru(dppe)Mn(CO)4 0.01 40 100 40 1490 37 126
EO Zn(PMe2Ph)2Br2 0.05 34 100 1 1640 1640 127
PO 0.043 CH2Cl2 7 120 4 1144 286 128
PO NaI/Ph3P/PhOH 2 40 (rt) 120 2 48 23.8 131

PO CaCl2/octyl3(Me)NCl 0.23 41 (rt) 170 8 419 52 132
SO ZnBr2/2[Bu4NI] 0.29 80 90 0.5 686 133
PO Bu3SnI/Bu4PI 2 50 40 1 50 50 134
PO [heptyl4N]6[R-SiW11O39Co] 0.1 N,N-dimethylformamide 35 150 2 820 410 135
PO p-MeC6H4OH/DMAP 0.4 CH2Cl2 36 120 48 246 5.1 137
a TOF: estimated from the literature.
The use of supercritical CO2 has attracted much interest propylene and ethylene carbonates are not. Hence, carbonates
in order to facilitate various chemical processes. Propylene are easily separated from the supercritical phase without
and ethylene oxides are soluble in supercritical CO2, while reducing the CO2 pressure. Facile catalyst recycling can be
Scheme 23. Facile Separation by scCO2 silicate and mesoporous silica also catalyze the reaction with
and without ammonium salts (Table 5).153,154
In light of homogeneous catalyst recycling, immobilization
is a promising approach. For cycloaddition of oxiranes and
CO2, polymer-supported catalysts155-164 as well as silica-
supported catalysts have been developed (Table 6).165-168 It
has been noted that silica-supported onium salts exhibit
hundred times higher catalytic activities compared to onium
salts alone. Thus, the silica-supported onium salts have
been applied to a flow reactor system; silica itself does not
display catalytic activity.168 In general, the catalytic activities
realized by using catalysts highly soluble in supercritical CO2 of homogeneous catalysts become lower upon immobiliza-
(e.g., perfluorophosphonium salts) (Scheme 23).138 tion. Hence, the observation that there is a large cooperative
LiBr has been reported to be a suitable catalyst in effect between the catalyst part and the solid support part is
supercritical CO2.139,140 Although it is reported that the unique.
reaction in supercritical CO2 proceeds without a catalyst in
the presence of dimethyl formamide, substrates seem to be 4.3. Reaction Mechanism
limited to styrene oxide derivatives.141
In view of catalyst separation and environmental issues The cycloaddition of monosubstituted oxirane catalyzed
(non-halogen processes), metal oxide-based catalysts are by a metal halide (MX) is discussed. First, anion X attacks
interesting. Heterogeneous catalysts such as SmOCl,142,143 the less hindered side of oxirane to open the ring. Next, the
ZnO-SiO2,144 Cs-P-SiO2,145 smectite,146 Al-Mg mixed resulting alkoxide part attacks CO2 to give the carbonate
oxides,147 magnesium oxide,148 Cs-modified zeolites,149,150 anion. Then, the carbonate anion undergoes a SN2 reaction,
hydroxyapatites,151 and zinc-substituted heteropolyacids with which simultaneously forms a five-membered ring and
sodium as cations152 have been reported as active. Titano- releases anion X (Scheme 24).
Table 5. Cyclic Carbonate Synthesis Catalyzed by Heterogeneous Catalysis

PCO2 temp time yield selectivity
expoxide catalyst solvent (bar) (°C) (h) (%) (%) ref
PO SmOCl N,N-dimethylformamide 140 200 8 99 99 142
PO 7% ZnO-SiO2 45 100 3 27 144
PO Cs-P-SiO2 80 200 8 94 96 145
PO Smectite(8[Si]-6.44[Mg]-2.81[Na-0.13K]) 80 150 15 81 94 146
PO 5[MgO]/AI2O3 N,N-dimethylformamide 5 120 24 88 92 147
PO MgO N,N-dimethylformamide 20 135 12 41 148
EO Cs-Zeolite 39 (rt) 150 3 14 150
SO 0.3 mmol/g[Zn(Ca10(PO4)6(OH)2]/4[Et3N] 5 100 20 98 >99 151
PO Na12[WZn3(H2O2)2(ZnWgO34)2]46H2O/3[DMAP] CH2Cl2 4 160 12 97 97 152
PO MCM-41 7 120 5 86 94 154
Table 6. Immobilized Catalysts for Cyclic Carbonate Synthesis
PCO2 temp time yield selectivity

