Convergent Activation Concept for CO2 Fixation in Carbonates

Article abstract of DOI:10.1002/adsc.201500941

Concepts to facilitate the conversion of epoxides with carbon dioxide to the corresponding cyclic carbonates commonly focus on the activation of the epoxide. Herein we report a catalytic system which allows the simultaneous activation of carbon dioxide and the epoxide. This convergent activation concept is realized by combining a suitable carbene as catalyst for the carbon dioxide activation with a second catalytic system based on potassium iodide for epoxide activation. Initial experiments showed synergistic effects and thus proving the feasibility of this activation concept. Moreover a standard protocol was developed and the substrate scope under these conditions has been studied. Under mild and solvent-free conditions 14 epoxides could be converted. The respective cyclic carbonates were obtained in good to excellent yields with selectivities ≥ 99 % after simple filtration.

Full text of DOI:10.1002/adsc.201500941

FULL PAPERS
DOI: 10.1002/adsc.201500941
Convergent Activation Concept for CO Fixation in Carbonates
2
a
a,
Willi Desens and Thomas Werner *
a
Leibniz-Institute of Catalysis, Albert-Einstein-Str. 29a, 18059 Rostock, Germany
Fax: (+49) 381 1281 51191; e-mail: Thomas.Werner@catalysis.de
Received: October 5, 2015; Revised: November 20, 2015; Published online: January 5, 2016
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201500941.
Abstract: Concepts to facilitate the conversion of ep- this activation concept. Moreover a standard proto-
oxides with carbon dioxide to the corresponding col was developed and the substrate scope under
cyclic carbonates commonly focus on the activation these conditions has been studied. Under mild and
of the epoxide. Herein we report a catalytic system solvent-free conditions 14 epoxides could be convert-
which allows the simultaneous activation of carbon ed. The respective cyclic carbonates were obtained
dioxide and the epoxide. This convergent activation in good to excellent yields with selectivities ꢀ 99%
concept is realized by combining a suitable carbene after simple filtration.
as catalyst for the carbon dioxide activation with
a second catalytic system based on potassium iodide Keywords: carbon dioxide fixation; catalysis; conver-
for epoxide activation. Initial experiments showed gent activation; cyclic carbonates; N-heterocyclic
synergistic effects and thus proving the feasibility of carbene
Introduction
zation reactions and intermediates in the synthesis of
[9]
fine chemicals. Numerous catalysts and catalytic sys-
The increase of the anthropogenic emissions of green- tems have been reported for the synthesis of cyclic
[10]
house gases is deemed to contribute to the global cli- carbonates from epoxides and CO2. However, the
[
1]
mate change. The largest share of those emissions development of novel active, tunable and selective
into the atmosphere is allotted to be carbon dioxide, catalytic systems is still a constant challenge. Recent-
[11]
[10c,12]
which arises mainly from the combustion of fossil ly, very efficient onium salts,
ionic liquid
as
fuels. Different strategies for managing carbon diox- well as alkali and transition metal based catalysts
[
2]
[10a,13]
ide emissions are frequently discussed. Sustainable have been reported.
Metal systems based on alu-
approaches are the reduction of carbon dioxide minum, sodium and potassium are highly attractive in
output as well as the utilization as a renewable C1 respect to economy and sustainability, since they are
[
3]
building block in synthetic chemistry. The latter re- usually cost efficient, readily available and non-
[
10a]
cently has given great attention in current research toxic.
In this context potassium iodide is the most
[
4]
and industry. Thus carbon dioxide might no longer frequently employed alkali metal salt. However, when
be regarded as a waste-product but instead as an used alone its catalytic activity is rather low and
abundant, cheap, non-toxic, easily available source of therefore usually additives such as 18-crown-6 are em-
carbon. The utmost challenge in carbon dioxide uti- ployed to enhance the solubility and activity of the
[
12c,d,14]
lization is its thermodynamic stability and kinetic iner- salt.
For example, Kuran et al. described a cata-
Hence, usually high energy starting materials lytic system consisting of KI and 18-crown-6 to syn-
and elevated reaction temperatures are required. thesize cyclic carbonates from epoxides and CO at
[2c,4f,5]
tia.
2
[15]
However, one of the major keys to efficiently convert 1208C, 40 bar CO2 and 4 h.
More recently,
CO into value-added products is the development of Schäffner et al. studied the utilization of potassium
2
suitable catalysts.
iodide in combination with various phase transfer cat-
[16]
The atom-economic reaction between carbon diox- alysts for the synthesis of oleochemical carbonates.
ide and epoxides producing five-membered cyclic car-
From a mechanistic point of view it is well recog-
bonates and polycarbonates is an attractive route for nized that commonly employed catalysts, also alkali
[
6]
carbon dioxide utilization. Those organic carbonates metal based systems, activate only the epoxide during
[
7]
[12b,13e,14b,f,17]
can be applied as polar aprotic solvents, electrolytes the reaction process.
The combination of
[
8]
in lithium-ion batteries, monomers in polymeri- a Lewis acidic catalyst and Lewis basic co-catalyst
6
22
ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2016, 358, 622 – 630

FULL PAPERS
Convergent Activation Concept for CO Fixation in Carbonates
2
Table 1. Test reaction and feasibility study for the conver-
[
a]
gent activation concept.
Scheme 1. Convergent activation concept for the synthesis
of cyclic carbonates 2 from epoxides 1 and CO . Cat. A:
2
Alkali metal salt MX and cat. B: Suitable carbene.
[b]
Entry 3a/mol% KI/mol% 18C6/mol% Yield 2a/%
1
2
3
4
5
6
7
8
9
1
-
2
-
-
2
-
2
2
2
2
-
-
2
-
-
2
2
2
2
2
-
-
-
2
2
2
-
2
2
-
0
[
10]
might lead to dual activation of the epoxide.
In
[c]
0 (0)
1
0
0
some cases those systems are highly active allowing
the conversion of epoxides with CO even at very
Notably, N-heterocyclic carbenes
NHC) can react with carbon dioxide to form imida-
These adducts can also be
employed as catalysts for the synthesis of cyclic carbo-
2
[
18]
mild conditions.
(
67
[
19]
[c]
85 (86)[
92 (88)
88
zolium-2-carboxylates.
c]
[
d]
[
19b,20]
nates from epoxides and CO2.
Even though
[e]
0
82
this is one of the rare examples for the activation
of carbon dioxide and subsequent conversion to
the cyclic carbonate, drastic reaction conditions
T ꢀ 1008C, p(CO ) ꢀ 20 bar) and long reaction
[
[
[
a]
Reaction conditions: 0 or 2 mol% 3a or 4a, 0 or 2 mol%
KI, 0 or 2 mol% 18C6, p(CO
3 h, neat.
)=10 bar, T=1008C, t=
2
(
2
b]
[
20]
Conversion and yields were determined by GC-FID with
times (t ꢀ 15 h) are required.
n-hexadecane as internal standard. The selectivity was ꢀ
We intended the development of a catalytic system
for the synthesis of cyclic carbonates based on a con-
vergent activation concept, which might operate
under milder conditions due to synergistic effects
9
2
2
2
9%.
c]
mol% 4a was employed instead of 3a.
mol% DBU was employed instead of 3a.
mol% TBAI was employed instead of KI.
[d]
[e]
(
Scheme 1). North et al. reported the activation of
CO by tributylamine which was formed in situ by the
2
decomposition of tetrabutylammonium bromide, iodide or 18-crown-6 (18C6) was employed separately
while an epoxide was activated by an aluminium(sa- (entries 2–4). Subsequently cross-over experiments
[
21]
len)complex.
