Recent advances in nucleophile-triggered CO₂-incorporated cyclization leading to heterocycles

Chemical Society Reviews, Journal Year: 2018, Volume and Issue: 48(1), P. 382 - 404

Published: Nov. 27, 2018

CO₂, as a sustainable, feasible, abundant one-carbon synthon, has been utilized in carboxylative cyclization, carbonylative and reductive cyclization.

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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Catalytic reduction of CO₂into fuels and fine chemicals

Green Chemistry, Journal Year: 2020, Volume and Issue: 22(13), P. 4002 - 4033

Published: Jan. 1, 2020

Catalytic reduction of CO₂is very challenging from both economics and green chemistry perspectives. This critical review highlights major advancements made in the CO₂reduction processes their future challenges.

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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Toward ideal carbon dioxide functionalization

Chemical Science, Journal Year: 2019, Volume and Issue: 10(14), P. 3905 - 3926

Published: Jan. 1, 2019

This Perspective recapitulates recent developments of carbon dioxide utilization in carbon-carbon bond formation reactions, with an intention paving a way toward sustainable CO2-functionalization and its tangible applications synthetic chemistry. CO2 functionalization reactions possess intrinsic drawbacks: the high kinetic inertness thermodynamic stability CO2. Numerous procedures for depend on energy-intensive processes (i.e. pressure and/or temperature), often solely relying reactive substrates, hampering general applications. Recent efforts thus have been dedicated to catalytic CO2-utilization under ambient reaction conditions, however, it is still limited few activation modes use substrates. Herein, ideal particular emphasis sustainability will be discussed based following sub-categories; (1) metal-catalyzed 'reductive' carboxylation halides, olefins allyl alcohols, (2) photochemical CO2-utilization, (3) redox-neutral CO2-functionalization, (4) enantioselective catalysis incorporating form C-CO2 bonds (excluding strain mediated epoxide- aziridine-based substrates). progress these fields proposed mechanisms selected examples, highlighting redox-neutral, umpolung, asymmetric postulate developed near future.

Language: Английский

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Sequential and direct multicomponent reaction (MCR)-based dearomatization strategies

Chemical Society Reviews, Journal Year: 2020, Volume and Issue: 49(23), P. 8721 - 8748

Published: Jan. 1, 2020

This review focuses on the comprehensive understanding of different multicomponent reaction (MCR) cascades involving dearomatization as characteristic step.

Language: Английский

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Reductive dearomative arylcarboxylation of indoles with CO2 via visible-light photoredox catalysis

Nature Communications, Journal Year: 2020, Volume and Issue: 11(1)

Published: June 29, 2020

Abstract Catalytic reductive coupling of two electrophiles and one unsaturated bond represents an economic efficient way to construct complex skeletons, which is dominated by transition-metal catalysis via electron transfer. Herein, we report a strategy visible-light photoredox-catalyzed successive single transfer, realizing dearomative arylcarboxylation indoles with CO 2 . This avoids common side reactions in catalysis, including ipso-carboxylation aryl halides β-hydride elimination. photoredox shows high chemoselectivity, low loading photocatalyst, mild reaction conditions (room temperature, 1 atm) good functional group tolerance, providing great potential for the synthesis valuable but difficultly accessible indoline-3-carboxylic acids. Mechanistic studies indicate that benzylic radicals anions might be generated as key intermediates, thus direction couplings other electrophiles, D O aldehyde.

Language: Английский

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Oxy-Alkylation of Allylamines with Unactivated Alkyl Bromides and CO₂ via Visible-Light-Driven Palladium Catalysis

Organic Letters, Journal Year: 2018, Volume and Issue: 20(10), P. 3049 - 3052

Published: May 2, 2018

A selective oxy-alkylation of allylamines with unactivated alkyl bromides and CO2 via visible-light-driven palladium catalysis is reported. The commercially available Pd(PPh3)4 used as the sole catalyst in this three-component reaction. variety tertiary, secondary, primary undergo reactions to generate important 2-oxazolidinones high yields selectivity. mild reaction conditions, easy scalability, facile derivatization products provide great potential for application organic synthesis pharmaceutical chemistry.

Language: Английский

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Oxy-Difluoroalkylation of Allylamines with CO₂ via Visible-Light Photoredox Catalysis

Organic Letters, Journal Year: 2017, Volume and Issue: 20(1), P. 190 - 193

Published: Dec. 27, 2017

A selective oxy-difluoroalkylation of allylamines with carbon dioxide (CO2) via visible-light photoredox catalysis is reported. These multicomponent reactions are efficient and environmentally friendly to generate a series important 2-oxazolidinones functionalized difluoroalkyl groups. The good functional group tolerance, broad substrate scope, easy scalability, mild reaction conditions, facile functionalization products provide great potential for application in organic synthesis pharmaceutical chemistry.

Language: Английский

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Visible-light-induced intramolecular charge transfer in the radical spirocyclisation of indole-tethered ynones

Chemical Science, Journal Year: 2019, Volume and Issue: 11(5), P. 1353 - 1360

Published: Dec. 13, 2019

Indole-tethered ynones form an intramolecular electron donor–acceptor complex that can undergo visible-light-induced charge transfer to promote thiyl radical generation from thiols. This initiates a novel chain sequence, based on dearomatising spirocyclisation with concomitant C–S bond formation. Sulfur-containing spirocycles are formed in high yields using this simple and mild synthetic protocol, which neither transition metal catalysts nor photocatalysts required. The proposed mechanism is supported by various mechanistic studies, the unusual initiation mode represents only second report of use synthesis.

Language: Английский

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