10.1002/anie.201805457
Angewandte Chemie International Edition
COMMUNICATION
Figure 3 shows the computed reaction energy diagram for
the conversion of FFCA-acetal to FDCA on a surface model
including an Au cluster on the most stable (111) termination of
CeO2 (Figures S8-S10). FFCA-acetal can be stabilized through
the coordination of one of the oxygen atoms of the cyclic acetal
group to Lewis acid centers on the CeO2 surface (IM1).
Nucleophilic attack of an OH- ion from the solution promotes
partial hydrolysis of the cyclic acetal (IM1 → IM2), which results
in the hemiacetal form of FFCA-acetal with a relatively low
activation barrier of 75 kJ mol-1 (TS1). Oxidative
dehydrogenation of IM2 facilitated by molecularly adsorbed O2
on the Au cluster yields the FDCA-monoester with 1,3-
propanediol (IM3). The activation energy barrier for this step
(TS2) is estimated to be 59 kJ mol-1. These first two steps are
highly exothermic. In contrast, the complete hydrolysis of the
hemiacetal form (IM2 → IM4), which leads to deprotection and
the formation of free FFCA, is energetically much less favorable
with a less stable transition state TS3 (Ea = 115 kJ mol-1).
Desorption from the CeO2 surface and facile hydrolysis of the
FDCA-ester yields FDCA. The outcomes of these density
functional theory (DFT) calculations are supported by the
experimental results; free FFCA was not detected in the reaction
mixture by 1H NMR spectroscopy measurements. The activation
barrier of 75 kJ mol-1 for the first step that produces the
hemiacetal is in good agreement with the experimental apparent
activation energy (78.6 kJ mol-1 in Table S3).
Acknowledgements
The authors thank Dr. Hirokazu Kobayashi (Hokkaido University)
and Dr. Takayuki Aoshima (Mitsubishi Chemical Corporation) for
useful discussion. This work was supported in part by a
KAKENHI, Grant-in-Aid for Young Scientists (A) (No. 15H05556)
from the Japan Society for the Promotion of Science (JSPS).
Keywords: biomass conversion • heterogeneous catalysis •
furan 2,5-dicarboxylic acid • acetalization • supported Au catalyst
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