Recent Advances in Electrochemical Carboxylation with CO₂

Accounts of Chemical Research, Journal Year: 2024, Volume and Issue: 57(18), P. 2728 - 2745

Published: Sept. 3, 2024

ConspectusCarbon dioxide (CO

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Catalytic Regio- and Enantioselective Boracarboxylation of Arylalkenes with CO₂ and Diboron

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(5), P. 2888 - 2894

Published: Jan. 26, 2024

Catalytic asymmetric carboxylation of readily available alkenes with CO2, an abundant and sustainable one-carbon building block, that gives access to value-added α-stereogenic carboxylic acids in atom- step-economic manner is highly attractive. However, it has remained a formidable challenge for the synthetic community. Here, first example Cu-catalyzed regio- enantioselective boracarboxylation reaction on various arylalkenes diboron under atmospheric pressure CO2 described, which afforded variety chiral β-boron-functionalized α-aryl up 87% yield 97% ee mild conditions. Importantly, α-substituted could also be subject this protocol excellent enantiopurities, thereby rendering efficient approach generation enantioenriched α-chiral all-carbon quaternary center. Moreover, high functional group tolerance, scalable synthesis, facile bioactive compounds, like (−)-scopolamine, (−)-anisodamine, (−)-tropicamide, further demonstrated utility strategy.

Language: Английский

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CO₂-Based Stable Porous Metal–Organic Frameworks for CO₂ Utilization

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(21), P. 14835 - 14843

Published: May 10, 2024

The transformation of carbon dioxide (CO2) into functional materials has garnered considerable worldwide interest. Metal–organic frameworks (MOFs), as a distinctive class materials, have made great contributions to CO2 capture and conversion. However, facile conversion stable porous MOFs for utilization remains unexplored. Herein, we present methodology using synthesize zirconium-based MOFs. Two CO2–Zr-DEP CO2–Zr-DEDP with face-centered cubic topology were obtained via sequential desilylation–carboxylation–coordination reaction. exhibit excellent crystallinity, verified through powder X-ray diffraction high-resolution transmission electron microscopy analyses. They also notable porosity high surface area (SBET up 3688 m2 g–1) good adsorption capacity (up 12.5 wt %). resulting abundant alkyne moieties, confirmed 13C cross-polarization/magic angle spinning nuclear magnetic resonance Fourier transform infrared spectra. Leveraging the catalytic prowess Ag(I) in diverse CO2-involved reactions, incorporated MOFs, capitalizing on their interactions carbon–carbon π-bonds alkynes, thereby forming heterogeneous catalyst. This catalyst demonstrates outstanding efficiency catalyzing propargylic alcohols cyclic carbonates, achieving >99% yield at room temperature atmospheric pressure conditions. Thus, this work provides dual strategy, encompassing synthesis CO2-based (20–24 % from CO2) subsequent application processes. approach significantly enhances overall utilization.

Language: Английский

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Visible-Light Photoredox-Catalyzed Intermolecular α-Aminomethyl/Carboxylative Dearomatization of Indoles with CO₂ and α-Aminoalkyl Radical Precursors

Organic Letters, Journal Year: 2024, Volume and Issue: 26(2), P. 467 - 472

Published: Jan. 5, 2024

Disclosed here is a visible-light photoredox-catalyzed intermolecular sequential α-aminomethyl/carboxylative dearomatization of indoles with CO2 and α-aminoalkyl radical precursors, affording series functionalized indoline-3-carboxylic acids lactams in good yields high regioselectivity. This multicomponent reaction provides green facile method for the synthesis diverse indolines by using as carboxylic carbonyl source.

Language: Английский

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CO2 capture and in-situ conversion to organic molecules

Journal of CO2 Utilization, Journal Year: 2024, Volume and Issue: 82, P. 102753 - 102753

Published: March 30, 2024

To address the CO2 accumulation in atmosphere, various initiatives have been proposed, among which capture and utilization (CCU) is regarded as an appealing strategy to reconcile carbon emission resource utilization. Especially, integrated (ICCU), i.e. performing in-situ conversion can circumvent energy-intensive desorption step thus facilitate establishing step- energy-efficient process, rendering at mild conditions particularly low pressure due substantial activation upon uptake. However, not simple add-up of these two processes. Its successful implementation relies on harmonization reagents, substrates corresponding catalysts. By far, tremendous efforts made this field a plethora reagents including inorganic bases, organic ionic liquids carbonaceous materials utilized protocols such hydrogenation, cycloaddition, carboxylative cyclization etc. explored for captured CO2. As result, valuable products containing methanol, methane, carbonates, carbamates, oxazolidinones, ureas, quinazolinone obtained from more importantly, chemistry theory also enriched via investigating structure reactivity reactions. In review, we summarize progress based reaction types absorbents. It's hoped that review shed light design inspire further development field.

