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Carbon dioxide utilization via carbonate-promoted C–H carboxylation
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Journal Article
Carbon dioxide utilization via carbonate-promoted C–H carboxylation
2016
Overview
Molten salts at intermediate temperatures enable efficient carbonate-promoted carboxylation of very weakly acidic C–H bonds, revealing a new way to transform inedible biomass and carbon dioxide into valuable feedstock chemicals.
CO
2
as a chemical feedstock
The idea that the greenhouse gas carbon dioxide might be used as a source of feedstock chemicals is attractive but usually impractical — although it reacts readily with carbon-centred nucleophiles, generating the nucleophiles requires a high energy input. But now, inspired by the RuBisCO enzyme which catalyses carbon fixation in plants, Aanindeeta Banerjee
et al
. demonstrate that molten salts containing alkali metals at intermediate temperatures enable efficient carbonate-promoted carboxylation of very weakly acidic C–H bonds. The potential of this chemistry was illustrated by converting 2-furoic acid (readily made from inedible biomass) into the useful bio-based feedstock furan-2,5-dicarboxylic acid.
Using carbon dioxide (CO
2
) as a feedstock for commodity synthesis is an attractive means of reducing greenhouse gas emissions and a possible stepping-stone towards renewable synthetic fuels
1
,
2
. A major impediment to synthesizing compounds from CO
2
is the difficulty of forming carbon–carbon (C–C) bonds efficiently: although CO
2
reacts readily with carbon-centred nucleophiles, generating these intermediates requires high-energy reagents (such as highly reducing metals or strong organic bases), carbon–heteroatom bonds or relatively acidic carbon–hydrogen (C–H) bonds
3
,
4
,
5
. These requirements negate the environmental benefit of using CO
2
as a substrate and limit the chemistry to low-volume targets. Here we show that intermediate-temperature (200 to 350 degrees Celsius) molten salts containing caesium or potassium cations enable carbonate ions (CO
3
2–
) to deprotonate very weakly acidic C–H bonds (p
K
a
> 40), generating carbon-centred nucleophiles that react with CO
2
to form carboxylates. To illustrate a potential application, we use C–H carboxylation followed by protonation to convert 2-furoic acid into furan-2,5-dicarboxylic acid (FDCA)—a highly desirable bio-based feedstock
6
with numerous applications, including the synthesis of polyethylene furandicarboxylate (PEF), which is a potential large-scale substitute for petroleum-derived polyethylene terephthalate (PET)
7
,
8
. Since 2-furoic acid can readily be made from lignocellulose
9
, CO
3
2–
-promoted C–H carboxylation thus reveals a way to transform inedible biomass and CO
2
into a valuable feedstock chemical. Our results provide a new strategy for using CO
2
in the synthesis of multi-carbon compounds.
Publisher
Nature Publishing Group UK,Nature Publishing Group
