Polymer‐Anchored Bifunctional Pincer Catalysts for Chemoselective Transfer Hydrogenation and Related Reactions

Abstract

A series of polymer‐supported cooperative PC(sp3)P pincer catalysts was synthesized and characterized. Their catalytic activity in the acceptorless dehydrogenative coupling of alcohols and the transfer hydrogenation of aldehydes with formic acid as a hydrogen source was investigated. This comparative study, examining homogeneous and polymer‐tethered species, proved that carefully designing a link between the support and the catalytic moiety, which takes into consideration the mechanism underlying the target transformation, might lead to superior heterogeneous catalysis.

Waste-Minimized Cyanosilylation of Carbonyls Using Fluoride on Polymeric Ionic Tags in Batch and under Continuous Flow Conditions

“…As a continuation of our interest in the use and development of stable and reusable heterogeneous catalytic systems, we have prepared a solid polymer support with enhanced mechanical and thermal stability due to the right selection of the cross-linker used in the preparation of the heterogeneous polystyrene support. From our previous studies, we found out that when solvent-free conditions (SolFC) are adopted effective polymeric supports are obtained by using largely spaced and generally rigid cross-linkers.…”

Selective Synthesis of Ketones and Chiral Allylic Alcohols from the Addition of Arylboronic Acids to α,β-Unsaturated Aldehydes Mediated by a Transition Metal/Monophosphorus Ligand System

“…For example, metals such as Pd, Ru, Ir, Rh, Fe, Mg, Co, and Ni have been used in the catalytic α-alkylation of ketones. Similarly, Ir, Cu, Ni, Co, and Mn complexes were employed in the dehydrogenative cross-coupling of alcohols to afford aryl alky ketones. In addition, self-hydrogen transferring isomerization, selective epoxide opening/alkylation, allylation of β-chloro ketones, α-arylation of enolates, chemoselective reduction of α,β-unsaturated ketones, and acylative Suzuki coupling have also been used.…”

Biomass Waste-Derived Pd–PiNe Catalyst for the Continuous-Flow Copper-Free Sonogashira Reaction in a CPME–Water Azeotropic Mixture

“…Our research program aims at developing efficient metal heterogeneous catalytic systems, − while we are also contributing to a circular economy approach working on biomass valorization. − Recently, we dedicated our attention to the valorization of urban waste and exploited biochar derived from local biomass as a viable alternative to carbonaceous supports for the preparation of Pd-based heterogeneous catalysts.…”