expoxide catalyst solvent (bar) (°C) (h) (%) (%) ref
SO 0.42 mmol/g[AI(salen)PEA]/1.8[N-methylimidazole] 100 80 15 78 88 159
EO 9.7 wt % [ZnBr2]/poly(4-vinylpyridine) 35 100 1 33 >99 161
PEPO 0.5 mmol/g[ClBu3P/PS] N,N-dimethylacetamide 1 90 24 94 162
PEPO 0.41 mmol/g[ClBu3P/PS1] toluene 1 100 24 93 163
SO 1.27 mmol/g[TBD-MCM-41] CH3CN 50 140 70 90 92 165
SO 0.14 mol % [Cr-salen/NH2SiO2]/ CH2Cl2 100 80 6 59 89 167
0.13 mmol [N-methylimidazole]
PO 0.85 mmol/g[SiO2-C3H6-PBu3I] 100 100 1 100 100 168
Scheme 24. Possible Mechanism of Cyclic Carbonate Synthesis: 1
Scheme 25. Possible Mechanism of Cyclic Carbonate Synthesis: 2
Table 7. Asymmetric Synthesis of Cyclic Carbonates
amount of PCO2 temp time TOF

epoxide catalyst cat. (mol %) (bar) (°C) (h) TON (h-1) % ee ref
PO 3a/Bu4NBr 0.1 15 25 2 490 245 50.5 108
PO 3b/Bu4NBr 0.1 15 25 2.5 508 203 51.6 108
DAPO 3c/0.5[Et2NSiMe3] 2 7 30 80 25 0.31 86 169
Another possible mechanism is for anion X to initially hand, the process of polycarbonate synthesis, such as in
attack CO2, followed by a nucleophilic attack of the resulting Scheme 6, uses cyclic carbonates on a large scale.
anion to form oxirane (Scheme 25). Catalysts for cyclic carbonate synthesis from oxiranes and
In order to elucidate the mechanism, the change in the CO2 are categorized into (1) ammonium or phosphonium
configuration of the methylene carbon has been investigated salts, (2) alkali metal salts (KI, LiBr, etc.), (3) metal
using D-labeled oxirane. The configuration is retained during complexes such as salen complexes, and (4) solid or
the reaction, which supports a mechanism that includes a immobilized catalysts such as SiO2-C3H6-P(Bu)3I. Future
double inversion by SN2 reactions, namely that shown in challenges include developing non-halogen catalysts, devel-
Scheme 24.108 oping immobilized or solid catalysts aimed at flow reactor
processes, utilizing new reaction media such as supercritical
4.4. Asymmetric Synthesis CO2 or ionic liquids, and asymmetric synthesis.
The synthesis of optically active cyclic carbonates (kinetic 5. Alternating Polymerization of Oxiranes and
resolution of racemic epoxides) is possible using asymmetric CO2
cobalt salen complexes as catalysts.108,169 The highest reported
enantiomeric excess of cyclic carbonates is about 86% ee 5.1. Reaction Outlines
(Table 7).
The alternating copolymerization shown in Scheme 26
4.5. Outlook comprises the same reactants as the synthesis of five-
membered cyclic carbonates; polymers are kinetic
Currently, the market for cyclic carbonates as electrolytes products, while cyclic carbonates are thermodynamic
for batteries is small. However, the demand should increase ones (Scheme 26).170 Aliphatic carbonates produced by
when electric vehicles are fully commercialized. On the other this reaction have been recently industrialized in China.171
Scheme 26. Alternating Polymerization of Oxirane and CO2 its application to bulk materials. On the other hand, a higher
Tg (115 °C) and the decomposition temperature (about
300 °C) of poly(cyclohexene carbonate) allow the
melt processing. The polymer is expected to be a substi-
tute for polystyrene. The characteristics of the polymers
are low oxygen permeability, biodegradability, and
The relatively low Tg (glass transition temperature) (35-40 complete thermal depolymerization to give cyclic
°C) of poly(propylene carbonate) seems to interfere with carbonates.
Table 8. Homogeneous Zinc Catalysts for Alternating Polymerization
amount of PCO2 temp time TOFa carbonate Mn

epoxide catalyst cat. (mol %) (bar) (°C) (h) TON (h-1) linkages (%) (×10-3) Mw/Mn ref
CHO 4a 0.1 7 50 0.5 172 345 94 25.5 1.10 54
CHO 4b 0.1 7 50 0.5 179 358 97 25.6 1.16 54
CHO 4c 80 80 69 2759 40 97 13.5 4.59 173
CHO 4d 0.3 20 85 20 108 5 99 23.0 8.91 174
CHO 4e 0.04 50 80 24 660 28 85 13 7.62 175
CHO 4f 0.36 55 80 69 183 3 91 38.0 4.5 176
CHO 4g 5 5 60 6 196 33 99 20.9 1.51 177
CHO 4h 0.1 7 50 2 449 224 95 19.1 1.07 178
CHO 4i 0.1 7 50 2 477 239 96 23.7 1.14 178
CHO 4j 0.1 7 50 2 515 257 99 32.1 1.14 178
CHO 4k 0.1 7 50 2 418 209 94 17.0 1.21 178
CHO 4l 0.1 7 50 5 265 53 93 14.8 1.10 178
CHO 4m 0.1 7 50 5 198 99 11.6 1.18 179
CHO 4n 0.1 10 60 2 312 156 97 39.8 1.11 180
CHO 4o 0.1 10 60 2 328 164 97 31.8 1.13 180
CHO 4p 0.1 10 60 2 270 135 95 20.8 1.30 180
CHO 4q 0.1 7 50 0.5 180 360 95 15.8 1.11 54
CHO 4r 0.1 7 50 0.5 216 431 97 17.3 1.15 54
CHO 4s 0.1 7 50 0.5 364 729 99 23.3 1.15 54
PO 4t 0.05 21 25 8 376 47 99 43.3 1.09 181
PO 4u 0.05 21 25 2 424 212 99 35.9 1.11 181
CHO 4v 0.1 40 90 2 367 183 88 24.5 1.15 182
CHO 4w 0.02 12 80 5 1560 312 94 225.0 1.70 183
Table 9. Homogeneous Cobalt Catalysts for Alternating Polymerization
cocatalyst amount of PCO2 temp time TOFa carbonate Mn

