Advances in the use of CO₂as a renewable feedstock for the synthesis of polymers

Chemical Society Reviews, Journal Year: 2019, Volume and Issue: 48(16), P. 4466 - 4514

Published: Jan. 1, 2019

Carbon dioxide offers an accessible, cheap and renewable carbon feedstock for synthesis. Current interest in the area of valorisation aims at new, emerging technologies that are able to provide new opportunities turn a waste into value. Polymers among most widely produced chemicals world greatly affecting quality life. However, there growing concerns about lack reuse majority consumer plastics their after-life disposal resulting increasing demand sustainable alternatives. New monomers polymers can address these issues therefore warranted, merging polymer synthesis with recycling tangible route transition towards circular economy. Here, overview relevant recent approaches CO2-based highlighted particular emphasis on transformation routes used involved manifolds.

Language: Английский

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Recent advances of 1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene (4CzIPN) in photocatalytic transformations

Chemical Communications, Journal Year: 2019, Volume and Issue: 55(38), P. 5408 - 5419

Published: Jan. 1, 2019

In this review, the recent advances of application 1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene (4CzIPN) as a photoredox catalyst in past three years (2016–2018) for various organic reactions are summarized.

Language: Английский

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Inside‐and‐Out Semiconductor Engineering for CO₂ Photoreduction: From Recent Advances to New Trends

Small Structures, Journal Year: 2020, Volume and Issue: 2(1)

Published: Sept. 30, 2020

Photocatalytic CO 2 reduction attracts substantial interests for the production of chemical fuels via solar energy conversion, but activity, stability, and selectivity products were severely determined by efficiencies light harvesting, charge migration, surface reactions. Structural engineering is a promising tactic to address aforementioned crucial factors boosting photoreduction. Herein, timely comprehensive review focusing on recent advances in photocatalytic conversion based design strategies over nano‐/microstructure, crystalline band structure, structure interface provided, which covers both thermodynamic kinetic challenges photoreduction process. The key parameters essential tailoring size, morphology, porosity, bandgap, surface, or interfacial properties photocatalysts are emphasized toward efficient selective into valuable chemicals. New trends structural meet demands prominent activity also introduced. It expected furnish guideline inside‐and‐out state‐of‐the‐art with well‐defined structures conversion.

Language: Английский

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Photocatalytic Late-Stage C–H Functionalization

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(8), P. 4237 - 4352

Published: Jan. 24, 2023

The emergence of modern photocatalysis, characterized by mildness and selectivity, has significantly spurred innovative late-stage C–H functionalization approaches that make use low energy photons as a controllable source. Compared to traditional strategies, photocatalysis paves the way toward complementary and/or previously unattainable regio- chemoselectivities. Merging compelling benefits with workflow offers potentially unmatched arsenal tackle drug development campaigns beyond. This Review highlights photocatalytic strategies small-molecule drugs, agrochemicals, natural products, classified according targeted bond newly formed one. Emphasis is devoted identifying, describing, comparing main mechanistic scenarios. draws critical comparison between established ionic chemistry photocatalyzed radical-based manifolds. aims establish current state-of-the-art illustrate key unsolved challenges be addressed in future. authors aim introduce general readership functionalization, specialist practitioners evaluation methodologies, potential for improvement, future uncharted directions.

Language: Английский

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Radical Carboxylative Cyclizations and Carboxylations with CO₂

Accounts of Chemical Research, Journal Year: 2021, Volume and Issue: 54(10), P. 2518 - 2531

