Radical Hydrocarboxylation of Unactivated Alkenes via Photocatalytic Formate Activation

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(20), С. 10991 - 10997

Опубликована: Май 15, 2023

Herein we disclose a strategy to promote the hydrocarboxylation of unactivated alkenes using photochemical activation formate salts. We illustrate that an alternative initiation mechanism circumvents limitations prior approaches and enables this challenging substrate class. Specifically, found accessing requisite thiyl radical initiator without exogenous chromophore eliminates major byproducts have plagued attempts exploit similar reactivity for alkene substrates. This redox-neutral method is technically simple execute effective across broad range Feedstock alkenes, such as ethylene, are hydrocarboxylated at ambient temperature pressure. A series cyclization experiments indicate how described in report can be diverted by more complex processes.

Язык: Английский

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

Organic Letters, Год журнала: 2024, Номер 26(2), С. 467 - 472

Опубликована: Янв. 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.

Язык: Английский

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Exploring the applications of carbon dioxide radical anion in organic synthesis

Science Bulletin, Год журнала: 2023, Номер 68(24), С. 3124 - 3128

Опубликована: Ноя. 8, 2023

Язык: Английский

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Translating Planar Heterocycles into Three‐Dimensional Analogs by Photoinduced Hydrocarboxylation**

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(30)

Опубликована: Май 18, 2023

The rapid preparation of complex three-dimensional (3D) heterocyclic scaffolds is a key challenge in modern medicinal chemistry. Despite the increased probability clinical success for small molecule therapeutic candidates with 3D complexity, new drug targets remain dominated by flat molecules due to abundance coupling reactions available their construction. In principle, heteroarene hydrofunctionalization offer an opportunity transform readily accessible planar into more three-dimensionally analogs through introduction single molecular vector. Unfortunately, dearomative limited. Herein, we report strategy enable hydrocarboxylation indoles and related heterocycles. This reaction represents rare example that meets numerous requirements broad implementation discovery. transformation highly chemoselective, scope, operationally simple, amenable high-throughput experimentation (HTE). Accordingly, this process will allow existing libraries heteroaromatic compounds be translated diverse exploration classes medicinally relevant molecules.

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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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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C(sp³)–H Carboxylation via Carbene/Photoredox Cooperative Catalysis

ACS Catalysis, Год журнала: 2025, Номер 15(2), С. 1287 - 1293

Опубликована: Янв. 7, 2025

C(sp3)–H bond functionalization is a powerful strategy for the synthesis of organic compounds due their abundance in simple starting materials. Photoredox catalysis has led to diverse array enabling activation strategies; however, general platform direct carboxylic acid derivatives remains elusive. Disclosed herein development cooperative NHC/photoredox-catalyzed esterification transformation. This method enables access benzylic, α-heteroatom, and formal β-esterification products moderate high yields under mild reaction conditions.

Язык: Английский

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