epoxide catalyst (equiv) cat. (mol %) (bar) (°C) (h) TON (h-1) linkages (%) (×10-3) Mw/Mn ref
PO 5a DMAQ (2) 0.07 11 25 3 354 118 >99 17.2 1.06 186
PO 5b DMAQ (2) 0.07 25 40 1.66 330 199 >99 17.4 1.07 186
PO 5c DMAQ (2) 0.07 11 25 5 430 86 >99 25.6 1.06 186
PO 5d DMAQ (2) 0.07 11 25 5 430 86 >99 21.3 1.06 186
PO 5e DMAQ (2) 0.07 11 25 5 485 97 >99 23.2 1.07 186
PO 5f 0.2 55 25 3 243 81 99 15.3 1.22 187
PO 5g 0.2 55 25 3 198 66 96 9.0 1.31 187
PO 5h 0.2 55 25 3 177 59 99 8.1 1.57 187
PO 5i PPNCl (1) 0.05 14 22 2 1040 520 >99 43.0 1.10 188
CHO 5i PPNCl (1) 0.05 7 22 2 320 160 97 14.9 1.14 189
PO 5j Bu4NCl (1) 0.05 20 25 3 771 257 >99 30.4 1.36 190
PO 5j PPNCl (1) 0.05 15 25 1.5 795 530 >99 30.9 1.20 191
a
Table 10. Homogeneous Chromium Catalysts for Alternating Polymerization
cocatalyst amount of PCO2 temp time TOFa carbonate Mn

epoxide catalyst (equiv) cat. (mol %) (bar) (°C) (h) TON (h-1) linkages (%) (×10-3) Mw/Mn ref
CHO 6a PPh3 (3) 0.04 55 80 4 157 39 96 22.7 1.55 192
CHO 6a PPNCl (1) 0.04 55 80 4 1004 251 >99 6.0 2.05 192
CHO 6b PCy3 (3) 0.04 55 80 10 391 98 97 10.8 1.54 192
CHO 6a N-Melm (2.25) 0.04 55 80 24 857 36 99 8.8 1.40 193
CHO 6b PPNCl (1) 0.04 55 80 4 1977 494 99 10.0 1.26 194
CHO 6b PPNN3 (1) 0.04 55 80 4 2423 608 99 14.0 1.54 194
CHO 6b DMAP (1) 0.04 55 80 4 1080 270 98 31.5 1.12 194
CHO 6c N-Melm (2.25) 0.04 59 80 24 1104 46 >99 8.9 1.20 195
PO 6c DMAP (0.5) 0.07 13 75 4 176 44 76 10.1 1.36 196
CHO 6d PPNN3 (1) 0.04 35 80 2.3 2686 1153 >99 50.0 1.13 197
CHO 6e PCy3 (1) 0.04 34 60 4 596 149 96 13.2 1.07 198
CHO 6e PPNN3 (1) 0.04 34 60 4 760 190 96 26.1 1.11 198
PO 6e DMAP (1) 0.07 35 75 4 640 160 98 16.7 1.38 196
CHO 6f 0.26 138 95 18 12 0.65 95 3.6 1.16 199
a
In order to realize large-scale commercialization of these The iminate complexes have been the most intensively
alternating copolymers, the plastic properties must be studied. Bulky substituents seem to promote the partial
improved and the catalytic activities for copolymerization dissociation of dinuclear species, which results in an
must be increased. increased catalytic activity. Under optimized conditions, a
high reaction rate, a high molecular weight, and a narrow
5.2. Catalyst polydispersity have been simultaneously achieved. The
Zinc complexes were the first generation of catalysts and activities of zinc diiminate catalysts are enhanced in the
are typified by (ZnEt2 + H2O).172 The structure of the real presence of SO2.185
active species may be multinuclear but is unknown. The Metal complexes other than zinc complexes have also been
catalytic performance has been unsatisfactory and has developed. For example, cobalt (Table 9),186-191 chromium
resulted in low reaction rates, large polydispersity, and (Table 10),192-199 lanthanide (Table 11),200,201 and manga-
irregular structures. nese202 complexes have been reported. Table 12 summarizes
As structurally well-characterized highly active catalysts, the structurally uncharacterized complexes.203-210 The cobalt-
various zinc complexes have been proposed (Table 8).54,173-184 catalyzed reactions proceed under very mild conditions
Table 11. Homogeneous Ln and Mn Catalysts for Alternating Polymerization
amount of PCO2 temp time TOFa carbonate Mn

