Article

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Efficient Fluoride-Catalyzed Conversion of CO2 to CO at Room

Temperature
Camille Lescot,† Dennis U. Nielsen,† Ilya S. Makarov,† Anders T. Lindhardt,*,‡ Kim Daasbjerg,†
and Troels Skrydstrup*,†
†
The Center for Insoluble Protein Structures (inSPIN), the Interdisciplinary Nanoscience Center (iNANO) and Department of
Chemistry, Aarhus University, Gustav Wieds Vej 14, 8000 Aarhus, Denmark
‡
The Interdisciplinary Nanoscience Center (iNANO), Biological and Chemical Engineering, Department of Engineering, Aarhus
University, Finlandsgade 22, 8200 Aarhus N, Denmark
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*
S Supporting Information

ABSTRACT: A protocol for the efficient and selective reduction of

carbon dioxide to carbon monoxide has been developed. Remarkably,
this oxygen abstraction step can be performed with only the presence of
catalytic cesium fluoride and a stoichiometric amount of a disilane in
DMSO at room temperature. Rapid reduction of CO2 to CO could be
achieved in only 2 h, which was observed by pressure measurements. To
quantify the amount of CO produced, the reduction was coupled to an
aminocarbonylation reaction using the two-chamber system, COware. The reduction was not limited to a specific disilane, since
(Ph2MeSi)2 as well as (PhMe2Si)2 and (Me3Si)3SiH exhibited similar reactivity. Moreover, at a slightly elevated temperature,
other fluoride salts were able to efficiently catalyze the CO2 to CO reduction. Employing a nonhygroscopic fluoride source,
KHF2, omitted the need for an inert atmosphere. Substituting the disilane with silylborane, (pinacolato)BSiMe2Ph, maintained
the high activity of the system, whereas the structurally related bis(pinacolato)diboron could not be activated with this fluoride
methodology. Furthermore, this chemistry could be adapted to 13C-isotope labeling of six pharmaceutically relevant compounds
starting from Ba13CO3 in a newly developed three-chamber system.

C arbon monoxide (CO) is an industrially important gas for

the production of aldehydes, carboxylic acids, alcohols,
and hydrocarbons.1 This diatomic molecule also serves as a
stoichiometric amounts of CO. As the carbon monoxide
precursors were prepared from CO2, we speculated whether we
could replace these precursors by CO2 and thereby identify
useful C1-building block in numerous transition-metal- suitable conditions for the reduction of CO2 to CO in this two-
catalyzed transformations for the construction of relevant chamber system. Furthermore, this deoxygenation step should
compounds of pharmaceutical and agrochemical interest.2 be sufficiently rapid in order to be useful for a Pd-catalyzed
Nevertheless, its high toxicity remains a significant disadvantage carbonylation reaction.
requiring specialized facilities for its handling. On the other In this paper, we report the successful identification of a
hand, if CO could be generated from a safe and inexpensive simple, efficient, and stoichiometric conversion of CO2 to CO
precursor, this would considerably enhance the utility of this performed at room temperature with catalytic cesium fluoride
gas. Carbon dioxide could represent a valuable CO source in the presence of a disilane. In particular, the process can be
being abundant, nonflammable, and nontoxic in low concen- coupled up to Pd-catalyzed amino- and alkoxycarbonylations
trations.3 Furthermore, there is an increasing interest in with aryl bromides and iodides, thereby allowing for the
identifying useful applications of this greenhouse gas as a synthesis of a range of known pharmaceuticals directly from
source for chemical production.4,5 A significant hurdle, though, this greenhouse gas.
for the transformation of CO2 to CO is the need to cleave a Our inspiration for the development of the catalytic
strong CO bond (bond energy = 804 kJ/mol).6 Although transformation of CO2 to CO came from the work of Sadighi9
considerable advances have been made applying photo- and and Kleeberg,10 demonstrating the possibility of the copper(I)
electrocatalytic processes, such systems are complex and their complex, (IPr)Cu−OtBu (IPr = 1,3-bis(2,6-diisopropyl-
optimization can be difficult.7 phenyl)imidazolidene), to catalyze this oxygen abstraction
We recently demonstrated the usefulness of a two-chamber process in the presence of excess bis(pinacolato)diboron or
reactor for performing a number of Pd-catalyzed carbonylation (pinacolato)BSiMe2Ph (Scheme 1). In the proposed catalytic
reactions.8 In this setup, the chemically controlled release of the cycles, the copper(I) complexes (IPr)Cu−Bpin and (IPr)Cu−
diatomic gas from a carbon monoxide precursor is spatially SiMe2Ph formed from a σ-bond metathesis pathway represent
separated from the CO consuming reaction (carbonylation
reaction) being connected by a bridge, thus simplifying workup Received: March 22, 2014
and allowing carbonylation reactions to be run with just Published: April 4, 2014

