A Practical and Regioselective Strategy for Aromatic C–H Difunctionalization via Site-Selective C–H Thianthrenation

Organic Letters, Год журнала: 2024, Номер 26(9), С. 1813 - 1818

Опубликована: Фев. 22, 2024

Herein, we present a novel Catellani-type reaction that employed aryl-thianthrenium salts as aryl substrates to trigger the subsequent palladium/norbornene cooperatively catalyzed progress. This strategy can achieve site-selective C–H difunctionalization of compounds without directing groups or known initiating reagent. A series functionalized syntheses bioactive molecules further demonstrated potential this strategy.

Язык: Английский

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Site‐Selective Electrochemical C−H Carboxylation of Arenes with CO₂

Angewandte Chemie International Edition, Год журнала: 2022, Номер 62(3)

Опубликована: Ноя. 16, 2022

Herein, a direct, metal-free, and site-selective electrochemical C-H carboxylation of arenes by reductive activation using CO2 as the economic abundant carboxylic source was reported. The electrocarboxylation carried out in an operationally simple manner with high chemo- regioselectivity, setting stage for challenging unactivated (hetero)arenes. robust nature strategy reflected broad scope substrates excellent atom economy unique selectivity. Notably, direct selective various worked well this approach, including electron-deficient naphthalenes, pyridines, phenyl derivatives, substituted quinolines. method benefits from being externally catalyst-free, metal-free base-free, which makes it extremely attractive potential applications.

Язык: Английский

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Photocatalytic Functionalization of Dehydroalanine‐Derived Peptides in Batch and Flow

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(19)

Опубликована: Март 18, 2024

Abstract Unnatural amino acids, and their synthesis by the late‐stage functionalization (LSF) of peptides, play a crucial role in areas such as drug design discovery. Historically, LSF biomolecules has predominantly utilized traditional synthetic methodologies that exploit nucleophilic residues, cysteine, lysine or tyrosine. Herein, we present photocatalytic hydroarylation process targeting electrophilic residue dehydroalanine (Dha). This possesses an α , β ‐unsaturated moiety can be combined with various arylthianthrenium salts, both batch flow reactors. Notably, setup proved instrumental for efficient scale‐up, paving way unnatural acids peptides substantial quantities. Our approach, being inherently mild, permits diversification even when they contain sensitive functional groups. The readily available salts facilitate seamless integration Dha‐containing wide range arenes, blueprints, natural products, culminating creation unconventional phenylalanine derivatives. synergistic effect high group tolerance modular characteristic aryl electrophile enables peptide conjugation ligation conditions.

Язык: Английский

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Reductive Radical-Polar Crossover Enabled Carboxylative Alkylation of Aryl Thianthrenium Salts with CO₂ and Styrenes

Organic Letters, Год журнала: 2024, Номер 26(3), С. 728 - 733

Опубликована: Янв. 12, 2024

Carboxylic functionalities are among the pivotal groups in bioactive molecules and synthesis of new lead compounds because their unique character formation hydrogen bonds possibility constructing molecular complexes via amide couplings. We adopt reductive radical-polar crossover strategy to introduce carboxyalkyl into arenes with styrenes CO2 thianthrenium salts. This protocol exhibits excellent potential as a straightforward modular platform for site-selective carboxylative derivation molecules.

Язык: Английский

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Copper‐Catalyzed C4‐selective Carboxylation of Pyridines with CO₂ via Pyridylphosphonium Salts

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(13)

Опубликована: Фев. 3, 2024

Abstract Pyridine motifs are widespread pharmacophores in many drugs. Installing various substituents through pyridine C−H bond functionalization is significant for new drug design and discovery. Developments of late‐stage reactions enrich the strategies selective pyridines. However, carboxylation pyridines a long‐standing challenge, especially selectively with CO 2 on motifs. Herein, we describe practical method C4−H via one‐pot phosphination copper‐catalyzed resulted phosphonium salts . The reaction conducted under mild conditions compatible multiple active groups several drugs, providing diverse valuable isonicotinic acid compounds, demonstrating application potential this strategy.

Язык: Английский

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Late-Stage C–H Functionalization of Dehydroalanine-Containing Peptides with Arylthianthrenium Salts and Its Application in Synthesis of Tentoxin Analogue

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Янв. 14, 2025

Dehydrophenylalanine has a characteristic unsaturated double bond that makes it indispensable in the context of peptides and proteins. In this study, we report Pd-catalyzed C(sp2)-H arylation dehydroalanine-containing with arylthianthrenium salts under mild base free conditions, which provides efficient access to dehydrophenylalanine-containing peptides. This approach enables coupling different drug scaffolds bioactive molecules Remarkably, method could be used for concise synthesis tentoxin its analogue.

Язык: Английский

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Diastereoselective Synthesis of Cyclopropanes from Carbon Pronucleophiles and Alkenes

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(21)

Опубликована: Март 16, 2023

Abstract Cyclopropanes are desirable structural motifs with valuable applications in drug discovery and beyond. Established alkene cyclopropanation methods give rise to cyclopropanes a limited array of substituents, difficult scale, or both. Herein, we disclose new cyclopropane synthesis through the formal coupling abundant carbon pronucleophiles unactivated alkenes. This strategy exploits dicationic adducts derived from electrolysis thianthrene presence substrates. We find that these dielectrophiles undergo methylene via alkenyl thianthrenium intermediates. protocol is scalable, proceeds high diastereoselectivity, tolerates diverse functional groups on both pronucleophile partners. To validate utility this procedure, prepared an substituted analogs established en route multiple pharmaceuticals.

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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Catalytic ortho C–H methylation and trideuteromethylation of arylthianthrenium salts via the Catellani strategy

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(12), С. 3333 - 3340

Опубликована: Янв. 1, 2024

We report a Pd/NBE cooperative catalyzed ortho C–H methylation and trideuteromethylation of arylthianthrenium salts, enabling the efficient synthesis wide variety (trideutero)methylated arenes in moderate to good yields.

Язык: Английский

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Energy-transfer-enabled photocatalytic transformations of aryl thianthrenium salts

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Ноя. 8, 2024

Aryl thianthrenium salts are valuable in photocatalysis but traditionally require external electron donors for activation. This study introduces an energy transfer (EnT) strategy the activation of aryl using 2,3,4,5,6-penta(carbazol-9-yl)benzonitrile (5CzBN) as a metal-free photocatalyst, eliminating need donors. Utilizing this EnT approach, we achieve C-H deuteration arenes under visible light with CDCl

Язык: Английский

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