Published: May 6, 2021

ConspectusCarbon dioxide (CO2) is not only a greenhouse gas and common waste product but also an inexpensive, readily available, renewable carbon resource. It important one-carbon (C1) building block in organic synthesis for the construction of valuable compounds. However, its utilization challenging owing to thermodynamic stability kinetic inertness. Although significant progress has been achieved, many limitations remain this field with regard substrate scope, reaction system, activation strategies.Since 2015, our group focused on CO2 synthesis. We are interested vast possibilities radical chemistry, although high reactivity radicals presents challenges controlling selectivity. hope develop highly useful transformations involving by achieving balance selectivity under mild conditions. Over past 6 years, we along other experts have disclosed radical-type carboxylative cyclizations carboxylations using CO2.We initiated research realizing Cu-catalyzed oxytrifluoromethylation allylamines heteroaryl methylamines generate 2-oxazolidones various precursors. Apart from Cu catalysis, visible-light photoredox catalysis powerful method achieve efficient cyclization. In these cases, single-electron-oxidation-promoted C–O bond formation between benzylic carbamates key step.Since carboxylic acids exist widely natural products bioactive drugs serve as bulk chemicals industry, realized further visible-light-promoted construct such chemicals. achieved selective umpolung imines, enamides, tetraalkylammonium salts, oxime esters successive single-electron-transfer (SSET) reduction. Using strategy, dearomative arylcarboxylation indoles CO2. addition incorporation 1 equiv per substrate, recently developed photoredox-catalyzed dicarboxylation alkenes, allenes, (hetero)arenes via SSET reduction, which allows two molecules into compounds diacids polymer precursors.In two-electron CO2, sought new strategies realize single-electron Inspired hypothetical electron-transfer mechanism iron–sulfur proteins, visible-light-driven thiocarboxylation alkenes catalytic iron salts promoters. The in-situ-generated Fe/S complexes likely able reduce anion, could react give stabilized radical. Moreover, charge-transfer complex (CTC) thiolate acrylate/styrene hydrocarboxylation generation or alkene anion. On basis novel CTC, organocatalytic Hantzsch ester effective reductant.

Language: Английский

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Coupling Strategy for CO₂Valorization Integrated with Organic Synthesis by Heterogeneous Photocatalysis

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(39), P. 21150 - 21172

Published: April 28, 2021

Photocatalytic reduction of CO2 to solar fuels and/or fine chemicals is a promising way increase the energy supply and reduce greenhouse gas emissions. However, conventional reaction system for photoreduction with pure H2 O or sacrificial agents usually suffers from low catalytic efficiency, poor stability, cost-ineffective atom economy. A recent surge developments, in which photocatalytic valorization integrated selective organic synthesis into one system, indicates an efficient modus operandi that enables sufficient utilization photogenerated electrons holes achieve goals sustainable economic social development. In this Review we discuss current advances cooperative photoredox systems integrate organics upgrading based on heterogeneous photocatalysis. The applications virtues strategy underlying mechanisms are discussed. ongoing challenges prospects area critically

Language: Английский

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Visible-Light-Driven Reductive Carboarylation of Styrenes with CO₂ and Aryl Halides

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(18), P. 8122 - 8129

Published: April 20, 2020

The first example of visible-light-driven reductive carboarylation styrenes with CO2 and aryl halides in a regioselective manner has been achieved. A broad range iodides bromides were compatible this reaction. Moreover, pyridyl halides, alkyl even chlorides also viable method. These findings may stimulate the exploration novel Meerwein arylation-addition reactions user-friendly as radical sources photocatalytic utilization CO2.

Language: Английский

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Visible-Light-Driven Catalytic Reductive Carboxylation with CO₂

ACS Catalysis, Journal Year: 2020, Volume and Issue: 10(19), P. 10871 - 10885

Published: Aug. 28, 2020

Carbon dioxide (CO2) is an important C1 source for the generation of carboxylic acids and derivatives. Stoichiometric catalytic carboxylation nucleophiles, including organometallic reagents, with CO2 has been widely investigated. Since many kinds reagents are prepared from electrophiles, transition-metal-catalyzed direct diverse electrophiles attracted much attention high step economy user-friendly protocols. Although significant progress achieved, use stoichiometric metallic or pyrophoric reductants common. The renaissance photochemistry seen numerous efforts devoted to light-driven CO2, which become one most active directions in this field. In Perspective, we summarize recent advances visible-light-driven reductive substrates, such as unsaturated hydrocarbons, organic (pseudo)halides, imines, presence mild electron donors, amines, Hantzsch esters, formates. We highlight mechanisms reactions, can proceed absence a photoredox catalyst dual visible light photoredox/transition metal system. also discuss future field offer some insight into challenges that remain.

Language: Английский

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Recent progress and perspectives in heterogeneous photocatalytic CO2 reduction through a solid–gas mode

Coordination Chemistry Reviews, Journal Year: 2021, Volume and Issue: 438, P. 213906 - 213906

Published: March 24, 2021

Language: Английский

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Photocarboxylation with CO₂: an appealing and sustainable strategy for CO₂ fixation

Green Chemistry, Journal Year: 2020, Volume and Issue: 22(21), P. 7301 - 7320

Published: Jan. 1, 2020

This review discusses recent advances in the photocatalytic carboxylation of C(sp³)–X (X = H, N) bonds, C(sp²)–X N, (pseudo)halide) bonds and C(sp)–H with CO₂.

Language: Английский

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