© 2014 American Chemical Society 6142 dx.doi.org/10.1021/ja502911e | J. Am. Chem. Soc. 2014, 136, 6142−6147
Journal of the American Chemical Society Article

Scheme 1. Selected Approaches for the Reduction of CO2 to Table 1. Copper Source Screening for the Reduction of CO2
CO to CO with Disilanea

entry copper source R3SiOSiR3 1 % convb,c amide 2 % convb

key intermediates followed by CO2 insertion to generate 1 CuI 0 0
(IPr)Cu−O2CBpin and (IPr)Cu−O2CSiMe2Ph, respectively. 2 CuCN 0 0
Initial efforts were set out to explore this reduction chemistry 3 Cu(acac)2 67 100
applying the two-chamber reactor for trapping the synthesized 4 Cu(OCOCF3)2 94 100
CO in a Pd-catalyzed aminocarbonylation. Furthermore, 5 Cu(OTf)2 0 0
another goal was to simplify the catalytic protocol for this a
Conditions: Chamber A was loaded with (MePh2Si)2 (0.75 mmol),
reduction step. After considerable experimentation, we copper salt (0.075 mmol), DPPBz (0.083 mmol), NMP (3.0 mL), and
discovered that the combination of a catalyst derived from last CO2 (21 mL, 0.85 mmol) by injection through the septum.
Cu(OAc)2 and the bidentate ligand, DPPBz,11 with stoichio- Chamber B was loaded with p-iodoanisole (0.50 mmol), n-hexylamine
metric amounts of dimethyltetraphenyldisilane in N-methyl- (1.0 mmol), Pd(dba)2 (0.025 mmol), PPh3 (0.050 mmol), Et3N (1.0
pyrrolidinone (NMP) at 150 °C, efficiently reduced CO2 to mmol), and dioxane (3.0 mL). The reaction mixture in Chamber B
carbon monoxide as measured by the formation of the was stirred at 80 °C for 18 h and in Chamber A at 150 °C for 18 h.
b
corresponding disiloxane 1. Coupling of this process in a Conversions were measured by analysis of the 1H NMR spectra of
two-chamber system with the Pd-catalyzed carbonylative the crude product mixtures in the individual chambers (see Supporting
Information). cSince 1.5 equiv of the disilane was used, only 67%
coupling of p-iodoanisole and n-hexylamine at 80 °C for 18 h conversion is needed for the full conversion to the amide 2.
provided the amide 2 in a 96% yield, as depicted in Scheme 2.12

