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. 2022 Dec 27;28(72):e202202771.
doi: 10.1002/chem.202202771. Epub 2022 Dec 20.

Influence of Pore Size in Benzoin Condensation of Furfural Using Heterogenized Benzimidazole Organocatalysts

Ivana Miletto  1 , Marta Meazza  2 , Geo Paul  3 , Maurizio Cossi  3 , Enrica Gianotti  4 , Leonardo Marchese  3 , Ramon Rios  2   5 , Marc Pera-Titus  6 , Robert Raja  2
Affiliations

Influence of Pore Size in Benzoin Condensation of Furfural Using Heterogenized Benzimidazole Organocatalysts

Ivana Miletto et al. Chemistry. .

Abstract

A designed N-heterocyclic carbene (NHC) catalyst was covalently anchored on a range of mesoporous and hierarchical supports, to study the influence of pore size in the benzoin condensation of furfural. The structural and spectroscopic characteristics of the anchored catalysts were investigated, also with the help of molecular dynamics simulations, in order to rationalize the degree of stability and recyclability of the heterogenized organocatalysts. Quantitative yields (99 %) and complete recyclability were maintained after several cycles, vindicating the design rationale.

Keywords: N-heterocyclic carbene based catalysts; benzoin condensation; furfural transformation; heterogeneous catalysis; organic-inorganic hybrid catalyst.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Scheme 1
Scheme 1
Synthesis and NHC anchoring on inorganic silica support.
Figure 1
Figure 1
Furoin conversion obtained for the different hybrid catalysts. The furoin selectivity is 100 % in all the tests, with a carbon balance >99 %.
Figure 2
Figure 2
29Si (A and B) and 13C (C and D) ss NMR spectra of NHC anchored on different supports before (A and C) and after reaction (B and D). Curve a: NHC/Davisil 150 Å, curve b: NHC/Davisil 30 Å, curve c: NHC/SBA‐15, curve d: NHC/HP‐SAPO‐5 and curve e: NHC/HP‐AlPO‐5. Detailed 13C assignments are given in the Supporting Information, as well as 29Si MAS NMR spectra of the pristine inorganic supports (Figure S3).
Figure 3
Figure 3
Models used in MD simulations. (A) bim catalyst (the arrow indicates the carbene atom followed during MD); (B) flat silica surface; (C) 3 nm wide mesopore; (D) 10 nm wide mesopore.
Figure 4
Figure 4
Snapshots extracted from the MD runs on 3 nm wide mesopore in vacuo (A1) and in DMF (A2), 10 nm wide pore in vacuo (B1) and in DMF (B2), and flat surface in vacuo (C1) and in DMF (C2), in all cases with low silanol concentration (i. e. 3 Si−OH nm−2). Bim catalyst represented as CPK, silica support as ball‐and‐stick, DMF as points.
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