Organocatalytic Polymers from Affordable and Readily Available Building Blocks for the Cycloaddition of CO₂ to Epoxides

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(8), P. 4894 - 4924

Published: Jan. 24, 2023

The catalytic cycloaddition of CO2 to epoxides afford cyclic carbonates as useful monomers, intermediates, solvents, and additives is a continuously growing field investigation way carry out the atom-economic conversion value-added products. Metal-free organocatalytic compounds are attractive systems among various catalysts for such transformations because they inexpensive, nontoxic, readily available. Herein, we highlight discuss key advances in development polymer-based materials that match these requirements affordability availability by considering their synthetic routes, supports employed. discussion organized according number (monofunctional versus bifunctional materials) type catalytically active moieties, including both halide-based halide-free systems. Two general approaches identified based on postsynthetic functionalization polymeric or copolymerization monomers bearing moieties. After review material syntheses activities, chemical structural features affecting performance discussed. Based analysis, some strategies future design affordable available organocatalysts with enhanced activity under mild conditions considered.

Language: Английский

---

Synthesis of Bifunctional Catalysts for the Cycloaddition of CO₂ to Epoxides through an Epoxide‐Driven Strategy

ChemCatChem, Journal Year: 2024, Volume and Issue: 16(10)

Published: Feb. 8, 2024

Abstract The design of molecular scaffolds bearing multiple functional groups for the activation and ring‐opening epoxides is a crucial challenge synthesis efficient homogeneous heterogeneous catalysts that are used cycloaddition reaction CO 2 to epoxides. Traditional approaches prepare such multifunctional often imply multistep synthetic procedures expensive building blocks. In this work we show bifunctional Lewis acid metal quaternary ammonium halide group can be prepared in just two steps starting from an opportunely designed epoxide precursor by using inexpensive substrates. Such readily accessible catalyst was applied series under atmospheric conditions generally leading quantitative substrate conversion high carbonate selectivities. Importantly, also epoxide‐driven concept developed preparation catalyst, could recyclable systems target reaction.

Language: Английский

---

Catalytic Strategies for the Cycloaddition of CO2 to Epoxides in Aqueous Media to Enhance the Activity and Recyclability of Molecular Organocatalysts

Molecules, Journal Year: 2024, Volume and Issue: 29(10), P. 2307 - 2307

Published: May 14, 2024

The cycloaddition of CO2 to epoxides afford versatile and useful cyclic carbonate compounds is a highly investigated method for the nonreductive upcycling CO2. One main focuses current research in this area discovery readily available, sustainable, inexpensive catalysts, catalytic methodologies that allow their seamless solvent-free recycling. Water, often regarded as an undesirable pollutant process, progressively emerging helpful reaction component. On one hand, it serves hydrogen bond donor (HBD) enhance performance ionic compounds; on other aqueous media development diverse protocols can boost or ease recycling molecular catalysts. An overview advances use biphasic systems provided work along with recommendations possible future developments.

Language: Английский

---

Exploring the potential of nanosized oxides of zinc and tin as recyclable catalytic components for the synthesis of cyclic organic carbonates under atmospheric CO2 pressure

Process Safety and Environmental Protection, Journal Year: 2023, Volume and Issue: 191, P. 630 - 645

Published: Feb. 7, 2023

Language: Английский

---

CO2 fixation: cycloaddition of CO2 to epoxides by practical metal-free recyclable catalysts

Chemical Communications, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 25, 2024

Recent works on practical and recyclable catalysts for the cycloaddition of CO 2 to epoxides are reviewed with an eye use inexpensive, readily-available, non-toxic materials future emerging designs.

Language: Английский

---

Cycloaddition Reactions of Epoxides and CO₂ Catalyzed by Bifunctional Rare‐Earth Metal Complexes Bearing Amino‐Bridged Tris(phenolato) Ligands

Chinese Journal of Chemistry, Journal Year: 2024, Volume and Issue: 42(14), P. 1571 - 1581

Published: March 15, 2024

Comprehensive Summary Eight zwitterionic rare earth metal complexes stabilized by amino‐bridged tris(phenolato) ligands bearing quaternary ammonium side‐arms were synthesized and characterized. These used as single‐component catalysts for the cycloaddition of CO 2 epoxides, their catalytic activities are obviously higher than those binary analogues. Further studies revealed that halide anions (Cl – , Br I ) influenced activity, lanthanum complex iodide anion showed highest activity this addition reaction. A variety mono‐substituted epoxides converted to cyclic carbonates in good excellent yields (55%—99%) with high selectivity (> 99%) at 30 °C 1 bar whereas internal required both reaction temperatures (60—120 °C) catalyst loading (2 mol%) yields. The was recyclable four times without noticeable loss activity. Based on results kinetic situ IR reactions, a plausible mechanism proposed.