Scheme 2. Initial Experiment on the CO2 Reduction and conversion was observed at all in both chambers (entries 2 and
Application in a Pd-Catalyzed Aminocarbonylation 3).
An increase in reactivity was nevertheless noted when
potassium acetate was replaced with 10 mol % potassium
fluoride. Hence, at 80 °C and even at 40 °C, the conversions to
1 and 2 were high (entries 4 and 5) implying that the CO2
reduction step was indeed effective at these temperatures. On
the other hand, negligible reactivity was again observed at 20
°C (entry 6). A screening of various solvents (entries 7−13)
proved rewarding and revealed that the use of DMSO
permitted the effective transformation of CO2 to CO at 20
°C (entry 13). Finally, after examining other fluoride sources
including TBAF, LiF, NaF, and CsF (entries 14−17), the latter
was found to exhibit the highest reactivity leading to complete
conversion in both chambers. Hence, cesium fluoride proved to
be an excellent catalyst for the room temperature and
In our efforts to optimize these new reduction conditions for stoichiometric reduction of CO2 to carbon monoxide with
the transformation of CO2 to CO with disilane, we decided to the disilane, (MePh2Si)2.
investigate the effect of the copper source (Table 1). The two Furthermore, the catalyst loading could be reduced down to
copper(I) salts that were examined were ineffective as shown in 5 mol% without lowering the conversions in both chambers
entries 1 and 2. Cu(acac)2 furnished disiloxane 1 from the (entry 18). Less reactive substrates for the aminocarbonylation
disilane with a conversion of 67% (entry 3), while Cu- reaction generally need a slight excess of CO.8 To meet this
(OCOCF3)2 in entry 4 proved to be almost as efficient as requirement a slight excess of CO was indirectly applied by
Cu(OAc)2 (94% conversion). On the other hand, Cu(OTf)2 increasing the amount of disilane. With these conditions, a 99%
did not lead to any conversion at all (entry 5). Due to the large isolated yield of amide 2 could be secured (entry 19).14
influence of the different counterions of the Cu(II) salts, we After optimizing the parameters for the catalytic activation of
speculated whether they would exhibit catalytic activity in the diphenylmethyldisilane for the reduction of CO2, it was decided
absence of copper. Hence, a similar set of experiments were to screen other disilanes (Table 3). Having only methyl or
performed as illustrated in Scheme 2, though with the phenyl groups present on the disilane proved detrimental for
exception that the Cu(OAc)2/DPPBz combination was the reaction (entries 1 and 2). However, it is worth noting that
replaced with KOAc.13 To our delight, complete conversion hexaphenyldisilane was insoluble in DMSO, which could
to the disiloxane 1 and amide 2 was observed (Table 2, entry 1) explain its lack of reactivity. Substituting two of the phenyl
with only 10 mol % of added potassium acetate suggesting that substituents with methyl groups provided the high activity of
indeed CO2 reduction to CO could be catalyzed by this simple the system (entry 3). The presence of o-methoxy substituents
salt. Lowering the reaction temperature to 80 °C led to a on the aromatic rings completely shuts down the reaction,
substantial drop in the conversion, whereas, at 20 °C, no which could possibly be explained by coordination between the
6143 dx.doi.org/10.1021/ja502911e | J. Am. Chem. Soc. 2014, 136, 6142−6147
Journal of the American Chemical Society Article

Table 2. Optimization of the Reduction of CO2 to CO with Table 3. Screening of Disilanes for the Reduction of CO2 at
Disilane Catalyzed by Simple Saltsa Room Temperaturea

R3SiOSiR3 1 amide 2
entry cat. solvent T [°C] % convb % convb
1 KOAc NMP 150 100 100
2 KOAc NMP 80 50 50
3 KOAc NMP 20 0 0
4 KF NMP 80 100 99
5 KF NMP 40 95 95
6 KF NMP 20 4 4
7 KF THF 20 0 0
8 KF dioxane 20 0 0
9 KF MeCN 20 0 0
10 KF toluene 20 0 0
11 KF DCE 20 0 0
12 KF DMF 20 75 75
13 KF DMSO 20 90 90
14 TBAF DMSO 20 0 0
15 LiF DMSO 20 0 0
16 NaF DMSO 20 0 0
17 CsF DMSO 20 100 100 a
18 CsFc DMSO 20 100 100
Conditions: Chamber A was loaded with disilane (0.50 mmol), CsF
(0.050 mmol), DMSO (3.0 mL), and last CO2 (21 mL, 0.85 mmol) by
19d CsF DMSO 20 100 100[99]e
a
injection through the septum. Chamber B was loaded with p-
Conditions: Chamber A was loaded with (MePh2Si)2 (0.50 mmol), iodoanisole (0.50 mmol), n-hexylamine (1.0 mmol), Pd(dba)2 (0.025
activator (0.050 mmol), solvent (3.0 mL), and last CO2 (21 mL, 0.85 mmol), PPh3 (0.050 mmol), Et3N (1.0 mmol), and dioxane (3.0 mL).
mmol) by injection through the septum. Chamber B was loaded with The reaction mixture in Chamber B was stirred at 80 °C for 18 h and
p-iodoanisole (0.50 mmol), n-hexylamine (1.0 mmol), Pd(dba)2 in Chamber A at 20 °C for 18 h. bBased on 1H NMR conversion.
(0.025 mmol), PPh3 (0.050 mmol), Et3N (1.0 mmol), and dioxane c
Disilane (0.17 mmol).
(3.0 mL). The reaction mixture in Chamber B was stirred at 80 °C for
18 h. bConversions were measured by analysis of the 1H NMR spectra
of the crude product mixtures in the individual chambers (see
Supporting Information). cLoading of CsF was reduced to 0.025
mmol. dLoading of disilane was increased to 0.75 mmol. eIsolated yield
(%) of amide 2.