We envisioned that a promising ap- were performed. The combination of 3a and 18C6 re-
proach to this convergent activation concept would be sulted also not in the formation of the desired cyclic
the combination of a carbene suitable for CO activa- carbonate 2a (entry 5). Moderate yield was obtained
2
tion with an alkali metal based system for the epoxide utilizing potassium iodide in combination with 18C6,
activation.
which has been previously reported by Kuran et al. as
[15]
catalyst system for this reaction (entry 6). Interest-
ingly, the combination of 3a or 4a and potassium
iodide in the absence of the crown ether gave 2a al-
ready in a good yield of 85% and 86%, respectively
Results and Discussion
Our first aim was to proof the general feasibility of (entry 7). However, employing 2 mol% of 3a in com-
the proposed convergent activation concept. We bination with equimolar amounts of potassium iodide
chose the conversion of 1,2-epoxybutane (1a) with and 18-crown-6 an excellent yield of 92% was ob-
CO to 1,2-butylene carbonate (2a) as a test reaction. tained (entry 8). A similar result could be achieved
2
The reaction conditions for the initial screening were utilizing carbene CO adduct 4a. Bicyclic amidines
2
[22]
determined to be 1008C, 10 bar CO pressure, 3 h re- are also known to activate CO2. Thus additionally
2
action time and a catalyst concentration of 2 mol% we tested DBU for the activation of CO in combina-
2
under solvent-free conditions (Table 1). As expected tion with potassium iodide and 18-crown-6 (entry 9).
no product formation was observed in the absence of Moreover we tested tetrabutylammonium iodide
a catalyst (entry 1). Notably, the same result was ob- (TBAI) as alternative to the potassium salt/crown
tained if carbene 3a, CO2 adduct 4a, potassium ether combination (entry 10). Even though in both
Adv. Synth. Catal. 2016, 358, 622 – 630
ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
623

Willi Desens et al.
FULL PAPERS
Table 2. Influence of the reaction parameters on the conver- (entry 5). Furthermore, the influence of the catalyst
sion of 1a to cyclic carbonate 2a utilizing the convergent ac-
tivation catalyst system.
amount was examined and the test reaction was per-
[a]
formed with different catalyst loadings. A decrease of
the amount of catalyst from 2 mol% to 1 mol% gave
2a in comparably lower yields of 63% (entry 6). No-
tably, even in the presence of 0.5 mol% the desired
product was obtained in 38% (entry 7). The reaction
temperature had the highest impact on the reaction
outcome. At 1208C a similar yield of 2a of 91% was
obtained compared to 92% at 1008C (entry 8). How-
ever, decreasing the temperature to 908C a significant
drop in activity was observed and merely 55% of 2a
was obtained (entry 9). A reduction of the catalyst
concentration to 1 mol% and a reaction time of 24 h
at 908C gave carbonate 2a in 91% (entry 10). How-
ever, a further decrease of the reaction temperature
to 608C led to only moderate yield of 49% even in
the presence of 2 mol% catalyst, demonstrating the
temperature dependency of this reaction (entry 11).
[
b]
Entry mol% T/
p/
bar
t/ yield [
TON TOF/
c]
À1
8
C
h
2a/%
h
1
2
3
4
5
6
7
8
9
1
1
1
1
2.0
2.0
2.0
2.0
2.0
1.0
0.5
2.0
2.0
1.0
2.0
0.1
0.1
100 10
100 20
100 50
100 10
100 10
100 10
100 10
120 10
90
90
60
140 10
140 10
3
3
3
6
1
3
3
3
3
92
84
64
95
58
63
38
91
55
46
42
32
48
29
63
76
46
27
92
24
15
14
11
8
29
21
25
15
9
10
10
10
0
1
2
3
24 91
24 49
4
1
1
2
23
40
228 228
403 202
[a]
Reaction conditions: 1,2-butylene oxide (1a, 25 mmol),
.1–2.0 mol% carbene 3a/KI/18C6 (1:1:1), T=60–1008C, In this context, utilizing 0.1 mol% of catalyst an in-
p(CO )=10–50 bar, t=1–24 h.
creased temperature of 1408C was necessary to ach-
b]
0
2
[
[
Please note that amount of catalyst employed refers to ieve 23% of carbonate 2a after 1 h in the model reac-
À1
an equimolar mixture carbene 3a/KI/18C6 (1:1:1).
Determined by GC-FID with n-hexadecane as internal
standard. The selectivity was ꢀ 99%. TON=n(product)/
n(catalyst).
tion (entry 12). Herein, an excellent TOF of 228 h
c]
was achieved. Extending the reaction time to 2 h the
turnover number (TON) was improved from 228 to
4
03 (entry 13).
We envisioned that the stability of the in situ
cases good yields for 2a were achieved the best result formed imidazolium carboxylate 4a might have a sig-
was achieved with the system combining the NHC, KI nificant impact on the overall activity of the catalytic
and 18-crown-6 (entry 8). Those results indicate the system. Louie et al. reported a detailed systematic
general feasibility of the proposed convergent activa- study of factors influencing the decarboxylation of ad-
[19d]
tion concept.
ducts 4.
They observed a significant impact of the
The scope and limitations of this catalytic system steric bulk of the N-substituent that even can override
were evaluated in respect to the reaction parameters electronic effects on the decarboxylation temperature.
(
Table 2). At first, the CO pressure was increased to We assumed that carbenes 3 which form more stable
2
2
0 bar, which led to a slight decrease in activity and imidazolium carboxylates 4 should be less active in
resulted in a yield of 84% of 2a (entry 2). Remarka- our catalyst system compared to carbenes, which form
bly, a further increase of the CO pressure to 50 bar weaker adducts 4. Thus, based on the decarboxylation
2
caused a significant drop in activity and merely 64% temperature (T ) ranging from 718C to 1628C, re-
D
of cyclic carbonate 2a was obtained (entry 3). Obvi- ported by Louie et al., we choose carboxylates 4a–4c
ously the CO pressure has a significant influence on as promising candidates to verify our assumption. The
2
the activity of this catalytic system, in which a higher respective carbenes 3a–3b and imidazolium salt 3c
CO pressure resulted in lower yield of cyclic carbon- were prepared according to literature procedures and
2
ate 2a. The lower activity by increasing CO pressure subsequently reacted with CO to yield the desired
2
2
might be explained by a dynamic equilibrium between products 4a–4c in excellent yields up to 97%
CO , the free carbene 3a and the corresponding CO
(Scheme 2).
2
2
[
20b]
adduct 4a.
Lu et al. proposed that an increase of
Subsequently we employed the prepared imidazoli-
um carboxylates 4a–4c in our test reaction. We re-
the CO concentration in the solution at a higher CO
2
2
pressure results thus shifting the equilibrium from the duced the reaction temperature and time to be able
carbene 3a to the respective imidazolium-2-carboxyl- to directly uncover activity differences. Initially, we
ate 4a. In our case this might hamper the overall effi- employed 3a under the modified conditions to set
ciency of the CO transfer from 4a to the substrate.
a benchmark (Table 3, entry 1).
2
Subsequently the influence of the reaction time on
We turned our attention to carboxylate 4b, which
the conversion of 1a to 2a was studied. After 6 h the shows the lowest TD of 718C. Thus, we expected 4b
yield of 2a increased to 95% (entry 4). Shortening to be the most active catalyst. Surprisingly, in the
the reaction time to 1 h a decrease in yield was ex- presence of 4b the product 2a was obtained in signifi-
pected, however still 58% of 2a was achieved cantly lower yield of 24% compared to the bench-
6
24
asc.wiley-vch.de
ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2016, 358, 622 – 630

FULL PAPERS
Convergent Activation Concept for CO Fixation in Carbonates
2
Table 4. Evaluation of the substrate scope under standard
[
a]
reaction conditions.
