Dedicated to Professor Cesare Gennari on the occasion of his 70th birthdayPhosphine ligands are of unique importance in catalysis, especially as ligands for transition metals. Homogeneous catalysis is by far the broadest application of phosphines in industrial processes. The heterogenization of phosphines is challenging even though it would appeal to the chemical industry as a valid strategy for recovery and reutilization. In this Review, we discuss approaches for the immobilization of phosphines through the synthesis of phosphine-functionalized porous polymers, such as metal-organic frameworks (MOFs), covalent organic frameworks (COFs), and porous organic polymers (POPs). We critically discuss the synthetic strategies for preparing monomers, linkers, and porous materials. We highlight the most successful applications of phosphine-based porous catalysts and correlate them with their properties, structure, and performance.

Cross-coupling reactions are a fundamental tool in the large scale synthesis of pharma-, agro- and fine chemicals. Homogeneous palladium complexes remain the state-of-the-art catalysts even though the use of heterogeneous...

A chiral aldehyde, obtained in both enantiomeric forms from renewable 2,5-Bis(hydroxymethyl)tetrahydrofuran by a chemoenzymatic procedure, was submitted to a modified diastereoselective Passerini reaction employing zinc dicarboxylates.

The synthesis of drug substances (DS) requires the continuous effort of the pharma industry to ensure high sustainability standards. The Suzuki-Miyaura cross coupling is a fundamental C–C bond-forming reaction to produce complex DS intermediates. The present contribution points out the way in which the synthesis of DS intermediates by C–C cross coupling can be economically competitive, while minimizing waste by selecting the appropriate heterogeneous catalyst. By comparing homogeneous, immobilized heterogeneous catalysts on silica and metal–organic framework (MOF) catalysts, while considering the perspectives of academia and industry, the critical parameters for a successful industrial application of heterogeneous catalytic Suzuki-Miyaura cross coupling reactions were identified. Heterogeneous catalysts, such as MOFs, may provide a complementary platform for reducing waste and the costs of production related to such transformations.

We report the effect of inorganic and organic acids and bases, in combination with different solvents, on the crystallinity and porosity of defective UiO-66 MOFs.