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. 2021 Dec 6;27(68):16889-16895.
doi: 10.1002/chem.202102300. Epub 2021 Sep 23.

Supported CuII Single-Ion Catalyst for Total Carbon Utilization of C2 and C3 Biomass-Based Platform Molecules in the N-Formylation of Amines

Xingchao Dai  1   2 , Xinzhi Wang  2 , Jabor Rabeah  1 , Carsten Kreyenschulte  1 , Angelika Brückner  1 , Feng Shi  2
Affiliations

Supported CuII Single-Ion Catalyst for Total Carbon Utilization of C2 and C3 Biomass-Based Platform Molecules in the N-Formylation of Amines

Xingchao Dai et al. Chemistry. .

Abstract

The shift from fossil carbon sources to renewable ones is vital for developing sustainable chemical processes to produce valuable chemicals. In this work, value-added formamides were synthesized in good yields by the reaction of amines with C2 and C3 biomass-based platform molecules such as glycolic acid, 1,3-dihydroxyacetone and glyceraldehyde. These feedstocks were selectively converted by catalysts based on Cu-containing zeolite 5A through the in situ formation of carbonyl-containing intermediates. To the best of our knowledge, this is the first example in which all the carbon atoms in biomass-based feedstocks could be amidated to produce formamide. Combined catalyst characterization results revealed preferably single CuII sites on the surface of Cu/5A, some of which form small clusters, but without direct linking via oxygen bridges. By combining the results of electron paramagnetic resonance (EPR) spin-trapping, operando attenuated total reflection (ATR) IR spectroscopy and control experiments, it was found that the formation of formamides might involve a HCOOH-like intermediate and . NHPh radicals, in which the selective formation of . OOH radicals might play a key role.

Keywords: C−C bond cleavage; amines; biomass-based feedstocks; electron paramagnetic resonance spectroscopy; formylation; selective oxidation.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Figure 1
Figure 1
EPR spectra of the catalysts measured at 93 and 298 K.
Figure 2
Figure 2
a) Normalized Cu K‐edge XANES spectra and b) k3‐weighted FT‐EXAFS spectra for Cu/5A.
Figure 3
Figure 3
a) Normalized EPR spectra of DMPO spin adducts. Hfs parameters: A N=14.9, A H=11.0 G for .OH, A N=13.4, A ßH=11.1, A γH=1.2 G for .OOH, A N=14.9, A H=21.6 G for .R, and A N=14.9, A H=16.3 G for .NHPh. b) Relative amount of the DMPO‐X (X=OH, OOH, R, NHPh) spin adducts. A: cat.+dioxane+H2O2, B: +GA, C: +aniline, D: +1.5 h, E: +3 h.
Figure 4
Figure 4
a) Operando ATR‐FTIR spectra. b) Second derivative of the ATR‐IR spectra of the formanilide standard sample in 1,4‐dioxane.
Scheme 1
Scheme 1
Control experiments.
Scheme 2
Scheme 2
Proposed reaction mechanism.
See this image and copyright information in PMC

References

    1. None
    1. Cho E. J., Trinh L. T. P., Song Y., Lee Y. G., Bae H.-J., Bioresour. Technol. 2020, 298, 122386; - PubMed
    1. Huber G. W., Iborra S., Corma A., Chem. Rev. 2006, 106, 4044–4098; - PubMed
    1. Chheda J. N., Huber G. W., Dumesic J. A., Angew. Chem. Int. Ed. 2007, 46, 7164–7183; - PubMed
    2. Angew. Chem. 2007, 119, 7298–7318.
    1. Göransson K., Söderlind U., He J., Zhang W., Renewable Sustainable Energy Rev. 2011, 15, 482–492.

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