Bidirectional Elongation Strategy Using Ambiphilic Radical Linchpin for Modular Access to 1,4-Dicarbonyls via Sequential Photocatalysis DOI
Akira Matsumoto, Natsumi Maeda, Keiji Maruoka

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(37), P. 20344 - 20354

Published: July 25, 2023

Organic molecules that can be connected to multiple substrates by sequential C-C bond formations utilized as linchpins in multicomponent processes. While they are useful for rapidly increasing molecular complexity, most of the reported linchpin coupling methods rely on use organometallic species strong carbon nucleophiles form bonds, which narrows functional group compatibility. Here, we describe a metal-free, radical-mediated approach using formyl-stabilized phosphonium ylide multifunctional under visible-light photoredox conditions. The present method uses ambiphilic character ylide, serves both nucleophilic and an electrophilic carbon-centered radical source. stepwise controllable generation these intermediates allows photocatalysis involving two mechanistically distinct additions, initiated same photocatalyst one pot with high tolerance. methodology enables bidirectional assembly electronically differentiated alkene fragments thus offers rapid modular access 1,4-dicarbonyl compounds versatile synthetic intermediates.

Language: Английский

Translating Planar Heterocycles into Three‐Dimensional Analogs by Photoinduced Hydrocarboxylation** DOI Creative Commons
Myriam Mikhael, Sara N. Alektiar, Charles S. Yeung

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(30)

Published: May 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.

Language: Английский

Citations

34
Transition-metal free oxidative carbo-carboxylation of alkenes with formate in air DOI
Pei Xu, Hui Xu, Sai Wang

et al.

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(8), P. 2013 - 2017

Published: Jan. 1, 2023

A synthetic route to oxindole-3-acetic acid derivatives is disclosed through a transition-metal free carbo-carboxylation reaction with CO 2 ˙ − as the C1 source in situ generated from formate under photo-induced conditions.

Language: Английский

Citations

26
Carbon Dioxide Radical Anion by Photoinduced Equilibration between Formate Salts and [11C, 13C, 14C]CO2: Application to Carbon Isotope Radiolabeling DOI
Augustin Malandain, Maxime Molins,

Alexandre Hauwelle

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(30), P. 16760 - 16770

Published: July 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.

Language: Английский

Citations

26
Recent Discovery, Development, and Synthetic Applications of Formic Acid Salts in Photochemistry DOI
Jadab Majhi,

Gary A. Molander

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

Citations

26
Divergent defluorocarboxylation of α-CF3 alkenes with formate via photocatalyzed selective mono- or triple C-F bond cleavage DOI
Xingyu Wang, Pei Xu, Wenwen Liu

et al.

Science China Chemistry, Journal Year: 2023, Volume and Issue: 67(1), P. 368 - 373

Published: Aug. 16, 2023

Language: Английский

Citations

24
Visible-light-driven alkene dicarboxylation with formate and CO2 under mild conditions DOI Creative Commons
Fulin Zhang, Xiaoyang Wu, Panpan Gao

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(16), P. 6178 - 6183

Published: Jan. 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

Language: Английский

Citations

12
Visible-Light-Induced Decarboxylative Annulation of α,β-Unsaturated Acids with Amines and α-Keto Acids for 2,4-Diarylquinoline Synthesis DOI
Suman Das, Souvik Maiti,

Soumya Mondal

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 3, 2025

An efficient and sustainable approach for the synthesis of 2,4-diarylquinolines has been developed via a visible-light-promoted metal-free three-component decarboxylative annulation pathway. This one-pot protocol combines readily available feed-stock α,β-unsaturated acids, aromatic amines, α-keto acids in cascade manner to access substituted quinolines under eco-benign conditions. Moreover, mechanistic insights suggest initial C-C cross coupling followed by 6π electrocyclic afford desired products. The broad substrates scope excellent functional group tolerance make this more attractive synthetically applicable toward construction complex N-heterocycles.

Language: Английский

Citations

1
Reinterpreting the Fate of Iridium(III) Photocatalysts─Screening a Combinatorial Library to Explore Light-Driven Side-Reactions DOI

Joseph C. Bawden,

Paul S. Francis, Stephen DiLuzio

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(25), P. 11189 - 11202

Published: June 15, 2022

Photoredox catalysts are primarily selected based on ground and excited state properties, but their activity is also intrinsically tied to the nature of reduced (or oxidized) intermediates. Catalyst reactivity often necessitates an inherent instability, thus these intermediates represent a mechanistic turning point that affords either product formation or side-reactions. In this work, we explore scope previously demonstrated side-reaction partially saturates one pyridine ring ancillary ligand in heteroleptic iridium(III) complexes. Using high-throughput synthesis screening under photochemical conditions, identified different chemical pathways, ultimately governed by composition. The was key factor determined stability. Following photoinitiated electron transfer from sacrificial tertiary amine, intermediate complexes containing 1,10-phenanthroline derivatives exhibited long-term contrast, 2,2′-bipyridines were highly susceptible hydrogen atom modification. Detailed characterization before after transformation showed differing effects reduction potentials dependent cyclometalating ligands states. implications catalyst stability model photoredox reaction.

Language: Английский

Citations

34
Visible-light-driven regioselective carbocarboxylation of 1,3-dienes with organic halides and CO2 DOI

Chunlin Zhou,

Xinchao Wang, Lei Yang

et al.

Green Chemistry, Journal Year: 2022, Volume and Issue: 24(16), P. 6100 - 6107

Published: Jan. 1, 2022

An unprecedented visible-light-driven regioselective carbocarboxylation of 1,3-dienes with CO 2 using aryl and alkyl halides under mild conditions is reported herein.

Language: Английский

Citations

34
γ-Butyrolactone Synthesis from Allylic Alcohols Using the CO2 Radical Anion DOI Creative Commons
Saeesh R. Mangaonkar, Hiroki Hayashi, Wataru Kanna

et al.

Precision Chemistry, Journal Year: 2024, Volume and Issue: 2(3), P. 88 - 95

Published: Feb. 16, 2024

γ-Butyrolactone structures are commonly found in various natural products and serve as crucial building blocks organic synthesis. Consequently, the development of methods for synthesizing γ-butyrolactones has garnered significant interest within synthesis community. In this study, we present a direct highly efficient approach from allylic alcohols. Notably, study represents first instance γ-butyrolactone initiated by radical hydrocarboxylation using CO2•–, generated metal formates, followed cyclization. This two-step process is achieved through synergistic interaction photoredox hydrogen atom transfer (HAT) catalysis, resulting production with exceptional efficiency. Additionally, when employing α,α-diaryl alcohol derivatives substrates, reaction involves 1,2-aryl migration, which occurs concomitantly CO2•– addition, leading to formation 4,5-substituted lactones good yield. The artificial force induced (AFIR) method identified preferred migration pathway along potential byproduct pathways, targeted 1,2-migration was be most plausible pathway.

Language: Английский

Citations

6