[a]
Entry
1
Product
Yield/%
81
Scheme 2. Synthesis of imidazolium carboxylates 4a–4c
from the respective carbenes 3a–3b and imidazolium salt
3
3
1
c, respectively. Conditions A: 1 atm CO , Et O, 0 8C,
0 min. Conditions B: i) KHMDS, toluene, 238C, 16 h; ii)
2a
2b
2c
2d
2e
2 f
2
2
atm CO , 08C, 1 h.
2
2
3
4
5
6
79
87
87
86
91
Table 3. Influence of the decarboxylation temperature (TD)
of different imidazolium carboxylates 4a-4c on the yield of
[a]
2
a in the test reaction.
[b]
[c]
[d]
Entry
2 mol% (1:1:1)
T /8C
D
Yield 2a/%
1
2
3
4
3a/KI/18C6
4b/KI/18C6
4a/KI/18C6
4c/KI/18C6
–
71
108
162
51
24
43
30
[a]
Reaction conditions: 1,2-butylene oxide (1a, 25 mmol),
2
.0 mol% 3a or 4/KI/18C6 (1:1:1), T=908C, p(CO )=
2
10 bar, t=2 h.
[b]
Please note that amount of catalyst employed refers to
an equimolar mixture of all three components.
Decarboxylation temperature according to ref. 19d.
Determined by GC-FID with n-hexadecane as internal
standard. The selectivity was ꢀ99%.
[
[
c]
7
8
9
2g
2h
2i
92
91
87
87
d]
mark (entry 1 and 2). If carboxylate 4a (T =1088C)
D
is used as catalyst instead of the corresponding car-
bene 3a the yield dropped to 43% (entry 3). More-
over the most stable adduct 4c (T =1628C) gave 10
2j
D
product 2a still in 30% yield. Since the obtained re-
sults were inconclusive, we reevaluated the decarbox-
[
23]
ylation temperature by TGA-MS. Even though the
determined values somewhat differed from the previ-
ously reported ones no clear conclusion could be
drawn from the obtained values. Apparently there is
no correlation between the decarboxylation tempera- 12
tures thus stability of the imidazolium carboxylate 4
and the catalytic activity.
Based on those results 2 mol% of the catalyst 13
system comprising equimolar amounts carbene 3a, KI
and 18C6 was selected to evaluate the substrate
1
1
2k
2l
76
91
91
2m
2n
[b]
14
32/61
scope. The standard reaction conditions were set to
008C, 10 bar CO2 for 3 h. Notably, the reactions
1
[
a]
Reaction conditions: epoxide (1, 1.0 equiv), 2.0 mol%
a/KI/18C6 (1:1:1), T=1008C, p(CO )=10 bar, t=3 h.
were performed under solvent-free conditions and all
products were obtained by simple filtration over silica
gel. The results of the substrate screening are sum-
marized in Table 4. The test substrate 1a was convert-
ed into the corresponding carbonate 2a in an isolated
yield of 81% (entry 1). Other aliphatic substituted ep-
3
2
Isolated yields after simple filtration over SiO are given.
2
[
b]
p(CO )=50 bar, t=6 h.
2
Adv. Synth. Catal. 2016, 358, 622 – 630
ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
625

Willi Desens et al.
FULL PAPERS
oxides 1b–1d were transformed with CO to the de-
2
sired products 2b–2d in yields from 79–87% (en-
tries 2–4). Furthermore, aromatic substituted epoxides
like styrene oxide (1e) and 4-chlorostyrene oxide (1 f)
were reacted with CO to form the carbonates 2e and
2
2
f in yields of 86% and 91%, respectively (entries 5
and 6). Furthermore, the glycidyl ether 1g–1j were
turned into carbonates 2g–2j in very good isolated
yields from 87–92% (entries 7–10). Glycidyl metha-
crylate (1k) is a more challenging substrate, because
[
24]
of its tendency to polymerize. However, under the
employed reaction conditions the corresponding
cyclic carbonate 2k was obtained in a yield of 76%
without polymeric by-products (entry 11). Also the
unsaturated alkyl substituted carbonate 2l was ob-
tained in 91% (entry 12). Even an activated epoxide
like epichlorohydrin (1m) was converted by this cata-
lytic system and transformed into carbonate 2m in
a yield of 91% (entry 13). The conversion of internal
epoxides with CO to produce five-membered cyclic
2
carbonates is even more challenging. Here, the addi-
tional substituent at the epoxide hinders the nucleo-
philic attack of the catalyst for the ring opening of the Scheme 3. Putative reaction mechanism for convergent acti-
[
25]
vation of epoxide 1a and CO in the synthesis of cyclic car-
bonates 2a.
epoxide.
Nevertheless, this catalytic system trans-
2
formed cyclohexene oxide (1n) into cyclohexene car-
bonate (2n) in an isolated yield of 32%.
Moreover, employing more drastic conditions by
raising the CO pressure to 50 bar and extending the oxide (1a) to the corresponding cyclic carbonate 2a.
2
reaction time to 6 h the yield was increased to 61% Furthermore, we investigated the proposed correla-
of 2n (entry 14).
tion between decarboxylation temperature of imida-
Based on the obtained results we propose the reac- zolium carboxylates 4 and the activity of the catalytic
tion mechanism for the conversion of the test sub- system. Different substituted carboxylates 4 were
strate 1a which is depicted in Scheme 3. This is based tested in the model reaction and the yield of 2a was
on the concept of convergent activation of the epox- determined. Remarkably, no correlation between the
ide 1a and CO by the metal halide and carbene 3a, decarboxylation temperatures and the activity in the
2
respectively. Herein, the iodide initiates the ring- test reaction was observed. Finally, we evaluated the
opening of the epoxide 1a via a nucleophilic attack to substrate scope and limitations under standard reac-
generate an alkoxide. This step is well recognized for tion conditions; 14 epoxides 1 were converted to the
the utilization of alkali metal salts for example, KI as corresponding cyclic carbonates 2 under solvent-free
[
10a,14b,f,26]
catalysts.
Simultaneously carbene 3a acti- conditions. Excellent isolated yields of up to 92%
vates carbon dioxide in situ by forming the imidazoli- could be achieved after simple filtration.
um-2-carboxylate 4a, a step which is also well recog-
[
27]
nized. A transcarboxylation of CO to the alkoxide
2
and subsequent intramolecular nucleophilic substitu-
tion regenerates carbene 3a and KI and simultane-
ously releases the cyclic carbonate 2a.
Experimental Section
General procedure (GP) for the conversion of CO2
and epoxide 1
Conclusions
A 45 mL stainless steel autoclave equipped with a magnetic
stirrer was charged with potassium iodide (0.02 equiv), 18-
crown-6 (0.02 equiv), carbene 3a (0.02 equiv) and epoxide
Based on the proposed convergent activation concept
for CO fixation in cyclic carbonates we introduced
2
1
(1.00 equiv). The reactor was sealed and pressurized with
a catalytic system for the simultaneous activation of
carbon dioxide and epoxides. This system consists of
readily available potassium iodide, 18-crown-6 and
10 bar of carbon dioxide until equilibrium was reached. Sub-
sequently the reactor was heated to 1008C for 3 h. The auto-
clave was cooled with an ice bath below 208C and the CO2
carbene 3a. The influence of various reaction parame- was slowly liberated from the vessel. The crude reaction
ters were studied for the conversion of 1,2-butylene mixture was extracted with dichloromethane and filtrated
6
26
asc.wiley-vch.de
ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2016, 358, 622 – 630

FULL PAPERS
Convergent Activation Concept for CO Fixation in Carbonates
2
through a silica gel plug. After removal of all volatiles under
3a (196 mg, 0.504 mmol). After workup the title compound
reduced pressure the cyclic carbonates 2 were obtained.
