Recent Advances in Reactions Involving Carbon Dioxide Radical Anion

ACS Catalysis, Год журнала: 2023, Номер 13(24), С. 15991 - 16011

Опубликована: Ноя. 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.

Язык: Английский

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Photoredox-Catalyzed Defluorinative Carboxylation of gem-Difluorostyrenes with Formate Salt

Organic Letters, Год журнала: 2024, Номер 26(4), С. 883 - 888

Опубликована: Янв. 22, 2024

Herein, we present a transition-metal-free, easy handling protocol for regioselective carboxylation of gem-difluorostyrenes with sodium formate as the C1 source. 30 examples α-fluoracrylates were obtained in yields to 80% under these conditions. A defluorinative monofluorovinyl intermediate and consecutive photoinduced electron transfer mechanism proposed after investigation.

Язык: Английский

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

Molecules, Год журнала: 2023, Номер 28(16), С. 6127 - 6127

Опубликована: Авг. 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

Язык: Английский

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

Angewandte Chemie International Edition, Год журнала: 2023, Номер 63(4)

Опубликована: Окт. 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

Язык: Английский

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Carbon Dioxide Radical Anion by Photoinduced Equilibration between Formate Salts and [¹¹C, ¹³C, ¹⁴C]CO₂: Application to Carbon Isotope Radiolabeling

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(30), С. 16760 - 16770

Опубликована: Июль 24, 2023

The need for carbon-labeled radiotracers is increasingly higher in drug discovery and development (carbon-14, β-, t1/2 = 5730 years) as well positron emission tomography (PET) vivo molecular imaging applications (carbon-11, β+, 20.4 min). However, the structural diversity of still systematically driven by narrow available labeled sources methodologies. In this context, emergence carbon dioxide radical anion chemistry might set forth potential unexplored opportunities. Based on a dynamic isotopic equilibration between formate salts [13C, 14C, 11C]CO2, C-labeled CO2•- could be accessed under extremely mild conditions within seconds. This methodology was successfully applied to hydrocarboxylation dicarboxylation reactions late-stage isotope labeling pharmaceutically relevant compounds. relevance method radiochemistry showcased whole-body PET biodistribution profile [11C]oxaprozin mice.

Язык: Английский

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Visible-light-driven alkene dicarboxylation with formate and CO₂ under mild conditions

Chemical Science, Год журнала: 2024, Номер 15(16), С. 6178 - 6183

Опубликована: Янв. 1, 2024

Low-cost formate salt was used as the reductant and part of carboxyl source in a visible-light-driven dicarboxylation diverse alkenes, including simple styrenes. The highly competing hydrocarboxylation side reaction successfully overridden. Good yields products were obtained under mild conditions at ambient temperature pressure CO

Язык: Английский

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Photochemical dearomative skeletal modifications of heteroaromatics

Chemical Society Reviews, Год журнала: 2024, Номер 53(12), С. 6600 - 6624

Опубликована: Янв. 1, 2024

Dearomatization has emerged as a powerful tool for rapid construction of 3D molecular architectures from simple, abundant, and planar (hetero)arenes. The field evolved beyond simple dearomatization driven by new synthetic technology development. With the renaissance photocatalysis expansion activation mode, last few years have witnessed impressive developments in innovative photochemical methodologies, enabling skeletal modifications dearomatized structures. They offer truly efficient useful tools facile highly complex structures, which are viable natural product synthesis drug discovery. In this review, we aim to provide mechanistically insightful overview on these innovations based degree alteration, categorized into dearomative functionalization editing, highlight their utilities.

Язык: Английский

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Enantioselective Total Synthesis of (−)-Daphenylline

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(2), С. 1262 - 1268

Опубликована: Янв. 5, 2024

A concise enantioselective total synthesis of (−)-daphenylline, a hexacyclic Daphniphyllum alkaloid with unique benzene ring, was achieved in 14 steps. The commences two chiral stereocenters, C2 and C18, readily installed via Carreira's Ir/amine dual-catalyzed allylation. allylic bridgehead amine 6 rapidly prepared through Wickens' photoredox-catalyzed hydrocarboxylation olefin CuBr2-catalyzed α-amination ketone. tetracycle 4 formed Pd-catalyzed reductive Heck reaction or, more concisely, by Krische's Rh-catalyzed 1,6-enyne cyclization. In this synthesis, newly reported used twice, Friedel–Crafts acylation thrice.

Язык: Английский

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Photochemical Reductive Carboxylation of N-Benzoyl Imines with Oxalate Accelerated by Formation of EDA Complexes

ACS Catalysis, Год журнала: 2024, Номер 14(13), С. 10053 - 10059

Опубликована: Июнь 20, 2024

Язык: Английский

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Divergent defluorocarboxylation of α-CF3 alkenes with formate via photocatalyzed selective mono- or triple C-F bond cleavage

Science China Chemistry, Год журнала: 2023, Номер 67(1), С. 368 - 373

Опубликована: Авг. 16, 2023

Язык: Английский

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