Language: Английский

---

Titanium Sulfonate-Based Metal–Organic Frameworks

Crystal Growth & Design, Journal Year: 2023, Volume and Issue: 23(5), P. 3778 - 3784

Published: March 23, 2023

Titanium-based metal–organic frameworks (Ti-MOFs) are one of the most active fields MOFs due to their intriguing catalytic properties; however, fast reaction between widely used carboxylate-based ligand (hard base) and Ti4+ ion acid) makes syntheses Ti-MOFs extremely challenging. In this work, we propose a new strategy by adopting sulfonic acid (soft as organic ligands synthesize based on hard soft base (HSAB) theory. As an example strategy, seven titanium sulfonate have been synthesized from 1,5-naphthalenedisulfonic (H2nds) isopropoxide structures determined single-crystal X-ray diffraction. These compounds exhibit permanent porosity, solvent stability, light adsorption ability with narrow band gap (2.67 eV). This work demonstrates powerful method for Ti-MOFs, which will greatly promote development Ti-MOFs.

Language: Английский

---

Samarium- and Ytterbium-Grafted Periodic Mesoporous Silica for Carbon Dioxide Capture and Conversion

Inorganic Chemistry, Journal Year: 2023, Volume and Issue: 62(43), P. 17972 - 17984

Published: Oct. 19, 2023

Immobilized coordination compounds of Lewis acidic metals are powerful catalytic components systems for the cycloaddition CO2 to epoxides that do not require sophisticated frameworks harness metal center and modulate its activity. Surface organometallic chemistry (SOMC) is a valuable methodology prepare well-defined site-isolated surface complexes on oxides, with ligand environments easily adjustable targeted reaction. In this work, SOMC applied SmII, YbII, SmIII alkoxide periodic mesoporous (organo)silica distinct pore symmetry/size application in The readily accessible by grafting bis(trimethylsilyl)amide precursors LnII[N(SiMe3)2]2(THF)2 (Ln = Sm, Yb) SmIII[N(SiMe3)2]3, followed exchange alcohols (ethanol neopentanol). use supports led hybrid materials relatively high areas sizes, affording good performance capture under mild conditions (60-80 °C, 1-10 bar). terms performance, recyclability, low amount added nucleophile TBAX (X Br, I), most active prepared work compare well variety previously reported SOMC-derived other heterogeneous acids displaying more elaborate environments.

Language: Английский

---

Preparation of Magnetic Nano-Catalyst Containing Schiff Base Unit and Its Application in the Chemical Fixation of CO2 into Cyclic Carbonates

Magnetochemistry, Journal Year: 2024, Volume and Issue: 10(5), P. 33 - 33

Published: April 26, 2024

The development of a catalyst for the conversion CO2 and epoxides to corresponding cyclic carbonates is still very attractive topic. Magnetic nano-catalysts are widely used in various organic reactions due their magnetic separation recycling properties. Here, nano-catalyst containing Schiff base unit was designed, synthesized as heterogeneous catalyze form without solvents co-catalysts. characterized using Fourier transform infrared (FTIR), X-ray diffraction (XRD), thermogravimetric (TG), VSM, SEM, TEM BET. results show that has high activity solvent-free cycloaddition reaction with epoxide under mild conditions, easily separated from mixture driven by external force. recovered maintains performance after five cycles.

Language: Английский

---

Cobalt complexes with α-amino acid ligands catalyze the incorporation of CO₂into cyclic carbonates

Dalton Transactions, Journal Year: 2023, Volume and Issue: 52(13), P. 4186 - 4199

Published: Jan. 1, 2023

A bioinspired Co( iii ) catalyst efficiently transforms epoxides and CO 2 into cyclic carbonates. The mechanism was found to combine the cooperative effects of metal center amino acid residues in outer coordination sphere.

Language: Английский

---