2 f (4.63 g, 21.5 mmol, 91%) was isolated as a colorless
[11b]
1
4
-Ethyl-1,3-dioxolan-2-one (2a):
,2-epoxybutane (1a, 1.89 g, 26.2 mmol) was allowed to
react with CO in the presence of KI (85 mg, 0.51 mmol),
According to the GP,
solid. H NMR (300 MHz, CDCl ): d=4.30 (dd, J=8.6 Hz,
3
1
7.9 Hz, 1H), 4.80 (t, J=8.4 Hz, 1H), 5.66 (t, J=8.0 Hz, 1H),
1
3
1
7.28–7.33 (m, 2H), 7.40–7.44 (m, 2H) ppm. C{ H} NMR
2
1
0
2
8-crown-6 (137 mg, 0.518 mmol) and carbene 3a (199 mg,
.512 mmol). After workup the title compound 2a (2.48 g,
1.4 mmol, 81%) was isolated as a colorless liquid. H NMR
(75 MHz, CDCl ): d=71.0 (CH ), 76.6 (CH), 127.2 (2”CH),
3
2
129.5 (2”CH), 134.2 (C), 135.7 (C), 154.5 (C=O) ppm.
1
[11b]
4-(Phenoxymethyl)-1,3-dioxolan-2-one (2g):
Accord-
(
300 MHz, CDCl ): d=0.99 (dt, J=7.5 Hz, 2.1 Hz, 3H),
ing to the GP, phenyl glycidyl ether (1g, 3.73 g, 24.8 mmol)
3
1
.67–1.82 (m, 2H), 4.06 (dt, J=7.7 Hz, 1.5 Hz, 1H), 4.50 (dt,
was allowed to react with CO in the presence of KI (83 mg,
0.50 mmol), 18-crown-6 (134 mg, 0.507 mmol) and carbene
2
1
3
1
J=8.1 Hz, 1.2 Hz, 1H), 4.60–4.70 (m, 1H) ppm. C{ H}
-
NMR (75 MHz, CDCl ): d=8.3 (CH ), 26.7 (CH ), 68.9
3a (194 mg, 0.499 mmol). After workup the title compound
3
3
2
(
CH), 77.9 (CH), 155.0 (C=O) ppm.
2g (4.41 g, 22.7 mmol, 92%) was isolated as a colorless
[11b]
1
4-Methyl-1,3-dioxolan-2-one (2b):
According to the
solid. H NMR (300 MHz, CDCl ): d=4.14 (dd, J=10.6 Hz,
3
GP, 1,2-epoxypropane (1b, 1.52 g, 26.2 mmol) was allowed
3.6 Hz, 1H), 4.25 (dd, J=10.6 Hz, 4.1 Hz, 1H), 4.54 (dd, J=
8.5 Hz, 6.0 Hz, 1H), 4.62 (t, J=8.4 Hz 1H), 5.00–5.07 (m,
1H), 6.89–6.94 (m, 2H), 7.00–7.05 (m, 1H), 7.28–7.35 (m,
to react with CO in the presence of KI (84 mg, 0.51 mmol),
2
1
0
2
8-crown-6 (133 mg, 0.503 mmol) and carbene 3a (194 mg,
.500 mmol). After workup the title compound 2b (2.10 g,
0.6 mmol, 79%) was isolated as a colorless liquid. H NMR
1
3
1
2H) ppm. C{ H} NMR (75 MHz, CDCl ): d=66.2 (CH ),
3
2
1
66.8 (CH ), 74.1 (CH), 114.5 (CH), 121.9 (2”CH), 129.6 (2”
2
(
8
4
300 MHz, CDCl ): d=1.47 (d, J=6.3 Hz, 3H), 4.01 (dd, J=
CH), 154.7 (C=O), 157.7 (C) ppm.
4-(tert-Butoxymethyl)-1,3-dioxolan-2-one (2h):
cording to the GP, tert-butyl glycidyl ether (1h, 3.25 g,
3
[
11b]
.4 Hz, 7.2 Hz, 1H), 4.55 (dd, J=8.4 Hz, 7.8 Hz, 1H), 4.79–
Ac-
1
3
1
.88 (m, 1H) ppm. C{ H} NMR (75 MHz, CDCl ): d=19.3
3
(
CH ), 70.6 (CH), 73.5 (CH ), 155.0 (C=O) ppm.
25.0 mmol) was allowed to react with CO in the presence
of KI (83 mg, 0.50 mmol), 18-crown-6 (136 mg, 0.514 mmol)
3
2
2
[11b]
4-Butyl-1,3-dioxolan-2-one (2c):
According to the GP,
1,2-epoxyhexane (1c, 2.58 g, 25.8 mmol) was allowed to
and carbene 3a (193 mg, 0.497 mmol). After workup the
react with CO in the presence of KI (83 mg, 0.50 mmol),
title compound 2h (3.94 g, 22.6 mmol, 91%) was isolated as
2
1
1
0
2
8-crown-6 (133 mg, 0.503 mmol) and carbene 3a (194 mg,
.499 mmol). After workup the title compound 2c (3.24 g,
2.5 mmol, 87%) was isolated as a colorless liquid. H NMR
a colorless liquid. H NMR (300 MHz, CDCl ): d=1.15 (s,
3
9H), 3.48 (dd, J=10.5 Hz, 3.5 Hz, 1H), 3.59 (dd, J=
10.5 Hz, 4.4 Hz, 1H), 4.34 (dd, J=8.3 Hz, 6.0 Hz, 1H), 4.45
1
13
1
(
(
300 MHz, CDCl ): d=0.89 (t, J=6.9 Hz, 3H), 1.30–1.45
m, 4H), 1.65–1.79 (m, 2H), 4.05 (dd, J=8.2 Hz, 7.4 Hz,
(dd, J=8.3 Hz, 7.1 Hz, 1H), 4.72–4.79 (m, 1H) ppm. C{ H}
NMR (75 MHz, CDCl ): d=27.1 (3”CH ), 61.1 (CH ), 66.4
3
3
3
2
1
H), 4.51 (dd, J=8.1 Hz, 8.1 Hz, 1H), 4.64–4.73 (m, 1H)
(CH ), 73.7 (C), 75.2 (CH), 155.1 (C=O) ppm.
4-(Isobutoxymethyl)-1,3-dioxolan-2-one (2i):
2
13
1
[11b]
ppm. C{ H} NMR (75 MHz, CDCl ): d=13.6 (CH ), 22.1
Accord-
3
3
(
(
CH ), 26.3 (CH ), 33.4 (CH ), 69.3 (CH ), 77.0 (CH), 155.0
ing to the GP, isobutyl glycidyl ether (1i, 3.30 g, 25.3 mmol)
2
2
2
2
C=O) ppm.
was allowed to react with CO in the presence of KI (83 mg,
2
[11b]
4-Hexyl-1,3-dioxolan-2-one (2d):
According to the GP,
0.50 mmol), 18-crown-6 (130 mg, 0.492 mmol) and carbene
1,2-epoxyoctane (1d, 3.36 g, 26.2 mmol) was allowed to
3a (193 mg, 0.497 mmol). After workup the title compound
react with CO in the presence of KI (84 mg, 0.51 mmol),
2i (3.82 g, 21.9 mmol, 87%) was isolated as a colorless
2
1
1
0
2
8-crown-6 (135 mg, 0.511 mmol) and carbene 3a (195 mg,
.502 mmol). After workup the title compound 2d (3.91 g,
2.7 mmol, 87%) was isolated as a colorless liquid. H NMR
liquid. H NMR (300 MHz, CDCl ): d=0.90 (d, J=6.7 Hz,
3
6H), 1.82–1.91 (m, 1H), 3.27 (d, J=6.7 Hz, 2H), 3.60 (dd,
J=11.0 Hz, 3.5 Hz, 1H), 3.68 (dd, J=11.1 Hz, 4.0 Hz, 1H),
4.41 (dd, J=8.3 Hz, 6.0 Hz, 1H), 4.50 (dd, J=8.5 Hz, 8.0 Hz,
1
(
(
300 MHz, CDCl ): d=0.87 (t, J=6.5 Hz, 3H), 1.28–1.50
m, 8H), 1.61–1.83 (m, 2H), 4.05 (dd, J=8.4 Hz, 7.2 Hz,
3
1
3
1
1H), 4.77–4.85 (m, 1H) ppm. C{ H} NMR (75 MHz,
1
H), 4.51 (dd, J=8.3 Hz, 7.9 Hz, 1H), 4.65–4.74 (m, 1H)
CDCl ): d=19.1 (CH ), 28.3 (CH), 66.3 (CH ), 69.8 (CH ),
3
3
2
2
13
1
ppm. C{ H} NMR (75 MHz, CDCl ): d=13.9 (CH ), 22.3
75.1 (CH), 78.8 (CH ), 155.0 (C=O) ppm.