silicon and oxygen. Interestingly, as opposed to hexamethyl-

disilane (entry 1), tris(trimethylsilyl)silane proved to be very
efficient even with a loading approximately 3 times less than
that for the other disilanes, which is undoubtedly due to the
presence of multiple Si−Si bonds in this structure (entry 5).
Surprisingly, it does not appear that the Si−H bond is involved
in this reduction step, as neither the silyl formate nor the
methoxysilane could be observed in the crude NMR.11,15
To further quantify the reactivity of the system, we followed Figure 1. Profile of the pressure measurement experiment.
the reduction of CO2 to CO by measuring the pressure of the Conditions: (PhMe2Si)2 (0.50 mmol), CsF (0.050 mmol), DMSO
system over time without the CO-consuming reaction (Figure (3.0 mL), CO2 (0.85 mmol) injected through a septum. The reaction
1). After the injection, carbon dioxide rapidly goes into mixture was stirred at 20 °C.
solution, causing a quick pressure decay. As the reaction
proceeds, the less soluble carbon monoxide is produced and
after 30 min the pressure commences to increase, achieving a (IPr)Cu−OtBu. Therefore, the substitution of CsF with a
constant value after approximately 2 h when the reduction is nonhygroscopic fluoride source should allow these trans-
complete. formations to be carried out without the need for an inert
Cesium fluoride is hygroscopic, and hence an inert atmosphere. Gratifyingly, the reaction setup in air with KHF2 as
atmosphere should be applied when working with this salt. a catalyst (10 mol %) under the otherwise optimal conditions
This is also the case with the previously reported systems for (Scheme 3) provided 63% conversion of p-iodoanisole into the
the CO2 to CO reduction by Sadighi9 and Kleeberg,10 when amide 2 after 18 h. The conversion is incomplete due to the
utilizing the air- and moisture-sensitive copper(I) complex, lower reactivity of potassium hydrogen fluoride; however, it can
6144 dx.doi.org/10.1021/ja502911e | J. Am. Chem. Soc. 2014, 136, 6142−6147
Journal of the American Chemical Society Article

Scheme 3. Reduction of CO2 in the Presence of Aira Scheme 5. Proposed Mechanism for CO2 Reduction with
CsF and Disilane

a
Conditions: Chamber A was loaded with (Ph2MeSi)2 (0.50 mmol),
KHF2 (0.050 mmol), DMSO (3.0 mL), and last CO2 (21 mL, 0.85
mmol) by injection through the septum. Chamber B was loaded with
p-iodoanisole (0.50 mmol), n-hexylamine (1.0 mmol), Pd(dba)2
(0.025 mmol), PPh3 (0.050 mmol), Et3N (1.0 mmol), and dioxane
(3.0 mL). The reaction mixture in Chamber B was stirred at 80 °C for
18 h and in Chamber A at specified temperature for 18 h.