epoxide catalyst cat. (mol %) (bar) (°C) (h) TON (h-1) linkages (%) (×10-3) Mw/Mn ref
CHO 7a 0.2 1 75 88 204 2.3 68 3.8 2.80 200
CHO 7b 0.2 1 75 24 173 7.2 92 7.1 1.50 200
CHO 7c 0.2 1 75 24 304 12.7 88 13.5 1.60 200
CHO 7d 0.25 12 70 24 10359 432 94 19.1 4.30 201
CHO 7e 0.25 12 70 24 7417 309 93 14.5 3.99 201
CHO 7f 0.25 12 70 24 12960 540 92 23.0 4.03 201
CHO 7g 0.2 51 80 24 390 16 99 6.7 1.30 202
Table 12. Non-Single-Site Zinc Catalysts for Alternating Polymerization

PCO2 temp time TOFa carbonate Mn
epoxide catalyst (bar) (°C) (h) (h-1) linkages (%) (×10-3) Mw/Mn ref
CHO ZnCl2/0.1[K3Co(CN)6]/poly(tetramethylene ether glycol) 86 80 2 356 80 10.2 1.77 203
PO ZnCl2/0.1[K3Co(CN)6]/poly(tetramethylene ether glycol) 86 80 2 172 39 2.6 1.39 203
PO Zn(OAC)2/glutaric acid/PE6400 21 60 40 2 60.0 2.70 204
PO Zn(glutarate)/3[montmorillonite] 52 60 40 2.6 >99 20.5 2.9 205
PO Zn(glutarate)/poly(aryl ether sulfone)s 50 60 40 0.29 36.0 206
PO ZnO/heptanedioic acid 52 60 40 2.05 >99 44.3 207
CHO ZnEt3/0.05[Y(CF3CO2)3]/2[glycerine] 28 80 12 2.63 >99 33.4 7.4 208
PO ZnEt3/0.05[Y(CF3CO2)3]/m-hydroxybenzoic acid 28 60 12 4.17 >99 13.5 4.7 209
CHO ZnEt3/0.1[Y(CF3CO2)3]/2[pyrogallol] 28 80 12 5.92 93 35.7 4.48 210
a
TOF: estimated from the literature.TOF ) (polymer - g)/(Zn - g)‚h.
Scheme 27. Possible Mechanism of Alternating Polymer

around room temperature (Table 9). It is noteworthy that
Synthesis
the cobalt complexes effectively execute the polymerization
of epoxides derived from acyclic alkenes such as propylene
oxides. Among heterogeneous catalysis, the alternating
copolymerization of cyclohexene oxide catalyzed by the Co-
Zn double metal cyanide is especially efficient (Table 12).
The turnover frequency is as large as that of the homoge-
neous catalysis using zinc diiminate complexes (Table 8).
From an economic point of view, ethylene and propylene
oxides are favorable as substrates for the reaction. However,
most papers use cyclohexene oxide as a substrate because
cyclohexene oxide selectively yields the polymer, while
ethylene and propylene oxides often afford cyclic carbonates.
On the other hand, the higher Tg of the polymer based on
cyclohexene oxide compared to the propylene oxide-based
polymer makes it favorable as a bulk material. The reaction
of limonene oxide as a biorenewable resource has recently
been explored.211
The reaction mechanism has been precisely investigated Scheme 28. Asymmetric Alternating Polymerization
using diiminate complexes (Scheme 27).54 Fundamentally,
the reaction mechanism for cyclic carbonate synthesis
(Scheme 24) is also applicable to the alternating copolym-
erization, as the structure of the polymer end supports this
mechanism. hexene oxide has been polymerized to give optically active
alternating copolymers in up to 88% ee.212,213
5.3. Asymmetric Polymerization
Asymmetric zinc complexes effectively produce enantio-
5.4. Immobilized Catalysts
selective polymerization (Scheme 28, Table 13). Using An alternating polymerization has been conducted using
optically active iminates and amino alcohol ligands, cyclo- zinc diiminate complexes immobilized on mesoporous silica
Table 13. Asymmetric Polymerization
amount of PCO2 temp time TOFa Mn % ee

epoxide catalyst cat. (mol %) (bar) (°C) (h) TON (h-1) (×10-3) Mw/Mn (R, R) ref
CHO 8a 1 7 20 24 100 4.2 14.7 1.35 86 212
CHO 8b 1 7 20 24 100 4.2 27.1 1.21 88 212
CHO 8c 2.5 30 40 16 23 1.4 11.8 15.7 49 213
CHO 8d 2.5 30 40 16 38 2.4 7.7 1.63 80 213
a
Table 14. Immobilized Catalysts for Alternating Polymerization
Zn loading PCO2 temp time TOFa carbonate Mn

epoxide catalyst (mmol/g of silica) (bar) (°C) (h) TON (h-1) linkages (%) (×10-3) Mw/Mn ref
CHO 9a 0.15 7 50 4 72 18 73 15.5 1.31 214
CHO 9b 0.14 7 50 4 60 12 65 21.4 1.40 214
CHO 9c 0.08 7 50 4 126 21 78 16.6 1.29 214
CHO 9d 0.09 7 50 4 78 13 72 19.7 1.36 214
Scheme 31. Urethane Synthesis with an Organic Halide