4-(Isopropoxymethyl)-1,3-dioxolan-2-one (2j):
3
3
2
[
11b]
(
(
CH ), 24.2 (CH ), 28.7 (CH ), 31.4 (CH ), 33.8 (CH ), 69.3
CH ), 77.0 (CH), 155.0 (C=O) ppm.
Accor-
2
2
2
2
2
ding to the GP, isopropyl glycidyl ether (1j, 2.98 g,
2
[11b]
4
-Phenyl-1,3-dioxolan-2-one (2e):
According to the
25.6 mmol) was allowed to react with CO in the presence
2
GP, styrene oxide (1e, 3.02 g, 25.1 mmol) was allowed to
of KI (83 mg, 0.50 mmol), 18-crown-6 (132 mg, 0.500 mmol)
react with CO in the presence of KI (83 mg, 0.50 mmol),
and carbene 3a (193 mg, 0.497 mmol). After workup the
2
1
0
2
8-crown-6 (133 mg, 0.503 mmol) and carbene 3a (195 mg,
.502 mmol). After workup the title compound 2e (3.53 g,
1.5 mmol, 86%) was isolated as a colorless solid. H NMR
title compound 2j (3.57 g, 22.3 mmol, 87%) was isolated as
1
a colorless liquid. H NMR (300 MHz, CDCl ): d=1.15 (d,
3
1
J=6.1 Hz, 6H), 3.57–3.68 (m, 3H), 4.38 (dd, J=8.3 Hz,
6.0 Hz, 1H), 4.48 (t, J=8.3 Hz, 1H), 4.75–4.81 (m, 1H)
(300 MHz, CDCl ): d=4.35 (dd, J=8.6 Hz, 7.9 Hz, 1H),
3
1
3
1
4
7
.80 (dd, J=8.6 Hz, 8.2 Hz, 1H), 5.68 (t, J=8.0 Hz, 1H),
ppm. C{ H} NMR (75 MHz, CDCl ): d=21.8 (CH ), 21.9
3
3
13
1
.34–7.48 (m, 5H) ppm. C{ H} NMR (75 MHz, CDCl ):
(CH ), 66.5 (CH ), 67.2 (CH ), 73.0 (CH), 75.2 (CH), 155.1
3
3
2
2
d=77.1 (CH ), 77.9 (CH), 125.8 (CH), 129.2 (2”CH), 129.7
(C=O) ppm.
2
[
11b]
(
2”CH), 135.7 (C), 154.8 (C=O) ppm.
(2-Oxo-1,3-dioxolan-4-yl)methyl methacrylate (2k):
According to the GP, glycidyl methacrylate (1k, 3.49 g,
[11b]
4-(4-Chlorophenyl)-1,3-dioxolan-2-one (2 f):
According
to the GP, 4-chlorostyrene oxide (1 f, 3.97 g, 25.7 mmol) was
24.6 mmol) was allowed to react with CO in the presence
2
allowed to react with CO in the presence of KI (84 mg,
of KI (83 mg, 0.50 mmol), 18-crown-6 (135 mg, 0.511 mmol)
2
0.50 mmol), 18-crown-6 (137 mg, 0.518 mmol) and carbene
and carbene 3a (194 mg, 0.499 mmol). After workup the
Adv. Synth. Catal. 2016, 358, 622 – 630
ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
627

Willi Desens et al.
FULL PAPERS
title compound 2k (3.49 g, 18.7 mmol, 76%) was isolated as
ing precipitate was filtered off and washed with diethyl
ether (3”30 mL). After removal of all volatiles under re-
duced pressure the title compound 4a (243 mg, 0.56 mmol,
1
a colorless liquid. H NMR (300 MHz, CDCl ): d=1.94 (t,
3
J=1.2 Hz, 3H), 4.29–4.37 (m, 2H), 4.43 (dd, J=12.6 Hz,
1
3
.1 Hz, 1H), 4.59 (t, J=8.6 Hz, 1H), 4.95–5.02 (m, 1H), 5.65
97%) was obtained as a colorless solid. H NMR (400 MHz,
1
3
1
(pent, J=1.5 Hz, 1H), 6.14–6.15 (m, 1H) ppm. C{ H}
NMR (75 MHz, CDCl ): d=18.1 (CH ), 63.4 (CH ), 66.0
CD Cl ): d=1.21 (d, J=6.9 Hz, 12H), 1.25 (d, J=6.8 Hz,
2 2
12H), 2.50 (sept, J=6.9 Hz, 4H), 7.17 (s, 2H), 7.31–7.34 (m,
3
3
2
1
3
(
CH ), 73.8 (CH), 127.2 (CH ), 135.1 (CH), 154.4 (C=O),
4H), 7.50–7.55 (m, 2H) ppm. C NMR (300 MHz, CD
Cl ):
2 2
2
2
1
66.6 (C=O) ppm.
d=23.5 (CH ), 24.4 (CH ), 29.5 (CH), 122.9 (CH), 124.4
3
3
[11b]
4-(But-3-en-1-yl)-1,3-dioxolan-2-one (2l):
According to
(CH), 131.0 (CH), 132.8 (C), 145.2 (C), 147.7 (C), 152.5 (C)
ppm.
the GP, 1,2-epoxy-5-hexene (1l, 2.69 g, 27.4 mmol) was al-
lowed to react with CO2 in the presence of KI (86 mg,
[
20a]
1,3-Di-tert-butylimidazolium-2-carboxylate (4b):
was bubbled through a solution of 1,3-di-tert-butylimidazol-
2-ylidene (3b, 518 mg, 3.32 mmol) in Et O (60 mL) for
0 min at 08C. The resulting precipitate was filtered off and
CO
2
0
3
2
.52 mmol), 18-crown-6 (158 mg, 0.598 mmol) and carbene
a (200 mg, 0.515 mmol). After workup the title compound
2
3
l (3.54 g, 24.9 mmol, 91%) was isolated as a colorless
1
washed with Et O (3”30 mL). After removal of all volatiles
liquid. H NMR (300 MHz, CDCl ): d=1.71–1.82 (m, 1H),
2
3
under reduced pressure the title compound 4b (694 mg,
1
7
1
.87–1.95 (m, 1H), 2.15–2.26 (m, 2H), 4.08 (dd, J=8.4 Hz,
.2 Hz, 1H), 4.52 (dd, J=8.2 Hz, 8.2 Hz, 1H), 4.68–4.74 (m,
H), 5.02–5.11 (m, 2H), 5.71–5.82 (m, 1H) ppm. C{ H}
1
3
.10 mmol, 96%) was obtained as a colorless solid. H NMR
1
3
1
(
300 MHz, CD Cl ): d=1.73 (s, 18H), 7.43 (s, 2H) ppm.
2 2
1
1
3
C{ H} NMR (300 MHz, CD Cl ): d=30.2 (CH ), 61.0 (C),
NMR (75 MHz, CDCl ): d=28.5 (CH ), 32.9 (CH ), 69.2
2
2
3
3
2
2
119.4 (CH), 135.9 (C) ppm. Elemental analysis: calcd. for
(
CH ), 76.3 (CH), 116.3 (CH ), 136.0 (CH), 154.9 (C=O)
2
2
C H N O C 64.26, H 8.99, N 12.49; found: C 64.36, H
ppm.