be increased to 100% by performing the CO2 reduction in

chamber A at 30 °C.
It was also interesting to compare the reactivity of the
disilanes with the two related reductants used in the copper(I)- Whether CO2 reacts with a free silyl anion under our reaction
catalyzed variants of the transformations of carbon dioxide to conditions or a hypervalent species A by fluoride coordination
carbon monoxide.9,10 Similar experiments were therefore to one of the two silyl atoms is at the moment not clear.
carried out as in the case for the disilanes applying a two- Nevertheless, subsequent CO2 insertion into A would generate
chamber system whereby chamber A was instead loaded with the O-silylated silacarboxylic acid B. Liberation of the
either bis(pinacolato)diboron or (pinacolato)BSiMe 2 Ph silacarboxylate generates the corresponding cesium salt C,
(Scheme 4). The reduction of CO2 with pinBSiMe2Ph led to which possibly undergoes a Brook rearrangement to liberate
CO and a silyloxide, in analogy to similar observations on the
Scheme 4. CsF-Catalyzed Reduction of CO2 with B2pin2 and fluoride and hydroxide promoted generation of CO from
pinBSiMe2Pha silacarboxylic acids.8b,17 Subsequent generation of the disilox-
ane from attack of the siloxide with the silyl fluoride regenerates
the cesium fluoride.
With this surprisingly simple catalytic protocol in hand for
the efficient conversion of CO2 into CO without the need of a
transition metal catalyst, we proceeded to investigate its
usefulness for the preparation of a number of pharmaceutically
relevant molecules as depicted in Scheme 6. As with the
a optimization studies, all reactions were run in a two-chamber
Conditions: Chamber A was loaded with pinBSiMe2Ph (0.50 mmol)
system and, for best coupling yields, 1.5 equiv of CO were
or B2pin2 (0.50 mmol), CsF (0.050 mmol), DMSO (3.0 mL), and last
CO2 (21 mL, 0.85 mmol) by injection through the septum. Chamber applied. Gratifyingly, all the amino- and alkoxycarbonylations
B was loaded with p-iodoanisole (0.50 mmol), n-hexylamine (1.0 proved to be highly efficient, indicating again that the CO2
mmol), Pd(dba)2 (0.025 mmol), PPh3 (0.050 mmol), Et3N (1.0 reduction step to CO performed exceptionally well.
mmol), and dioxane (3.0 mL). The reaction mixture in Chamber B Further studies were also undertaken to validate this protocol
was stirred at 80 °C for 18 h and in Chamber A at 20 °C for 18 h. for selective 13C-carbon isotope labeling of the same bioactive
compounds. As a convenient source of 13CO2, we chose
an 89% conversion of p-iodoanisole into the amide 2 and full commercially available 13C-labeled Ba13CO3. This required a
consumption of the silylborane after 18 h at room temperature. closed three-chamber system, whereby CO2 is liberated in one
The incomplete conversion of CO2 into CO is most likely due of the three chambers by the treatment of the barium carbonate
to some unidentified side reactions.10 This experiment with camphorsulfonic acid.18 As shown in the results in Scheme
demonstrates that cesium fluoride is a more active catalyst for 6, the addition of a third reaction in an additional chamber did
deoxygenating CO2 with pinBSiMe2Ph than (IPr)Cu−OtBu not have a detrimental effect on the efficiency of the carbon
used by Kleeberg. Indeed, with 20 mol % of this copper species, dioxide reduction step or the Pd-catalyzed transformation, and
1 equiv of carbon dioxide is completely consumed after 79 h hence, all 13C-isotopically labeled pharmaceutical compounds
giving approximately 70% of CO,10 whereas with CsF (10 mol were prepared in good yields.
%) the same consumption is achieved after only 18 h and the In conclusion, a simple and mild protocol for the conversion
yield of carbon monoxide is higher. Unlike the disilanes and of CO2 to CO has been developed, which does not require a
silylborane, B2pin2 was unreactive under our optimized transition metal catalyst. Notably, this transformation is
conditions. These results suggest that the presence of a silicon promoted by catalytic cesium fluoride in the presence of a
atom is necessary for the fluoride to be an active catalyst for the disilane and at room temperature. This is the first example
CO2 to CO reduction. utilizing a disilane for the reduction of CO2 to CO.19
A possible catalytic cycle for the fluoride promoted reduction Furthermore, the process can be coupled to Pd-catalyzed
of CO2 to carbon monoxide with disilane is depicted in Scheme amino- and alkoxycarbonylations in a two-chamber system
5. Hiyama and co-workers have earlier demonstrated the ability providing excellent coupling yields of a range of pharmaceuti-
to generate metal-free silyl anions from the treatment of cally relevant compounds. Finally, with a three-chamber system,
disilanes with tetrabutylammonium fluoride in HMPA.16 13
C-isotope labeling of the same compounds with Ba13CO3
6145 dx.doi.org/10.1021/ja502911e | J. Am. Chem. Soc. 2014, 136, 6142−6147
Journal of the American Chemical Society Article

Scheme 6. Combining the CO2 to CO Reduction Protocol with the Pd-Catalyzed Amino- and Alkoxycarbonylation

could be achieved. Further work is currently in progress to Notes

provide a more detailed understanding of this intriguing oxygen The authors declare no competing financial interest.

■
abstraction step from CO2. This work will be reported in due
course. ACKNOWLEDGMENTS

■
*
ASSOCIATED CONTENT
S Supporting Information
We are deeply appreciative of generous financial support from
the Danish National Research Foundation, (Grant No.
DNRF59), the Villum Foundation, the Danish Council for
Copies of 1H NMR, 13C and 19F NMR spectra for all the Independent Research: Technology and Production Sciences,
coupling products, and details on experimental procedures. the Carlsberg Foundation, and Aarhus University for generous
This material is available free of charge via the Internet at financial support of this work.

■
http://pubs.acs.org.

■ AUTHOR INFORMATION
Corresponding Authors
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