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. 2024 Jun 27;14(13):1103.
doi: 10.3390/nano14131103.

URJC-1: Stable and Efficient Catalyst for O-Arylation Cross-Coupling

Elena García-Rojas  1 , Pedro Leo  1 , Jesús Tapiador  1 , Carmen Martos  1 , Gisela Orcajo  1
Affiliations

URJC-1: Stable and Efficient Catalyst for O-Arylation Cross-Coupling

Elena García-Rojas et al. Nanomaterials (Basel). .

Abstract

The design of metal-organic frameworks (MOFs) allows the definition of properties for their final application in small-scale heterogeneous catalysis. Incorporating various catalytic centers within a single structure can produce a synergistic effect, which is particularly intriguing for cross-coupling reactions. The URJC-1 material exhibits catalytic duality: the metal centers act as Lewis acid centers, while the nitrogen atoms of the organic ligand must behave as basic centers. The impact of reaction temperature, catalyst concentration, and basic agent concentration was evaluated. Several copper-based catalysts, including homogeneous and heterogeneous MOF catalysts with and without the presence of nitrogen atoms in the organic ligand, were assessed for their catalytic effect under optimal conditions. Among the catalysts tested, URJC-1 exhibited the highest catalytic activity, achieving complete conversion of 4-nitrobenzaldehyde with only 3% mol copper concentration in one hour. Furthermore, URJC-1 maintained its crystalline structure even after five reaction cycles, demonstrating remarkable stability in the reaction medium. The study also examined the impact of various substituents of the substrate alcohol on the reaction using URJC-1. The results showed that the reaction had high activity when activating substituents were present and for most cyclic alcohols rather than linear ones.

Keywords: MOF catalyst; O-arylation; aldehyde; copper MOFs; fine chemistry; phenol.

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Conflict of interest statement

The authors declare no conflicts of interest.

Figures

Scheme 1
Scheme 1
C-O cross-coupling reaction of phenol with 4-nitrobenzaldehyde.
Figure 1
Figure 1
Organic linkers of selected copper-based MOF.
Figure 2
Figure 2
Influence of catalyst concentration on cross-coupling reaction.
Figure 3
Figure 3
(a) XRD patterns of URJC-1 before and after reaction. (b) Hot filtration test.
Figure 4
Figure 4
Influence of base concentration in cross-coupling reaction.
Figure 5
Figure 5
Influence of temperature in cross-coupling reaction.
Figure 6
Figure 6
Catalytic activity of URJC-1 versus copper oxide and copper nitrate tested in O-arylation cross-coupling.
Figure 7
Figure 7
Catalytic activity of different copper-based MOF materials tested in O-arylation cross-coupling.
Figure 8
Figure 8
(a) Recyclability of URJC-1 in O-arylation cross-coupling. (b) XRD patterns of URJC-1 after different cycles in recyclability study.
Figure 9
Figure 9
4-NB conversion obtained with different alcohols in O-arylation cross-coupling after 1 h.
Figure 10
Figure 10
Proposed mechanism for O−arylation cross-coupling catalyzed by URJC-1.
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