12 20
2
2
[11b]
9.284, N 12.30.
,3-Dimethylimidazolium-2-carboxylate (4c): Potassium
4-(Chloromethyl)-1,3-dioxolan-2-one (2m):
According
[
30]
1
to the GP, epichlorohydrin (1m, 2.34 g, 25.3 mmol) was al-
lowed to react with CO2 in the presence of KI (86 mg,
bis(trimethylsilyl)amide (11.2 g, 56.1 mmol) was added por-
tion wise to a suspension of 1,3-dimethylimidazolium iodide
0
3
2
.52 mmol), 18-crown-6 (136 mg, 0.514 mmol) and carbene
a (195 mg, 0.502 mmol). After workup the title compound
(9.65 g, 43.1 mmol) in toluene (40 mL). The reaction mixture
was stirred for 16 h and subsequently filtered through
m (3.15 g, 23.1 mmol, 91%) was isolated as a colorless
1
Celite. CO was bubbled through the filtrate for 1 h at 238C.
liquid. H NMR (300 MHz, CDCl ): d=3.72 (dd, J=
2
3
The resulting white precipitate was collected by filtration
12.2 Hz, 3.7 Hz, 1H), 3.80 (dd, J=12.2 Hz, 5.2 Hz, 1H), 4.40
and washed with Et O (2”30 mL). After removal of all vol-
2
(
1
dd, J=8.9 Hz, 5.8 Hz, 1H), 4.59 (dd, J=8.8 Hz, 8.3 Hz,
H), 4.95–5.03 (m, 1H) ppm. C{ H} NMR (75 MHz,
13
1
atiles under reduced pressure the title compound 4c (5.56 g,
1
3
(
9.7 mmol, 92%) was obtained as a colorless solid. H NMR
CDCl ): d=43.8 (CH ), 66.9 (CH ), 74.3 (CH), 154.2 (C=O)
3
2
2
13
1
300 MHz, D O): d=3.97 (s, 6H), 7.36 (s, 2H) ppm. C{ H}
2
ppm.
Cyclohexene carbonate (2n):
[11b]
NMR (75 MHz, D O):=39.3 (2”CH ), 125.6 (2”CH), 142.2
2
3
According to THE GP,
(C), 160.8 (C=O) ppm.
cyclohexene oxide (1n, 2.60 g, 26.5 mmol) was allowed to
react with CO2 (50 bar) in the presence of KI (84 mg,
0.50 mmol), 18-crown-6 (138 mg, 0.522 mmol) and carbene
3
a (195 mg, 0.502 mmol) for 6 h. After workup the title
Acknowledgements
compound 2n (2.29 g, 16.1 mmol, 61%) was isolated as a col-
orless solid. H NMR (300 MHz, CDCl ): d=1.36–1.47 (m,
2
2
1
3
We wish to thank the Federal Ministry of Research and Edu-
cation (BMBF) for financial support (Chemische Prozesse
und stoffliche Nutzung von CO : Technologien für Nachhal-
H), 1.57–1.69 (m, 2H), 1.87–1.92 (m, 4H), 4.65–4.72 (m,
13
1
H) ppm. C{ H} NMR (75 MHz, CDCl ): d=19.1 (2”
3
2
CH ), 26.7 (2”CH ), 75.7 (2”CH), 155.3 (C=O) ppm.
2
2
[
28]
tigkeit und Klimaschutz, grant 01 RC 1004 A).
1
,3-Bis(2,6-diisopropylphenyl)imidazole-2-ylidene (3a):
Potassium tert-butoxide (4.60 g, 41.0 mmol) was added por-
tionwise to a solution of 1,3-bis(2,6-diisopropylphenyl)imi-
dazolium chloride (15.5 g, 36.4 mmol) in THF (185 mL).
After the reaction mixture was stirred for 2 h at 238C all
volatiles were removed in vacuo and the resulting residue
was extracted with hot toluene (2”40 mL) and filtered
through Celite. The toluene was removed under reduced
References
[
1] a) Climate Change 2013: The Physical Science Basis.
Contribution of Working Group I to the Fifth Assess-
ment Report of the Intergovernmental Panel on Climate
Change, (Eds.: T. F. Stocker, D. Qin, G.-K. Plattner,
M. M. B. Tignor, S. K. Allen, J. Boschung, A. Nauels, Y.
Xia, V. Bex, P. M. Midgley), Cambridge University
Press, 2013; b) International Energy Outlook 2013, U. S.
Energy Information Administration (EIA), http://
www.eia.gov/forecasts/archive/ieo13/, 2013.
pressure to yield the title compound 3a (11.3 g, 29.1 mmol,
1
8
0%) as a pale yellow solid. H NMR (300 MHz, THF-d ):
8
d=1.17 (J=7.0 Hz, 12H), 1.20 (d, J=6.9 Hz, 12H), 2.81
(
sept, J=6.9 Hz, 4H), 7.21 (s, br, 2H), 7.24–7.27 (m, 4H),
13
7
2
1
.34–7.39 (m, 2H) ppm. C NMR (300 MHz, THF-d ): d=
8
3.6 (4”CH ), 24.7 (4”CH ), 29.1 (4”CH), 122.5 (2”CH),
3
3
23.8 (4”CH), 129.2 (2”CH), 146.6 (4”C) ppm.
[2] a) G. Tangen, E. G. B. Lindeberg, A. Nøttvedt, S.
Eggen, Energy Procedia 2014, 51, 326–333; b) M.
Takht Ravanchi, S. Sahebdelfar, Appl. Petrochem. Res.
2014, 4, 63–77; c) P. Markewitz, W. Kuckshinrichs, W.
Leitner, J. Linssen, P. Zapp, R. Bongartz, A. Schreiber,
1
,3-Bis(2,6-diisopropylphenyl)imidazol-2-carboxylate
[
29]
(
4a): CO was bubbled through a solution of 1,3-bis(2,6-
2
diisopropylphenyl)imidazole-2-ylidene
(3a,
224 mg,
0
.577 mmol) in Et O (60 mL) at 08C for 30 min. The result-
2
6
28
asc.wiley-vch.de
ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2016, 358, 622 – 630

FULL PAPERS
Convergent Activation Concept for CO Fixation in Carbonates
2
T. E. Müller, Energy Environ. Sci. 2012, 5, 7281–7305;
d) G. A. Olah, G. K. S. Prakash, A. Goeppert, J. Am.
Chem. Soc. 2011, 133, 12881–12898.
1528; g) M. North, R. Pasquale, C. Young, Green
Chem. 2010, 12, 1514–1539; h) W. Dai, S. Luo, S. Yin,
C. Au, Front. Chem. Eng. China 2010, 4, 163–171; i) T.
Sakakura, K. Kohno, Chem. Commun. 2009, 1312–
1330.
[
3] a) A. Dibenedetto, A. Angelini, P. Stufano, J. Chem.
Technol. Biotechnol. 2014, 89, 334–353; b) Transforma-
tion and Utilization of Carbon Dioxide (Eds.: B. M.
Bhanage, M. Arai), Springer, 2014; c) M. Hçlscher, C.
