Electroreductive Arylcarboxylation of Styrenes with CO₂ and Aryl Halides via a Radical–Polar Crossover Mechanism

Organic Letters, Год журнала: 2024, Номер 26(21), С. 4427 - 4432

Опубликована: Май 17, 2024

2,3-Diaryl propanoic acids are important structures as a result of their widespread presence in numerous bioactive compounds. However, the limitations existing synthetic techniques include requirement for costly catalysts and limited substrates. Here, we developed novel electroreductive arylcarboxylation alkenes with CO2 based on radical–polar crossover pathway assisted by easily accessible dimethyl terephthalate reductive mediator. This method will provide an efficient strategy synthesis 2,3-diarylpropanoic acids.

Язык: Английский

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Palladium-Catalyzed Domino Conversion of Aryl–Thianthreniums with Anhydrides: Rapidly Building Highly Functionalized Fluorenones

Organic Letters, Год журнала: 2024, Номер 26(16), С. 3332 - 3337

Опубликована: Апрель 15, 2024

As a class of rising electrophilic coupling reagents, aryl–thianthreniums (aryl-TTs) have been gaining immense attention. Herein, novel palladium-catalyzed domino annulation aryl-TTs with anhydrides is proposed to rapidly assemble collection highly functionalized fluorenones. This finding presents an innovative reaction pattern wherein the version first involved. Heavily compared existing conversions aryl-TTs, this identified process successively functions as four aryl C–H bonds.

Язык: Английский

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Visible light-promoted defluorinative alkylation/arylation of α-trifluoromethyl alkenes with thianthrenium salts

Green Chemistry, Год журнала: 2024, Номер 26(17), С. 9371 - 9377

Опубликована: Янв. 1, 2024

Defluorinative alkylation and arylation between thianthrenium salts α-trifluoromethyl alkene to afford gem -difluoroolefins by easily recycling thianthrene under visible light irradiation free of metal photocatalyst.

Язык: Английский

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Palladium-Catalyzed Hiyama-Type Coupling of Thianthrenium and Phenoxathiinium Salts

Organic Letters, Год журнала: 2024, Номер 26(31), С. 6681 - 6686

Опубликована: Июль 26, 2024

Here, we demonstrate palladium-catalyzed Hiyama-type cross-coupling reactions of aryl thianthrenium or phenoxathiinium salts. By employing stable and inexpensive organosilanes, the arylation, alkenylation, alkynylation were realized in high efficiency using commercially available Pd(tBu3P)2 as catalyst, thus providing a reliable method for preparation biaryls, styrenes, acetylenes with broad functional group tolerance under mild conditions. Given accessibility salts from simple arenes remarkable regioselective fashion, this protocol also provides an attractive approach late-stage modification complex bioactive scaffolds.

Язык: Английский

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Visible Light-Induced Radical Cascade Functionalization of Quinoxalin-2(1H)-ones: Three-Component 1,2-Di(hetero)arylation Approach with Styrenes and Thianthrenium Salts

Organic Letters, Год журнала: 2024, Номер 26(41), С. 8821 - 8826

Опубликована: Окт. 9, 2024

The additive-free visible light-induced three-component 1,2-di(hetero)arylation of styrenes was developed using quinoxalin-2(1

Язык: Английский

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Mechanochemically Induced Thianthrenium Salts-Based Arylation of Diverse Heterocyclic Scaffolds

ACS Sustainable Chemistry & Engineering, Год журнала: 2024, Номер 12(34), С. 12808 - 12818

Опубликована: Авг. 15, 2024

Herein, a mechanochemically triggered C–H arylation of coumarins, quinoline-N-oxides, and uracil molecules with aryl thianthrenium salts is described. Aryl are primarily acknowledged for their expedient reusability adherence to atom economy principles. Mechanistic studies suggested that mechanical stress promoted the homolytic scission C–S bond salts, forming radical intermediate. Later, intermediate engaged in addition reaction above heterocycles, leading desired products good yields. This versatile protocol accommodates wide range functional groups facilitates synthesis bioactive compounds drug molecules.

Язык: Английский

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Alkene Carboxy-Alkylation via CO₂^•–

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(51), С. 35035 - 35042

Опубликована: Дек. 12, 2024

Herein, we introduce a new platform for alkene carboxy-alkylation. This reaction is designed around CO

Язык: Английский

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Photoactivation of Thianthrenium Salts: An Electron-Donor–Acceptor (EDA)-Complex Approach

The Journal of Organic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Май 14, 2025

Thianthrenium salts have emerged as one of the most versatile reagents, gaining significant popularity within synthetic community for their utility in construction C-C and C-X (X = N, O, S, P, halogens) bonds. The use photoredox transition metal catalysis with thianthrenium C-heteroatom bond formation is well established. However, these methods require elevated temperatures, expensive catalysts, ligands under stringent conditions effective execution. In contrast, photocatalysis- transition-metal-free approaches constructing bonds using salt derivatives become increasingly sought after. this regard, electron-donor-acceptor (EDA)-complex reactions a powerful strategy organic synthesis, eliminating need photocatalysts visible light irradiation. EDA-complex photochemistry exploits electron-acceptor properties salts, facilitating rapid generation radical intermediates via C-S cleavage. These play pivotal role enabling variety valuable formations. Perspective, we highlight advances EDA-complex-mediated involving mechanisms, substrate scope, limitations For sake brevity, article organized into five main sections: (1) Nitrogen-based donor reactions, (2) Oxygen-based (3) Sulfur-based (4) Phosphorus-based (5) π-based focus on C-C, C-S, C-B C-P

Язык: Английский

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Visible-Light-Induced Arylcarboxylation of Activated Alkenes with Aryl Halides and Oxalate Enabled by Electron Donor–Acceptor Complex Formation

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Май 29, 2025

Simultaneous construction of two new C-C bonds in the alkene substrates regioselectively is significantly challenging. Herein, we report an unprecedented regioselective arylcarboxylation strategy activated alkenes with readily available aryl halides and tetrabutylammonium oxalate as reductant C1 source under visible-light-induced conditions. The reaction proceeds smoothly to access various carboxylic acids absence any catalysts, additives, metal promoters, or pre-established CO2 atmosphere. electron donor-acceptor (EDA) complex formed between stoichiometric amounts trigger single-electron reduction relay process after irradiation visible light. situ generated oxalic radical anion species undergoes homolysis bond releases potent source, respectively, facilitate reductive carboxylation.

Язык: Английский

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Unusual Regio‐ and Chemoselectivity in Oxidation of Pyrroles and Indoles Enabled by a Thianthrenium Salt Intermediate

Angewandte Chemie International Edition, Год журнала: 2024, Номер unknown

Опубликована: Июнь 3, 2024

A dearomative oxidation of pyrroles to Δ

Язык: Английский

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