Recent Advances in Reactions Involving Carbon Dioxide Radical Anion

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(24), P. 15991 - 16011

Published: Nov. 28, 2023

Carbon dioxide radical anion (CO2•–) is a highly reactive nucleophilic species that has recently emerged in organic chemistry as strong single electron donor (reductant) and reactant for the synthesis of carboxylic acids. In general, CO2•– can be generated by either direct reduction CO2 or HAT formate salts. Achievements reactions involving have been witnessed recent years. This Review summarizes advances highlighting some challenges identifying potential areas improvement, which may offer inspiration future studies.

Language: Английский

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Highlights on U.S. FDA-approved fluorinated drugs over the past five years (2018–2022)

European Journal of Medicinal Chemistry, Journal Year: 2023, Volume and Issue: 256, P. 115476 - 115476

Published: May 15, 2023

Language: Английский

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Recent Advances in C–H Functionalisation through Indirect Hydrogen Atom Transfer

Molecules, Journal Year: 2023, Volume and Issue: 28(16), P. 6127 - 6127

Published: Aug. 18, 2023

The functionalisation of C–H bonds has been an enormous achievement in synthetic methodology, enabling new retrosynthetic disconnections and affording simple equivalents for synthons. Hydrogen atom transfer (HAT) is a key method forming alkyl radicals from substrates. Classic reactions, including the Barton nitrite ester reaction Hofmann–Löffler–Freytag reaction, among others, provided early examples HAT. However, recent developments photoredox catalysis electrochemistry have made HAT powerful tool capable introducing wide range functional groups into bonds. Moreover, greater mechanistic insights stimulated development increasingly site-selective protocols. Site-selectivity can be achieved through tuning electron density at certain using additives, judicious choice reagent, solvent system. Herein, we describe latest methods functionalizing C–H/Si–H/Ge–H indirect between 2018–2023, as well critical discussion reagents, aspects, substrate scopes, background contexts

Language: Английский

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Recent Discovery, Development, and Synthetic Applications of Formic Acid Salts in Photochemistry

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(4)

Published: Oct. 9, 2023

The advancement of sustainable photoredox catalysis in synthetic organic chemistry has evolved immensely because the development versatile and cost-effective reagents. In recent years, a substantial effort been dedicated to exploring utility formic acid salts various photochemical reactions. this context, formates have demonstrated diverse capabilities, functioning as reductants, sources carbonyl groups, reagents for hydrogen atom transfer. Notably, CO

Language: Английский

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Photocatalytic organosulfur reagent-promoted selective mono-(deutero)hydrodechlorination

Green Chemistry, Journal Year: 2024, Volume and Issue: 26(9), P. 5167 - 5172

Published: Jan. 1, 2024

Selective partial C–Cl bond reduction represents an important strategy for the construction of valuable chlorine-containing skeletons.

Language: Английский

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Arenethiolate-Catalyzed 1,5-HAT of Aryl Halides: Synthesis of γ-Spirolactams

Organic Letters, Journal Year: 2024, Volume and Issue: 26(15), P. 3081 - 3085

Published: April 3, 2024

γ-Spirolactam is a privileged building block that found in wide range of natural products and bioactive compounds. Herein, we report an arenethiolate-catalyzed 1,5-HAT aryl halides to obtain γ-spirolactams through SET reduction/intramolecular 1,5-HAT/cyclization/HAT process. This protocol features metal-free conditions broad substrate scope, furnishing the moderate excellent yields. Notably, bromides, chlorides even fluorides are well tolerated this transformation. A mechanism involving arenethiolate as catalyst proposed based on DFT calculation.

Language: Английский

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o-Phosphinodiarylamides as Reductive Photocatalysts for Dehalogenative and Deaminative Cross-Couplings

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(17), P. 11753 - 11761

Published: Aug. 22, 2023

The strong electron-donating ability in the photoactivated state and structural flexibility of organic anions have led to a growing interest utilizing photoexcited as reductive photocatalysts activate inert chemical bonds. Phenolate thiolate been extensively studied utilized catalysts wide range photocatalytic transformations. In contrast, employing nitrogen for radical generation received less attention despite vast possibilities designing adjusting catalyst properties. this work, we reported that diaryl amides possessing ortho-diphenylphosphaneyl substituents function visible-light photoredox activation aryl halides (chloride bromide) ammonium salts generate radicals phosphorylation, borylation, arylation, alkylation with corresponding interceptors. o-phosphinodiarylamide also trifluoromethyl groups trifluoromethylarene, trifluoroacetate, trifluoroacetamide defluoroalkylation alkenes. Notably, methods using o-phosphinodiarylamides are very efficient from large π-extended halides, spiro-conjugated poly indicating advantages anion-based approach application synthesizing conjugated molecules electronic materials interface modification without recourse transition-metal catalysis.

Language: Английский

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Light-induced aryldifluoromethyl-sulfonylation/thioetherification of alkenes using arenethiolates as a photoreductant and sulfur source

Green Chemistry, Journal Year: 2023, Volume and Issue: 25(22), P. 9292 - 9300

Published: Jan. 1, 2023

A novel ATRA reaction was developed from simple and widely accessible alkenes, thiols, trifluoromethylarenes vis photo-induced EDA complex strategy. Several complicated bioactive molecules undergo smoothly the one-pot photosynthetic process.

Language: Английский

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Visible-light-mediated C–F bond cleavage for the synthesis of polyfluorinated compounds

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(13), P. 3341 - 3346

Published: Jan. 1, 2023

Herein, we describe a novel and efficient photo-redox catalytic difluorinated ester radical addition/defluoroalkylation coupling reaction between trifluoroacetic acid derivatives α-trifluoromethyl alkenes.

Language: Английский

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Nickel-catalysed chelation-assisted reductive defluorinative sulfenylation of trifluoropropionic acid derivatives

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(17), P. 2405 - 2408

Published: Jan. 1, 2024

Nickel-catalysed chelation-assisted reductive cross-coupling of trifluoropropanamides/esters with disulfides to afford thioacrylamides/esters high E selectivity, involving triple C–F bond cleavage.

Language: Английский

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