Gürtler, W. Keim, T. E. Müller, M. Peters, W. Leitner,
Z. Naturforsch. 2012, 67b, 961–975; d) I. Omae, Coord.
Chem. Rev. 2012, 256, 1384–1405; e) E. A. Quadrelli,
G. Centi, J.-L. Duplan, S. Perathoner, ChemSusChem
[11] a) H. Büttner, J. Steinbauer, T. Werner, ChemSusChem
2015, 8, 2655–2669; b) H. Büttner, K. Lau, A. Spannen-
berg, T. Werner, ChemCatChem 2015, 7, 459–467; c) T.
Werner, H. Büttner, ChemSusChem 2014, 7, 3268–3271;
d) B. Chatelet, L. Joucla, J.-P. Dutasta, A. Martinez, V.
Dufaud, Chem. Eur. J. 2014, 20, 8571–8574; e) Q.-W.
Song, L.-N. He, J.-Q. Wang, H. Yasuda, T. Sakakura,
Green Chem. 2013, 15, 110–115.
2011, 4, 1194–1215; f) G. Centi, G. Iaquaniello, S. Pera-
thoner, ChemSusChem 2011, 4, 1265–1273; g) Carbon
Dioxide as Chemical Feedstock, (Ed.: M. Aresta),
Wiley-VCH, 2010; h) M. Aresta, A. Dibenedetto,
Dalton Trans. 2007, 2975–2992.
[
12] a) A.-L. Girard, N. Simon, M. Zanatta, S. Marmitt, P.
Goncalves, J. Dupont, Green Chem. 2014, 16, 2815–
2825; b) M. H. Anthofer, M. E. Wilhelm, M. Cokoja,
[
4] a) G. Fiorani, W. S. Guo, A. W. Kleij, Green Chem.
I. I. E. Markovits, A. Pothig, J. Mink, W. A. Herrmann,
F. E. Kuhn, Catal. Sci. Technol. 2014, 4, 1749–1758;
2015, 17, 1375–1389; b) Carbon Dioxide Utilisation:
Closing the Carbon Cycle (Eds.: P. Styring, E. A. Quad-
relli, K. Armstrong), Elsevier 2014; c) C. Maeda, Y.
Miyazaki, T. Ema, Catal. Sci. Technol. 2014, 4, 1482–
c) T. Werner, N. Tenhumberg, J. CO Util. 2014, 7, 39–
2
45; d) T. Werner, N. Tenhumberg, H. Büttner, Chem-
CatChem 2014, 6, 3493–3500; e) T.-Y. Shi, J.-Q. Wang,
J. Sun, M.-H. Wang, W.-G. Cheng, S.-J. Zhang, RSC
Adv. 2013, 3, 3726–3732; f) W. Cheng, X. Chen, J. Sun,
J. Wang, S. Zhang, Catal. Today 2013, 200, 117–124.
13] a) M. Adolph, T. A. Zevaco, C. Altesleben, S. Staudt,
E. Dinjus, J. Mol. Catal. A 2015, 400, 104–110; b) M.
Taherimehr, J. P. C. C. Sert¼, A. W. Kleij, C. J. White-
oak, P. P. Pescarmona, ChemSusChem 2015, 8, 1034–
1497; d) J. Langanke, A. Wolf, J. Hofmann, K. Bohm,
M. A. Subhani, T. E. Muller, W. Leitner, C. Gurtler,
Green Chem. 2014, 16, 1865–1870; e) G. Centi, E. A.
Quadrelli, S. Perathoner, Energy Environ. Sci. 2013, 6,
[
1
711–1731; f) M. Peters, B. Kçhler, W. Kuckshinrichs,
W. Leitner, P. Markewitz, T. E. Müller, ChemSusChem
011, 4, 1216–1240; g) M. Mikkelsen, M. Jorgensen,
2
F. C. Krebs, Energy Environ. Sci. 2010, 3, 43–81.
1042; c) J. Martínez, J. A. Castro-Osma, A. Earlam, C.
[
[
5] M. Aresta, A. Dibenedetto, A. Angelini, in: Advances
Alonso-Moreno, A. Otero, A. Lara-Sµnchez, M. North,
A. Rodríguez-DiØguez, Chem. Eur. J. 2015, 21, 9850–
in Inroganic Chemistry Vol. 66, CO Chemistry (Eds.:
2
M. Aresta, R. V. Eldik), Elsevier, 2014, pp 259–288.
6] a) A. Dibenedetto, A. Angelini, in: Advances in Inor-
ganic Chemistry, Vol. 66, CO2 Chemistry (Eds.: M.
Aresta, R. V. Eldik), Elsevier, 2014, pp 25–81; b) D. J.
Darensbourg, in Advances in Inorganic Chemistry, Vol.
9862; d) M. E. Wilhelm, M. H. Anthofer, M. Cokoja,
I. I. E. Markovits, W. A. Herrmann, F. E. Kühn, Chem-
SusChem 2014, 7, 1357–1360; e) C. J. Whiteoak, N.
Kielland, V. Laserna, F. Castro-Gómez, E. Martin,
E. C. Escudero-Adµn, C. Bo, A. W. Kleij, Chem. Eur. J.
66, CO2 Chemistry (Eds.: M. Aresta, R. V. Eldik),
2014, 20, 2264–2275; f) C. J. Whiteoak, N. Kielland, V.
Elsevier, 2014, pp 1–23.
Laserna, E. C. Escudero-Adµn, E. Martin, A. W. Kleij,
J. Am. Chem. Soc. 2013, 135, 1228–1231.
[
[
[
7] a) B. Schaeffner, F. Schaeffner, S. P. Verevkin, A.
Bçrner, Chem. Rev. 2010, 110, 4554–4581; b) J. Bayar-
don, J. Holz, B. Schäffner, V. Andrushko, S. Verevkin,
A. Preetz, A. Bçrner, Angew. Chem. 2007, 119, 6075–
[
14] a) Z.-Z. Yang, D.-E. Jiang, X. Zhu, C. Tian, S. Brown,
C.-L. Do-Thanh, L.-N. He, S. Dai, Green Chem. 2014,
16, 253–258; b) K. R. Roshan, A. C. Kathalikkattil, J.
6078; Angew. Chem. Int. Ed. 2007, 46, 5971–5974.
Tharun, D. W. Kim, Y. S. Won, D. W. Park, Dalton
Trans. 2014, 43, 2023–2031; c) L. Zhou, Y. Liu, Z. He,
Y. Luo, F. Zhou, E. Yu, Z. Hou, W. Eli, J. Chem. Res.
8] a) O. Crowther, D. Keeny, D. M. Moureau, B. Meyer,
M. Salomon, M. Hendrickson, J. Power Sources 2012,
202, 347–351; b) R. F. Nelson, R. N. Adams, J. Electroa-
2013, 37, 102–104; d) B. Xiao, J. Sun, J. Wang, C. Liu,
nal. Chem. 1967, 13, 184–187; c) R. Jasinski, J. Electroa-
nal. Chem. 1967, 15, 89–91.
W. Cheng, Synth. Commun. 2013, 43, 2985–2997; e) J.
Tharun, G. Mathai, A. C. Kathalikkattil, R. Roshan, J.-
Y. Kwak, D.-W. Park, Green Chem. 2013, 15, 1673–
9] a) R. Zevenhoven, S. Eloneva, S. Teir, Catal. Today
2006, 115, 73–79; b) A.-A. G. Shaikh, S. Sivaram,
1677; f) J. Ma, J. Liu, Z. Zhang, B. Han, Green Chem.
Chem. Rev. 1996, 96, 951–976.
2012, 14, 2410–2420; g) S. Liang, H. Liu, T. Jiang, J.
[
10] a) J. W. Comerford, I. D. V. Ingram, M. North, X. Wu,
Green Chem. 2015, 17, 1966–1987; b) C. Martín, G.
