Recyclable Porous Polymer‐Supported Copper Catalysts for Glaser and Huisgen 1,3‐Diolar Cycloaddition Reactions

Abstract

A family of polymer-attached phenanthrolines was prepared from solvothermal copolymerization of divinylbenzene with N-(1,10-phenanthroline-5-yl)acrylamide in different ratios. The polymer-supported copper catalysts were obtained through typical impregnation with copper(II) salts. The polymers and supported copper catalysts have been characterized by N2 adsortion, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and thermogravimetric analysis (TG); they exhibit a high surface area, hierarchical porosity, large pore volume, and high thermal and chemical stabilities. The copper catalyst has proved to be highly active for Glaser homocoupling of alkynes and Huisgen 1,3-diolar cycloaddition of alkynes with benzyl azide under mild conditions at low catalyst loading. The heterogeneous copper catalyst is more active than commonly used homogeneous and nonporous polystyrene-supported copper catalysts. In particular, the catalyst is easily recovered and can be recycled at least ten times without any obvious loss in catalytic activity. Metal leaching was prevented due to the strong binding ability of phenanthroline and products were not contaminated with copper, as determined by ICP analysis.

Copper supported on phenanthroline‐functionalized porous polymer as an active catalyst for the oxidative carbonylation of methanol

“…CO (99.99%) and O 2 (99.99%) were purchased from a local manufacturer. N ‐[1,10]phenanthroline‐5‐yl‐acrylamide (Phen‐MA) was prepared according to the reported synthesis procedures . Phen‐MA, 1 H nuclear magnetic resonance (NMR; 400 MHz, CDCl 3 , 25 °C, tetramethylsilane): δ 9.50 (s, 1H), 8.73 (d, 2H, J = 27.8 Hz), 8.26–8.30 (m, 1H), 7.88–7.92 (m, 2H), 7.38–7.43 (m, 1H), 6.43–6.82 (m, 2H), 5.70 (d, 1H, J = 11.4 Hz) ppm.…”

Recent Advances Utilized in the Recycling of Homogeneous Catalysis

“…A polymer‐supported copper based catalyst containing phenanthrolines ligand was synthesized by the solvothermal copolymerization reaction of divinylbenzene with N ‐(1,10‐phenanthroline‐5‐yl)acrylamide (Scheme ) . This catalyst showed high activity for the Glaser homocoupling reaction of alkynes and Huisgen 1,3‐dipolar cycloaddition reaction of alkynes with benzyl azide.…”

Hyper‐Cross‐Linked Polyacetylene‐Type Microporous Networks Decorated with Terminal Ethynyl Groups as Heterogeneous Acid Catalysts for Acetalization and Esterification Reactions

“…Chain‐growth copolymerization of divinylbenzene (DVB) with sodium p ‐styrene sulfonate followed by ion exchange with sulfuric acid provided acid PPCs of the hyper‐cross‐linked polymer network type ( S BET up to 535 m 2 g −1 ) active in acetic acid esterification . The organometallic PPC active in Huisgen 1,3‐dipolar cycloaddition and in Glaser homocoupling of alkynes was prepared using the same type of copolymerization of DVB with N‐( 1,10‐phenanthroline‐5‐yl)acrylamide followed by metalation of the 1,10‐phenanthroline segments of the porous networks with Cu 2+ . The hyper‐cross‐linked PPCs prepared by chain‐growth homopolymerization (referred to as self‐polymerization) have also been described in a review .…”