(SBA-15) and porous glass as the catalyst. However, the
catalytic activities are slightly diminished compared to
homogeneous catalysts (Table 14).214
Scheme 32. Urethane Synthesis Catalyzed by Mesoporous
Silica
6. Synthesis of Urea and Urethane Derivatives
Carbon dioxide readily reacts with nucleophiles. For
example, urea is industrially produced by a reaction with
ammonia (Scheme 29).215-217 In order to obtain substituted Scheme 33. Urethane Synthesis with an Alcohol
ureas, dehydration is the key. Recently, the synthesis of N,N′-
dialkylurea has been achieved by removing water using
hydrophilic ionic liquids as reaction media (Scheme 29).215
On the other hand, secondary or primary amines react with
CO2 to give carbamic acids (Scheme 30).218 Reactions of in
situ generated carbamic acids with electrophiles such as
organic halides result in the formation of urethanes (car-
bamates) (Scheme 31). Various homogeneous and hetero- work as effective catalysts even without an additional base
geneous catalysts are applicable to synthesize urethane.219-224 (Scheme 32).154,225
Mesoporous silica containing ammonium salts as the template In Scheme 31, if organic halides can be replaced by
and adenine-modified Ti-incorporated mesoporous silica alcohols, then the byproduct (H-X) becomes water; the
process is environmentally friendly (Scheme 33).226,227
Scheme 29. Urea Synthesis from CO2 However, yields are limited to a very low level due to
thermodynamic limitations and catalyst deactivation caused
by the coproduced water. Hence, dehydration of the reaction
mixture is the key for high yields, and a method, which was
Scheme 30. Carbamic Acid Formation developed for the dialkyl carbonate synthesis, namely
dehydration using ketals, works effectively.37 Challenges in
the near future include improving the productivity (reaction
Scheme 34. Urethane Synthesis from an Alkene Scheme 40. Oxazolidinone from Propargylalcohol
Scheme 35. Isocyanate from Urethane Scheme 41. Carboxylic Acid from Organometallic
Scheme 36. Quinazoline Synthesis from CO2

Scheme 42. CO2 Insertion into a Tin-Carbon Bond
Scheme 43. CO2 Insertion into a Boron-Carbon Bond

Scheme 37. Oxazolidinone Synthesis
Scheme 38. Polyurethane from CO2
Scheme 44. Acrylic Acid from CO2
Scheme 39. Oxazolidinone from Aminoalcohol Scheme 45. Acrylic Acid from CO2 by Metal Complexation
rate) and incorporating aromatic amines as substrates.

Carbamates can also be synthesized through nucleophilic Scheme 46. Acrylic Acid Derivative from Acetylene
addition of carbamic acids to alkenes (Scheme 34).228
Schemes 31-34 are important as non-phosgene routes to
yield isocyanates because thermolysis of carbamates gives
isocyanates (Scheme 35).229
Intramolecular nucleophilic attack of carbamic acid to
nitrile results in quinazoline formation (Scheme 36).230-232
Addition of DBU under supercritical conditions enhances
the reaction rate.
Like cyclic carbonate synthesis, a nitrogen-containing
three-membered ring (aziridine) reacts with CO2, which leads compounds, and metal enolates attack CO2 under relatively
to a nitrogen-containing five-membered ring (oxazolidinone) mild conditions to generate carboxylic acids (Scheme
(Scheme 37).233-237 Although the reaction proceeds without 41).248-252 Palladium and rhodium complexes catalyze the
a catalyst, the presence of various compounds promotes the insertion of CO2 into tin-carbon and boron-carbon bonds
reaction; typical catalysts are alkali metal salts, quaternary (Schemes 42 and 43).253,254
ammonium salts, chromium salen complexes, etc.238-242 Acrylic acid, a typical unsaturated carboxylic acid, is
Ring-opening polymerization under supercritical conditions currently consumed on a large industrial scale as a raw
to yield polyurethanes has also been reported (Scheme 38). material for water-absorbing polymers. The acid is produced
The resulting polymer undergoes a phase change according by oxidation of propylene via acrolein. If the acid can be
to the pH and temperature.238 directly synthesized from ethylene and CO2, it would be quite
Although the reaction of 1,2-aminoalcohols with CO2 attractive (Scheme 44). Because the reaction is thermody-
produces five-membered urethanes (oxazolidinones), the namically possible,255 the key is to develop an efficient
conversion is poor without dehydrating agents (Scheme catalyst. The stoichiometric formation of acrylic acid on a
39).243 Oxazolidinones can also be obtained by reacting molybdenum complex has been reported (Scheme 45).256-258
carbamic acids and acetylenic compounds in the presence Five-membered metallalactones are obtained by the reac-
of a copper catalyst (Scheme 40).244-247 tion of a low-valent metal complex, CO2, and an unsaturated
compound (Scheme 4).22 Although a stoichiometric amount
of metal is consumed, desired unsaturated carboxylic acids
7. Synthesis of Carboxylic Acid are selectively synthesized via metallacycles (Schemes 46-
Along with carbonates, carboxylic acids are suitable 50).259-263 In many cases, DBU promotes the reactions,
synthetic targets starting from CO2. Carbon nucleophiles such presumably by trapping CO2 as a carbamate or a bicarbonate
as Grignard reagents, alkyl lithiums, active methylene form.264,265
Scheme 47. Acrylic Acid Derivative from Acetylene Scheme 55. Carboxylic Acid Formation by C-H Bond
Activation
Scheme 48. Acrylic Acid Derivative from Acetylene

