Humins-Like Solid Support for Palladium Immobilization: Highly Efficient and Recyclable Catalyst for Cross-Coupling Reactions

Author(s)

Galaverna, Renan S. ; Fernandes, Lucas P. ; da Silva, Vitor H. Menezes ; de Siervo, Abner ; Pastre, Julio C.

• Document type: Journal article
• Source: EUROPEAN JOURNAL OF ORGANIC CHEMISTRY; v. 2022, n. 24, p. 11-pg., 2022-06-27.

Abstract

In the present work, a new humins-like resin was prepared using 2,5-bis(hydroxymethyl)furan (DHMF) and maleic anhydride in 2 min at 110 degrees C. Such a new material was used as a solid support for palladium immobilization. For metal anchoring, encapsulation was the method of choice and palladium was encapsulated by in-situ polymerization. This resulting Pd@DHMF-based catalyst was characterized by solid-state C-13 NMR, FT-IR, SEM, TGA, DSC, XRD, and XPS. To demonstrate proof of concept, Heck and Suzuki cross-coupling reactions were selected to evaluate the activity and reusability of the catalyst. Green solvents such as gamma-valerolactone (GVL), Cyrene (TM) and ethylene carbonate proved to be excellent reaction media for Heck coupling, whereas EtOH/H2O was preferred for Suzuki coupling. Yields of up to 99 % were obtained in both cases. The recyclability of the Pd@DHMF-based catalyst was also demonstrated, 7 cycles have been achieved without loss of catalytic activity in both Heck and Suzuki reactions. (AU)

• FAPESP's process: 14/26378-2 - Development of methodologies and synthetic processes employing a new technological platform: micro and meso reactor assisted synthesis of natural products and derivatives with potential pharmacological activity
• Grantee: Júlio Cezar Pastre
• Support Opportunities: Research Grants - Young Investigators Grants
• FAPESP's process: 14/25770-6 - New frontiers in cross-coupling reactions promoted by palladium: combining enantioselective catalysis, C-H activations, new materials and in flux reactions aiming at high efficiency and sustainability in synthetic processes
• Grantee: Carlos Roque Duarte Correia
• Support Opportunities: Research Projects - Thematic Grants
• FAPESP's process: 20/11578-7 - Enabling technologies allied to green chemistry: synthesis of high value-added compounds from biomass derivatives
• Grantee: Júlio Cezar Pastre
• Support Opportunities: Program for Research on Bioenergy (BIOEN) - Regular Program Grants