A general alkene aminoarylation enabled by N-centred radical reactivity of sulfinamides

Nature Chemistry, Год журнала: 2024, Номер 16(4), С. 599 - 606

Опубликована: Янв. 16, 2024

Язык: Английский

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Arylthianthrenium Salts as the Aryl Sources: Visible Light/Copper Catalysis-Enabled Intermolecular Azidosulfonylation of Alkenes

Organic Letters, Год журнала: 2024, Номер 26(9), С. 1845 - 1850

Опубликована: Фев. 26, 2024

The difunctionalization of alkenes using aryl thianthrenium salts as the sources has been reported sporadically. However, four-component on basis not thus far and still remains a challenge. Herein, visible light/copper catalysis-enabled reaction salts, DABCO·(SO

Язык: Английский

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1,4‐Aminoarylation of Butadienes via Photoinduced Palladium Catalysis

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(14)

Опубликована: Фев. 9, 2024

Abstract A visible‐light‐induced, three‐component palladium‐catalyzed 1,4‐aminoarylation of butadienes with readily available aryl halides and aliphatic amines has been developed, affording allylamines excellent E ‐selectivity. The reaction exhibits exceptional control over chemo‐, regio‐, stereoselectivity, a broad substrate scope, high functional group compatibility, as demonstrated by the late‐stage functionalization bioactive molecules. Mechanistic investigations are consistent photoinduced radical Pd(0)‐Pd(I)‐Pd(II)‐Pd(0) Heck‐Tsuji–Trost allylation cascade.

Язык: Английский

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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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Standardized Approach for Diversification of Complex Small Molecules via Aryl Thianthrenium Salts

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Янв. 21, 2025

Thianthrenation is a useful strategy for the late-stage diversification of complex small molecules owing to positional selectivity and synthetic versatility thianthrenium salts as electrophilic linchpins. However, substrate-dependent identification suitable reaction conditions thianthrenation can be difficult. Reported functionalization vary significantly and, in some instances, lack robustness practicality. Herein, we report generalized approach preparation two manifolds practical, robust, parallel salts.

Язык: Английский

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Synthetic Applications of Sulfonium Salts as Aryl Radical Precursors

European Journal of Organic Chemistry, Год журнала: 2023, Номер 26(43)

Опубликована: Сен. 13, 2023

Abstract The utilization of aryl radicals as open‐shelled intermediates has become an essential tool for both conventional and state‐of‐the‐art synthetic chemistry. However, the current methods generating are still inefficient, greatly impeding their practical applications. Encouragingly, sulfonium salts have emerged appealing sources a wide range transformations aimed at creating novel chemical bonds driven by distinctive structural attributes tendencies. This review primarily focuses on specific reaction mechanisms underlying cleavage C−S in salts, leading to generation corresponding within diverse conditions.

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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Generation and Application of Aryl Radicals Under Photoinduced Conditions

Chemistry - A European Journal, Год журнала: 2024, Номер 30(31)

Опубликована: Март 28, 2024

Abstract Photoinduced aryl radical generation is a powerful strategy in organic synthesis that facilitates the formation of diverse carbon‐carbon and carbon‐heteroatom bonds. The synthetic applications photoinduced complex compounds, including natural products, physiologically significant molecules, functional materials, have received immense attention. An overview current developments production methods their uses given this article. A generalized idea how to choose reagents approach for radicals described, along with techniques associated mechanistic insights. Overall, article offers critical assessment results as well selection reaction parameters specific context cascades, cross‐coupling reactions, functionalization, selective C−H functionalization substrates.

Язык: Английский

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Triple Radical Sorting: Aryl-Alkylation of Alkenes

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(23), С. 15693 - 15700

Опубликована: Май 31, 2024

The cross-coupling of aryl bromides with alkenes can provide access to diverse combinatorial chemical space. Two-component couplings between these partners are well-known, but three-component aryl-functionalizations unactivated remain underdeveloped. In particular, the aryl-alkylation would allow for rapid construction molecular complexity and expedient exploration a pharmaceutically relevant C(sp3)-rich structural landscape. Herein, we report general approach toward through triple radical sorting mechanism. Over course reaction, high energy radical, primary hindered alkyl simultaneously formed. Through mediation by nickel-based catalyst, three radicals sorted into productive bond-forming pathways efficient alkenes. A wide range electronically sterically differentiated precursors be used complex scaffolds. This method was further applied synthesis highly substituted semisaturated fused heterocycles.

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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