Scheme 56. Carboxylic Acid Formation by C-H Bond
Activation
Scheme 49. Acrylic Acid Derivative from 1,3-Butadiene
Scheme 57. Carboxylic Acid Formation by C-H Bond

Activation
Scheme 50. Acrylic Acid Derivative from Allene
Scheme 58. Carboxylation with CO2
Scheme 51. Acrylic Acid Derivative from Acetylene

Scheme 59. Carboxylation with Organic Halide
Scheme 52. Asymmetric Cyclization-Carboxylation with

CO2
Scheme 60. Carboxylation of Ethylene
temperature and pressure (Henkel-type reaction) (Scheme

55),273 and the vanadium- or palladium-catalyzed reaction
with CO2 in the presence of an oxidizing reagent such as
K2S2O8 (Scheme 56).274,275 C-H bond activation by the Pd-
Scheme 53. Dicarboxylation of Allene with CO2 K2S2O8-CF3CO2H system is widely applicable to various
reactions.276 As for the reaction of CO2 under electrophilic
conditions using AlCl3 as a Lewis acid, the direct activation
of aromatic C-H bonds (Scheme 57)277 and the utilization
of silylated aromatic compounds have been demonstrated
Scheme 54. Kolbe-Schmidt Reaction (Scheme 58).278,279 Metal-catalyzed reactions of organic
halides, CO2, and hydrogen have also produced carboxylic
acids (Scheme 59).280-282 Although forming carboxylic acids
by reacting olefins and CO2 under acidic conditions has been
reported, the details are unknown (Scheme 60).283
The addition of a stoichiometric amount of dialkyl zincs
regenerates a low valent nickel complex through reductive
elimination, and thus, nickel is catalytic (Schemes 51-
8. Synthesis of Esters and Lactones
53).266-269 Asymmetric synthesis can be conducted using Combining various unsaturated compounds and CO2
optically active phosphine ligands (Scheme 52).267 results in the formation of esters and lactones. For example,
Carboxylation with CO2 can be carried out under either polymerization of vinyl ethers under CO2 in the presence of
basic (Schemes 54 and 55) or acidic (Schemes 56-60) aluminum compounds affords polymers that incorporate CO2
conditions. Hydroxybenzoic acid is one of the few chemicals into the main chain (Scheme 61). However, the yields of
that is industrially produced from CO2 (Kolbe-Schmidt these polymers are very low and further improvement is
reaction) (Scheme 54).270-272 In addition, the following are required.284-286 A similar CO2 incorporation has also been
examples of a hydrocarbon transformation to carboxylic reported for the polymerization of a three-component system,
acids: the reaction with metal carbonates under a high which contains a phosphorus compound (Scheme 62).287
Scheme 61. Copolymerization of Vinyl Ether with CO2 Scheme 65. Lactone from Allene
Scheme 66. Lactone from Acetylene
Scheme 62. Three-Component Polymerization
Scheme 63. Palladacycle Formation

Scheme 67. Cyclic Polymerization of Diacetylene with CO2
Scheme 68. Polymerization of Diacetylene
Scheme 64. Lactone from 1,3-Butadiene
Scheme 69. Three-Component Cyclization with Benzyne
In the 1980s a lot of research was conducted on five-

membered nickellacycles.22 The X-ray structures of five-
membered palladacycles have also been reported (Scheme
63, Figure 3).288 The insertion of other unsaturated com- benzynes (Scheme 69),303 and so forth. Nickel complexes
pounds leads to the ring expansion of the metallacycles. The with bulky carbene ligands efficiently catalyze the 2 + 2 +
continuing reductive elimination yields lactones and regener- 2 cycloaddition between the diyne parts and CO2 under very
ates low valent metal complexes to complete the catalytic mild reaction conditions (60 °C, 1 bar) to yield six-membered
cycle. Unsaturated compounds used for these reactions are cyclic lactones (Scheme 70).304,305
dienes (Scheme 64),289-291 allenes (Scheme 65),292 acetylenes A five-membered ring, which can be obtained through the
(Scheme 66),293,294 diynes (Schemes 67 and 68),295-302 oxidative cyclization of CO2 and oxygen with a palladium
Figure 3. Molecular structures of palladalactone and palladacyclopentane.