Language: Английский

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Nitrogen-Rich Barium–Organic Framework for Capture and Cocatalysts Free Chemical Fixation of CO₂ via Cyclic Carbonates and Oxazolidinones

ACS Applied Materials & Interfaces, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 17, 2025

The carbon dioxide (CO2) capture and utilization strategy has emerged as an innovative multifaceted approach to counteract emissions. In this study, a highly porous muffin polyhedral barium (Ba) ̵ organic framework (BaTATB; H3TATB = 4,4',4″-s-triazine-2,4,6-triyl-tribenzoic acid) was synthesized solvothermally. three-dimensional honeycomb pore architectures were densely populated with Lewis acidic Ba(II) metal sites basic nitrogen-rich triazines. BaTATB demonstrated selective CO2 adsorption high heat of adsorption. Its abundance (Ba clusters) (triazine) makes ideal catalyst for the cycloaddition epoxides in two- three-component reactions. Furthermore, is exceptional recyclable aromatic amines, enabling high-yield synthesis cyclic carbonates oxazolidinone at 1 bar under moderate, solvent-free, cocatalyst-free conditions. Additionally, recycled nine seven consecutive cycles carbonate no substantial decrease catalytic activity. Using density functional theory, we rational design metal-organic frameworks that exhibit excellent conversion.

Language: Английский

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Research Status, Challenges, and Future Prospects of Carbon Dioxide Reduction Technology

Energy & Fuels, Journal Year: 2024, Volume and Issue: 38(6), P. 4836 - 4880

Published: March 12, 2024

The survival and sustainable development of humanity are gravely threatened by climate change, which has recently been elevated to the status one greatest threats humanity's security on a worldwide scale. In response global how obtain renewable clean fuels is an important challenge for human society. order reach carbon peak attain neutrality, using CO2 as resource become crucial aim civilization. Converting into chemical products with higher added value, that is, utilization technology can not only achieve emission reduction but also have certain economic benefits. technologies primarily include photocatalytic reduction, electrocatalytic thermal catalytic relay catalysis. This paper mainly summarizes mechanism conversion research related catalysts, discusses prospects system (catalyst modification, product selectivity improvement, etc.). ideas guidance provided efficient stable catalysts application in areas environment energy.

Language: Английский

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Cobalt porphyrin-based hypercrosslinked ionic polymers as biomimetic nanoreactors for CO₂ conversion to cyclic carbonates

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(12), P. 1599 - 1602

Published: Jan. 1, 2024

Cobalt porphyrin-based hypercrosslinked ionic polymers act as bifunctional catalysts for the conversion of CO 2 into cyclic carbonates due to high surface areas, densely located groups and highly dispersed cobalt sites.

Language: Английский

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Value‐Added Cascade Synthesis Mediated by Paired‐Electrolysis Using an Ultrathin Microenvironment‐Inbuilt Metalized Covalent Organic Framework Heterojunction

Advanced Energy Materials, Journal Year: 2024, Volume and Issue: 14(27)

Published: April 25, 2024

Abstract Energy‐saving and value‐added management in advanced catalysis is highly desirable but challenged by the limitations of multifunctional catalysts catalytic modules. Herein, an azo‐linked phthalocyanine‐porphyrin covalent organic framework (COF) with ultrathin layered nanostructure grown on carbon nanotubes (NiPc‐azo‐H2Pp@CNTs) has been designed synthesized, which can serve as a active stable bifunctional heterojunction electrocatalyst for selective paired‐electrosynthesis through coupling anodic iodide oxidation reaction cathodic CO 2 conversion. Particularly, inbuilt local microenvironment conferred dihydroporphyrin moieties COF act proton reservoir to promote relay at interface during electrocatalytic process. Moreover, cascade construction dual electrocatalytic/organocatalytic modules, cathode‐generated be further converted dimethyl carbonate yield 6.21 mmol L −1 h , while anode‐produced iodine derived into iodoform hundred‐milligram scale. It worth noting that synthesis mediated paired‐electrolysis using distinctive high‐powered electrocatalysts will help advance sustainable development industrial intelligent manufacturing.

Language: Английский

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Electrochemical E-Selective Semireductive Dicarboxylation of Aryl Alkynes with CO₂

Organic Letters, Journal Year: 2024, Volume and Issue: 26(15), P. 3241 - 3246

Published: April 5, 2024

Herein, we report an electrochemical protocol for the dicarboxylation of aryl alkynes using CO2. With a graphite rod as cathode and Al sacrificial anode, series valuable butenedioic acids are obtained in moderate to excellent yields with E/Z ratio up 50:1. This method features high E-selectivity, step atom economy, easy scalability, nice substrate scope, which renders it appealing promising applications organic synthesis materials chemistry.

Language: Английский

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