Fiorani, A. W. Kleij, ACS Catal. 2015, 5, 1353–1370;
c) B.-H. Xu, J.-Q. Wang, J. Sun, Y. Huang, J.-P. Zhang,
X.-P. Zhang, S.-J. Zhang, Green Chem. 2015, 17, 108–
Song, G. Yang, B. Han, Chem. Commun. 2011, 47,
131–2133; h) J. Song, Z. Zhang, B. Han, S. Hu, W. Li,
2
Y. Xie, Green Chem. 2008, 10, 1337–1341.
[
15] A. Rokicki, W. Kuran, B. P. Marcinick, Monatsh. Chem.
1984, 115, 205–214.
122; d) V. D’Elia, J. D. A. Pelletier, J.-M. Basset, Chem-
CatChem 2015, 7, 1906–1917; e) M. Cokoja, M. E. Wil-
helm, M. H. Anthofer, W. A. Herrmann, F. E. Kuehn,
ChemSusChem 2015, 8, 2436–2454; f) Q. He, J. W.
OꢁBrien, K. A. Kitselman, L. E. Tompkins, G. C. T.
Curtis, F. M. Kerton, Catal. Sci. Technol. 2014, 4, 1513–
[16] B. Schäffner, M. Blug, D. Kruse, M. Polyakov, A. Kçck-
ritz, A. Martin, P. Rajagopalan, U. Bentrup, A. Brück-
ner, S. Jung, D. Agar, B. Rüngeler, A. Pfennig, K.
Müller, W. Arlt, B. Woldt, M. Graß, S. Buchholz,
ChemSusChem 2014, 7, 1133–1139.
Adv. Synth. Catal. 2016, 358, 622 – 630
ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
629

Willi Desens et al.
FULL PAPERS
[
[
17] Y. Ren, C.-H. Guo, J.-F. Jia, H.-S. Wu, J. Phys. Chem.
A 2011, 115, 2258–2267.
18] For an example under ambient conditions by insertion
Launay, D. W. Franco, J. Org. Chem. 2004, 69, 8005–
8011.
[23] For further experimental details see supporting infor-
mation.
of CO in a metal-oxide bond generated by epoxide
2
ring opening see: a) J. MelØndez, M. North, R. Pas-
quale, Eur. J. Inorg. Chem. 2007, 3323–3326; b) A.
Monassier, V. D’Elia, M. Cokoja, H. Dong, J. D. A. Pel-
letier, J.-M. Basset, F. E. Kuehn, ChemCatChem 2013,
[24] M. O. Sonnati, S. Amigoni, E. P. Taffin de Givenchy, T.
Darmanin, O. Choulet, F. Guittard, Green Chem. 2013,
15, 283–306.
[25] a) M. Taherimehr, S. M. Al-Amsyar, C. J. Whiteoak,
5, 1321–1324; c) V. D’Elia, A. A. Ghani, A. Monassier,
A. W. Kleij, P. P. Pescarmona, Green Chem. 2013, 15,
J. Sofack-Kreutzer, J. D. A. Pelletier, M. Drees, S. V. C.
Vummaleti, A. Poater, L. Cavallo, M. Cokoja, J.-M.
Basset, F. E. Kuehn, Chem. Eur. J. 2014, 20, 11870–
3083–3090; b) M. W. Lehenmeier, C. Bruckmeier, S.
Klaus, J. E. Dengler, P. Deglmann, A.-K. Ott, B.
Rieger, Chem. Eur. J. 2011, 17, 8858–8869; c) D. J.
Darensbourg, J. C. Yarbrough, C. Ortiz, C. C. Fang, J.
Am. Chem. Soc. 2003, 125, 7586–7591.
11882; d) B. Dutta, J. Sofack-Kreutzer, A. A. Ghani, V.
D’Elia, J. D. A. Pelletier, M. Cokoja, F. E. Kuehn, J.-M.
Basset, Catal. Sci. Technol. 2014, 4, 1534–1538.
[
[
26] a) J.-Q. Wang, K. Dong, W.-G. Cheng, J. Sun, S.-J.
Zhang, Catal. Sci. Technol. 2012, 2, 1480–1484; b) F.
Castro-Gómez, G. Salassa, A. W. Kleij, C. Bo, Chem.
Eur. J. 2013, 19, 6289–6298.
[
19] a) L. Yang, H. Wang, ChemSusChem 2014, 7, 962–998;
b) H. Zhou, Y.-M. Wang, W.-Z. Zhang, J.-P. Qu, X.-B.
Lu, Green Chem. 2011, 13, 644–650; c) H. Zhou, W.-Z.
Zhang, Y.-M. Wang, J.-P. Qu, X.-B. Lu, Macromolecules
27] a) S. N. Riduan, Y. Zhang, J. Y. Ying, Angew. Chem.
2
009, 42, 5419–5421; d) B. R. Van Ausdall, J. L. Glass,
K. M. Wiggins, A. M. Aarif, J. Louie, J. Org. Chem.
009, 74, 7935–7942; e) H. A. Duong, T. N. Tekavec,
2009, 121, 3372–3375; Angew. Chem. Int. Ed. 2009, 48,
3322–3325; b) F. Huang, G. Lu, L. Zhao, H. Li, Z.-X.
2
Wang, J. Am. Chem. Soc. 2010, 132, 12388–12396;
c) New and Future Developments in Catalysis: Activa-
tion of Carbon Dioxide (Ed.: S. L. Suib), Elsevier,
A. M. Arif, J. Louie, Chem. Commun. 2004, 112–113;
f) N. Kuhn, M. Steimann, G. Weyers, Z. Naturforsch.
1999, 54b, 427–433.
2013; d) S. Das, F. D. Bobbink, G. Laurenczy, P. J.
[
[
20] a) Y. Kayaki, M. Yamamoto, T. Ikariya, Angew. Chem.
Dyson, Angew. Chem. 2014, 126, 13090–13093; Angew.
Chem. Int. Ed. 2014, 53, 12876–12879.
2
009, 121, 4258–4261; Angew. Chem. Int. Ed. 2009, 48,
4194–4197; b) H. Zhou, W.-Z. Zhang, C.-H. Liu, J.-P.
[
28] a) A. J. Arduengo III, R. Krafczyk, R. Schmutzler,
H. A. Craig, J. R. Goerlich, W. J. Marshall, M. Unver-
zagt, Tetrahedron 1999, 55, 14523–14534; b) O. Hollócz-
ki, P. T. Terleczky, D. N. Szieberth, G. Mourgas, D.
Gudat, L. S. Nyulµszi, J. Am. Chem. Soc. 2010, 133,
Qu, X.-B. Lu, J. Org. Chem. 2008, 73, 8039–8044.
21] For example of activation of CO and an epoxide see:
2
a) M. North, R. Pasquale, Angew. Chem. 2009, 121,
2990–2992; Angew. Chem. Int. Ed. 2009, 48, 2946–2948;
for recent examples on the simultaneous activation of
780–789.
CO and a substrate, e. g. propagyl alcohol, see: b) J.
2
Hu, J. Ma, Q. Zhu, Q. Qian, H. Han, Q. Mei, B. Han,
Green Chem. 2016, DOI: 10.1039/C5GC01870F.
[29] A. Tudose, A. Demonceau, L. Delaude, J. Organomet.
Chem. 2006, 691, 5356–5365.
[30] N. J. Bridges, C. C. Hines, M. Smiglak, R. D. Rogers,
[
22] E. R. PØrez, R. H. A. Santos, M. T. P. Gambardella,
L. G. M. de Macedo, U. P. Rodrigues-Filho, J.-C.
Chem. Eur. J. 2007, 13, 5207–5212.
6
30
asc.wiley-vch.de
ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2016, 358, 622 – 630