Scheme 70. Lactone from Diacetylene Scheme 73. Isocyanate Synthesis with CO2
Scheme 74. Hydrogenation Using scCO2
Scheme 71. O2 Activation by a Metal Complex

Scheme 75. Ester Formation Wia Hydrogenation
Scheme 76. Amide Formation Wia Hydrogenation
Scheme 72. Stille-Type Three-Component Coupling

Scheme 77. Hydrogenation by an Active Rh Complex
Scheme 78. Hydroformylation with CO2
complex, has been structurally characterized by X-ray

diffraction (Scheme 71).306 A similar rhodium compound Scheme 79. Methanol Homologation with CO2
has also been reported.307 Applying these complexes to
catalytic oxidation reactions with molecular oxygen seems
interesting, but there have not been successful reports.
Palladium-catalyzed C-C cross coupling under a CO2
atmosphere can give esters. The first successful report was
a palladium-catalyzed C-C coupling between allyl chloride
and allyl(tributyl)tin (Scheme 72).308 Because the reactant supercritical CO2 (Scheme 74).311-313 The merits of employ-
is limited to allyl compounds, this reaction is not very ing supercritical CO2 for hydrogenation are that the solvent
practical. does not produce waste and enormously high hydrogen
concentrations can be realized. The hydrogenation of CO2
9. Synthesis of Isocyanates under supercritical conditions in the presence of methanol
and dimethyl amine has resulted in the very efficient
By dehydrating carbamic acids, which are in equilibrium synthesis of methyl formate (Scheme 75)314 and N,N-dimethyl
with amine and CO2, isocyanates can be synthesized without formamide (Scheme 76), respectively.315 It is noteworthy that
employing phosgene. Researchers at Monsanto have been although the reaction mixture is initially homogeneous, the
investigating this process. For example, isocyanates can be mixture becomes biphasic shortly after the reaction; the
synthesized by dehydration with POCl3 or P4O10 in the ruthenium complex catalyst exists in the lower phase. A very
presence of tertiary amines (Scheme 73).309,310 Conducting high reaction rate, as in supercritical CO2, can also be
this reaction on a large industrial scale will be difficult obtained using bulky bidentate phosphines in polar organic
because the reaction requires an equimolar amount of solvents (Scheme 77).316 Unusual three-coordinate, 14-
dehydrating agents as well as bases, and produces a large
electron complexes have been proposed as the active catalytic
amount of waste. As for closely related technology, namely
species.
urethane thermolysis, please see section 6 (Scheme 35).229
Under high-pressure CO2 and hydrogen, alkenes are
hydroformylated to yield alcohols and aldehydes in the
10. Hydrogenation and Hydroformylation, and presence of a ruthenium complex (Scheme 78).317 Presum-
Alcohol Homologation ably, the reaction proceeds via the formation of carbon
Depending on the reaction conditions, hydrogenation of monoxide through a reverse water gas shift reaction. Ho-
CO2 by homogeneous catalysts yields carbon monoxide, mologation of alcohols using carbon dioxide is also reported
formic acid, methanol, etc. The procedure to use supercritical in the presence of hydrogen (Scheme 79). As was the case
CO2 as a substrate and as a reaction medium for the CO2 of the hydroformylation (Scheme 78), carbon monoxide
hydrogenation gave rise to numerous studies on catalysis in generated from CO2 would be the real reactant.318,319
Scheme 80. Carboxylation of an Organic Halide already been industrialized. Second, we have to grow
seedling to large trees. Some candidates of such promising
reactions include carboxylic acid synthesis and ester syn-
thesis. It is especially important to improve reactions with
low catalytic performance or those under severe conditions
such as copolymerization of vinyl ethers and CO2, and
isocyanate synthesis from CO2. Third, it is important to
establish foundations for science to search for new reactions
and new catalysts, and to elucidate reaction mechanisms at
the molecular level. Examples of interesting research subjects
Scheme 81. Carboxylation of an Organic Halide include acrylic acid synthesis from ethylene and CO2, and
direct carboxylation of C-H bonds. Such fundamental
research will lead to the new seeds for industrialization.
13. Abbreviations
acac acetylacetonato
bmim 1-butyl-3-methylimidazolium
CHO cyclohexene oxide
COD 1,5-cyclooctadiene
dba dibenzylideneacetonato
DAPO N,N-diphenylaminomethyl oxirane
DBU 1,8-diazabicyclo[5.4.0]undec-7-ene
11. Electrochemical Reaction dcpc 1,4-bis(dicyclohexylphosphino)butane
DMAP 4-dimethylaminopyridine
Electrochemical reduction of carbon dioxide alone results DMAQ N,N-dimethylaminoquinoline
in the formation of oxalic acid and its derivatives such as dppb 1,4-bis(diphenylphosphino)butane
glycolic acid, glyoxylic acid, etc.320 These reactions are not dppe 1,2-bis(diphenylphosphino)ethane
selective enough. By the electrochemical reactions of alkenes, dppp 1,3-bis(diphenylphosphino)propane
ketones, or organic halides under CO2, carboxylic groups EO ethylene oxide
are introduced to organic substrates. For example, allylic N-Melm N-methylimidazole
halides are converted to the corresponding carboxylic acids OTf trifluoromethanesulfonato
PCy3 tricyclohexylphosphine
(Scheme 80),321 while carbonyl compounds are transformed PEPO 1,2-epoxy-3-phenoxypropane
into R-hydroxycarboxylic acids. A similar electrochemical PhCN benzonitrile
carboxylation of a benzylic chloride is promoted under PO propylene oxide
supercritical conditions; the procedure was applied to the PPN bis(triphenylphosphine)iminium
synthesis of Ibuprofen (Scheme 81).322 rt room temperature
SO styrene oxide
TOF turnover frequency
12. Prospects of CO2 Transformation323 TON turnover number
Establishing a chemical industry based on a renewable
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Chem. Rev.

