Revisiting the Electrochemical Carboxylation of Naphthalene with CO₂: Selective Monocarboxylation of 2-Substituted Naphthalenes

Organic Letters, Год журнала: 2023, Номер 25(23), С. 4231 - 4235

Опубликована: Июнь 2, 2023

Numerous remarkable reactions based on electrochemical carboxylations using CO2 have recently attracted considerable attention. In contrast to more recent examples, the carboxylation of naphthalene had already been established in 1959, whereby a dearomative dicarboxylation selectively produces 1,4-dicarboxylated 1,4-dihydronaphthalene derivatives. Here, we report that use electron-deficient derivatives presence redox mediator such as p-terphenyl and H2O under bubbling affords trans-1,2-disubstituted 1,2-dihydronaphthalene

Язык: Английский

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Decatungstate‐Photocatalyzed Diastereoselective Dearomative Hydroalkylation of Indoles

European Journal of Organic Chemistry, Год журнала: 2024, Номер 27(22)

Опубликована: Апрель 16, 2024

Abstract In this study, we present an efficient and straightforward dearomative hydroalkylation of indoles. By utilizing alkanes or ethers as alkyl radical sources employing TBADT a cost‐effective photocatalyst for direct hydrogen atom transfers (HAT), achieved successful conversion these heterocyclic derivatives into 2‐alkylindolines with good to excellent yields high diastereoselectivity under mild reaction conditions.

Язык: Английский

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Dearomatization of (Hetero)arenes through Photodriven Interplay between Polysulfide Anions and Formate**

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(40)

Опубликована: Авг. 16, 2023

Abstract The facile construction of C(sp 3 )‐rich carbo‐ and heterocyclic compounds is a pivotal synthetic strategy to foster contemporary drug discovery programs. downstream dearomatization readily accessible two‐dimensional (2D) planar arenes represents direct pathway towards accessing three‐dimensional (3D) aliphatic scaffolds. Here, we demonstrate that polysulfide anions are capable catalyzing process substituted naphthalenes, indoles, other related heteroaromatic in the presence potassium formate methanol under visible light irradiation. developed protocol exhibits broad functional group tolerance, operational simplicity, scalability, cost‐effectiveness, representing practical sustainable tool for arene dearomatization.

Язык: Английский

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γ-Butyrolactone Synthesis from Allylic Alcohols Using the CO₂ Radical Anion

Precision Chemistry, Год журнала: 2024, Номер 2(3), С. 88 - 95

Опубликована: Фев. 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.

Язык: Английский

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Photocatalytic deuterocarboxylation of alkynes with oxalate

Chemical Science, Год журнала: 2024, Номер 15(32), С. 13041 - 13048

Опубликована: Янв. 1, 2024

Herein, a catalytic photoredox-neutral strategy for alkyne deuterocarboxylation with tetrabutylammonium oxalate as the carbonyl source and D

Язык: Английский

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CO₂ Radical Anion in Photochemical Dicarboxylation of Alkenes

ChemCatChem, Год журнала: 2023, Номер 15(17)

Опубликована: Июнь 25, 2023

Abstract CO 2 radical anion (CO ⋅ − ) is a highly reductive species ( E red =−2.2 V vs SCE), which can undergo Giese addition to an unsaturated C−C bond and install carbonyl group synthesize acids. Normally, it has been generated through the direct reduction of gas or from formate salts via HAT (hydrogen atom transfer) as BDE (bond dissociation energy) C−H in only around 86 kcal/mol. This concept highlights recent developments on alkenes dicarboxylation reaction with and/or sources. In these reactions, played significant roles carboxylation step.

Язык: Английский

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Quantum chemical calculations for reaction prediction in the development of synthetic methodologies

Chemical Science, Год журнала: 2023, Номер 14(42), С. 11601 - 11616

Опубликована: Янв. 1, 2023

This perspective showcases how quantum chemical calculations drive predictive strategies to explore unknown reactions, catalysts, and synthetic routes toward complex molecules in methodology development.

Язык: Английский

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Iron-Catalyzed Photoredox Intermolecular Dearomatization of Benzothiazoles with Alkanes

ACS Sustainable Chemistry & Engineering, Год журнала: 2023, Номер 11(35), С. 13142 - 13148

Опубликована: Авг. 24, 2023

Benzothiazolines, with their versatile nature, serve as fundamental building blocks for the synthesis of significant biological compounds. However, methods preparation benzothiazolines from readily available starting materials are limited. An efficient benzothiazoline via photoredox-catalyzed dearomatization benzothiazole derivatives has been achieved at room temperature. This catalysis proceeds a ligand to metal charge transfer process, and FeCl3 plays dual role an indirect HAT reagent reducing agent. methodology can be conveniently scaled up, most alkylated products purified without chromatography. In addition, this process exhibited advantages low cost, high reaction efficiency, mild conditions.

Язык: Английский

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A novel approach for synthesizing α-amino acids via formate mediated hydrogen transfer using a carbon source

Green Chemistry, Год журнала: 2023, Номер 25(21), С. 8539 - 8543

Опубликована: Янв. 1, 2023

We report an unprecedented synthesis of α-amino acid derivatives utilizing HCOO − as a carbon and hydrogen source. This method employs firstly commercially available 2-naphthalenethiol organic photocatalyst for radical-radical cross-coupling.

Язык: Английский

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Photo-catalyst-free photomediated pinacol coupling of ketones/aldehydes by formate at room temperature

Green Chemistry, Год журнала: 2023, Номер 25(23), С. 9665 - 9671

Опубликована: Янв. 1, 2023

In this work, a highly effective metal-free and photo-catalyst-free method for the reductive coupling of carbonyl compounds to produce pinacols using formate under photoirradiation has been reported.

Язык: Английский

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