Photocatalytic Late-Stage C–H Functionalization

Chemical Reviews, Год журнала: 2023, Номер 123(8), С. 4237 - 4352

Опубликована: Янв. 24, 2023

The emergence of modern photocatalysis, characterized by mildness and selectivity, has significantly spurred innovative late-stage C–H functionalization approaches that make use low energy photons as a controllable source. Compared to traditional strategies, photocatalysis paves the way toward complementary and/or previously unattainable regio- chemoselectivities. Merging compelling benefits with workflow offers potentially unmatched arsenal tackle drug development campaigns beyond. This Review highlights photocatalytic strategies small-molecule drugs, agrochemicals, natural products, classified according targeted bond newly formed one. Emphasis is devoted identifying, describing, comparing main mechanistic scenarios. draws critical comparison between established ionic chemistry photocatalyzed radical-based manifolds. aims establish current state-of-the-art illustrate key unsolved challenges be addressed in future. authors aim introduce general readership functionalization, specialist practitioners evaluation methodologies, potential for improvement, future uncharted directions.

Язык: Английский

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Organothianthrenium salts: synthesis and utilization

Chemical Science, Год журнала: 2022, Номер 13(46), С. 13690 - 13707

Опубликована: Янв. 1, 2022

This review summarizes the synthesis of diverse organothianthrenium salts from various precursors and their applications in organic to forge new C–C, C–H C–heteroatom bonds by C–S bond cleavage with different mechanistic considerations.

Язык: Английский

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Selective Fluorosulfonylation of Thianthrenium Salts Enabled by Electrochemistry

Organic Letters, Год журнала: 2023, Номер 25(4), С. 581 - 586

Опубликована: Янв. 25, 2023

A practical electrochemically driven method for fluorosulfonylation of both aryl and alkyl thianthrenium salts has been disclosed. The strategy does not need external redox reagents or metal catalysts. In combination with C-H thianthrenation aromatics, this provides a new tool the site-selective drugs.

Язык: Английский

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Meerwein‐type Bromoarylation with Arylthianthrenium Salts

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(47)

Опубликована: Сен. 7, 2022

Herein, we report a photocatalyzed Meerwein-type bromoarylation of alkenes with stable arylthianthrenium salts, formed by site-selective C-H thianthrenation. This protocol can be applied to late-stage functionalization variety biomolecules that are difficult access other aryl coupling reagents. Halogen introduction allows for follow-up transformations, affording numerous biologically active skeletons.

Язык: Английский

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Thianthrenium-Enabled Phosphorylation of Aryl C–H Bonds via Electron Donor–Acceptor Complex Photoactivation

Organic Letters, Год журнала: 2023, Номер 25(20), С. 3784 - 3789

Опубликована: Май 16, 2023

An efficient strategy for the preparation of aryl phosphonates via blue-light-promoted single electron transfer process an EDA complex between phosphites and thianthrenium salts has been demonstrated. The corresponding substituted were obtained in good to excellent yields, byproduct thianthrene can be recovered reused quantity. This developed method realizes construction through indirect C-H functionalization arenes, which potential application value drug discovery development.

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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Direct Synthesis of Sulfonamides via Synergetic Photoredox and Copper Catalysis

ACS Catalysis, Год журнала: 2023, Номер 13(17), С. 11580 - 11588

Опубликована: Авг. 18, 2023

Despite the frequent occurrence of sulfonamides in contemporary pharmaceuticals and agrochemicals, synthesis these compounds is limited by availability preexisting sulfur functionality, amine nucleophilicity, functional group compatibility. Herein, we report use synergetic photoredox copper catalysis to synthesize from a variety aryl radical precursors, readily available amines, dioxide source air at room temperature. The reactions proceeded smoothly with various electron-rich electron-deficient amines generate single-step process. Oxygen was deemed be essential for both catalytic cycles, acting as catalyst. Experimental studies, including electron paramagnetic resonance spectroscopy, provided insights into possible mechanism.

Язык: Английский

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Synthesis of Sulfilimines via Aryne and Cyclohexyne Intermediates

Organic Letters, Год журнала: 2023, Номер 25(27), С. 5157 - 5161

Опубликована: Июль 5, 2023

An efficient and metal-free approach for the synthesis of sulfilimines from sulfenamides with aryne cyclohexyne precursors has been developed. The reaction proceeds through unusual S–C bond formation, which offers a novel practical entry to access wide range in moderate good yields excellent chemoselectivity. Moreover, this protocol is amenable gram-scale applicable transformation products into useful sulfoximines.

Язык: Английский

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Metal-Free Chemoselective S-Arylation of Sulfenamides To Access Sulfilimines

The Journal of Organic Chemistry, Год журнала: 2023, Номер 88(13), С. 9352 - 9359

Опубликована: Июнь 16, 2023

A novel and efficient S-arylation of sulfenamides with diaryliodonium salts for the synthesis sulfilimines is developed. The reaction proceeds smoothly under transition-metal-free air conditions, giving rapid access to in good excellent yields via selective S-C bond formation. This protocol scalable exhibits a broad substrate scope, functional group tolerance, chemoselectivity.

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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