2007, 107, 2365−2387 2365

Transformation of Carbon Dioxide

Received December 19, 2006

Contents Scheme 1. CO2 as a Green Carbon Resource

Scheme 4. Typical Transformations of Carbon Dioxide

Jun-Chul Choi was born in 1968 in Korea and studied Chemistry at

Scheme 8. Dialkyl Carbonate Synthesis with CO2

Scheme 5 summarizes examples of organic synthesis

Scheme 9. Synthesis of Dialkyl Carbonate from CO2

Because acetone appears to be the most convenient

2.4. Heterogeneous Catalysis

Scheme 15. DMC Synthesis Using an Inorganic Dehydrating

Figure 1. Molecular structure of [Me2Sn(OMe)(OCO2Me)]2.

Scheme 16. DMC Synthesis in the Presence of Methyl

Figure 2. Time dependence of dimethyl carbonate synthesis from

between these two parts, has been designed; molecular sieves

Table 1. Dimethyl Carbonate Synthesis from Epoxides, Methanol, and CO2

epoxidea MeOH catalyst PCO2 temp time yield

Table 2. Cyclic Carbonate Synthesis Catalyzed by Salen and Phthalocyanine Complexes

amount of PCO2 temp time TOFa

Table 3. Cyclic Carbonate Synthesis Catalyzed by Onium Salts

amount of PCO2 temp time TOFa

Table 4. Various Homogeneous Catalysts for Cyclic Carbonate Synthesis

PO NaI/Ph3P/PhOH 2 40 (rt) 120 2 48 23.8 131

Table 5. Cyclic Carbonate Synthesis Catalyzed by Heterogeneous Catalysis

Table 6. Immobilized Catalysts for Cyclic Carbonate Synthesis

PCO2 temp time yield selectivity

Scheme 24. Possible Mechanism of Cyclic Carbonate Synthesis: 1

Scheme 25. Possible Mechanism of Cyclic Carbonate Synthesis: 2

Table 7. Asymmetric Synthesis of Cyclic Carbonates

amount of PCO2 temp time TOF

amount of PCO2 temp time TOFa carbonate Mn

Table 9. Homogeneous Cobalt Catalysts for Alternating Polymerization

cocatalyst amount of PCO2 temp time TOFa carbonate Mn

Table 10. Homogeneous Chromium Catalysts for Alternating Polymerization

cocatalyst amount of PCO2 temp time TOFa carbonate Mn

Table 11. Homogeneous Ln and Mn Catalysts for Alternating Polymerization

amount of PCO2 temp time TOFa carbonate Mn

Table 12. Non-Single-Site Zinc Catalysts for Alternating Polymerization

Scheme 27. Possible Mechanism of Alternating Polymer

Table 13. Asymmetric Polymerization

amount of PCO2 temp time TOFa Mn % ee

Table 14. Immobilized Catalysts for Alternating Polymerization

Zn loading PCO2 temp time TOFa carbonate Mn

Scheme 31. Urethane Synthesis with an Organic Halide

Scheme 36. Quinazoline Synthesis from CO2

Scheme 43. CO2 Insertion into a Boron-Carbon Bond

Scheme 38. Polyurethane from CO2

Scheme 44. Acrylic Acid from CO2

rate) and incorporating aromatic amines as substrates.

Scheme 48. Acrylic Acid Derivative from Acetylene

Scheme 49. Acrylic Acid Derivative from 1,3-Butadiene

Scheme 57. Carboxylic Acid Formation by C-H Bond

Scheme 50. Acrylic Acid Derivative from Allene

Scheme 58. Carboxylation with CO2

Scheme 51. Acrylic Acid Derivative from Acetylene

Scheme 52. Asymmetric Cyclization-Carboxylation with