Engaging Alkenes in Metallaphotoredox: A Triple Catalytic, Radical Sorting Approach to Olefin-Alcohol Cross-Coupling

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(18), С. 12300 - 12309

Опубликована: Апрель 24, 2024

Metallaphotoredox cross-coupling is a well-established strategy for generating clinically privileged aliphatic scaffolds via single-electron reactivity. Correspondingly, expanding metallaphotoredox to encompass new C(

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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Strategies and Mechanisms of First-Row Transition Metal-Regulated Radical C–H Functionalization

Chemical Reviews, Год журнала: 2024, Номер 124(17), С. 10192 - 10280

Опубликована: Авг. 8, 2024

Radical C–H functionalization represents a useful means of streamlining synthetic routes by avoiding substrate preactivation and allowing access to target molecules in fewer steps. The first-row transition metals (Ti, V, Cr, Mn, Fe, Co, Ni, Cu) are Earth-abundant can be employed regulate radical functionalization. use such is desirable because the diverse interaction modes between metal complexes species including addition center, ligand complexes, substitution single-electron transfer radicals hydrogen atom noncovalent complexes. Such interactions could improve reactivity, diversity, selectivity transformations allow for more challenging reactions. This review examines achievements this promising area over past decade, with focus on state-of-the-art while also discussing existing limitations enormous potential high-value regulated these metals. aim provide reader detailed account strategies mechanisms associated

Язык: Английский

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Alcohols as Alkyl Synthons Enabled by Photoredox-Catalyzed Deoxygenative Activation

ACS Catalysis, Год журнала: 2024, Номер 14(17), С. 13451 - 13496

Опубликована: Авг. 26, 2024

Alcohols are abundant with versatile structural variety and have ample use as pivotal functional groups in numerous organic processes. Because of their frequent occurrence enumerable natural products, bioactive molecules, medicinal components, alcohol functionalities provide a promising scope research to advance the operational diversity for improving clinical success. Recent years witnessed design modern C–C C–heteroatom bond-forming approaches easily accessible commercially available unactivated aliphatic alcohols native adaptive sp3 handles, hence offering groundbreaking transformative pathways functionalization complex molecular architectures. The judicial application appropriate activating generate alkyl radical from through C–O bond fragmentation employ it potential alkylating agent unfolds unique synthetic strategies, thereby replacing obvious requirement halides. This review elaborately discusses recent trends regarding using C(sp3)-centered various chemical transformations by exploiting different activation modes disrupter under photoredox catalysis. presentation is organized nature scaffolds, kind formation, progress achieved this domain since original discovery providing illustrative examples mechanistic details, focus on difficulties future prospects.

Язык: Английский

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Aminoalkylation of Alkenes Enabled by Triple Radical Sorting

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

Опубликована: Янв. 9, 2025

The direct synthesis of C(sp3)-rich architectures is a driving force for innovation in synthetic organic chemistry. Such scaffolds impart beneficial properties onto drug molecules that correlate with greater clinical success. Consequently, there strong impetus to develop new methods by which access sp3-rich from commercial feedstocks, such as alkenes. Herein, we report three-component aminoalkylation reaction utilizes the principles triple radical sorting regioselectively add N-centered and C-centered radicals across This process relies upon photoredox catalysis transform alkyl bromides reductively activated precursors into high-energy species redox-neutral fashion. A broad scope coupling partners demonstrated, multiple applications, including facile syntheses pharmacophoric substituted N-heterocycles.

Язык: Английский

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Ni-Catalyzed Regioselective Alkylarylation of Unactivated Alkenes in Amines Enabled by Cooperative Ligand Effects of Nitriles and Electron-Deficient Alkenes

Journal of the American Chemical Society, Год журнала: 2025, Номер 147(2), С. 1667 - 1676

Опубликована: Янв. 7, 2025

We report a Ni-catalyzed vicinal alkylarylation of unactivated alkenes in γ,δ- and δ,ε-alkenylamines with aryl halides alkylzinc reagents. The reaction is enabled by amine coordination can use all primary, secondary, tertiary amines. constructs two new C(sp3)-C(sp3) C(sp3)-C(sp2) bonds produces δ- ε-arylamines C(sp3)-branching at the γ- δ-positions. A variety heteroaryl iodides both primary secondary reagents be used as coupling carbon sources. Mechanistic studies suggest that cooperative effect organic nitriles electron-deficient (EDAs) ligands.

Язык: Английский

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Ligand-enabled, Ni-catalyzed dicarbofunctionalization of alkenyl alcohols

Chem Catalysis, Год журнала: 2025, Номер unknown, С. 101261 - 101261

Опубликована: Фев. 1, 2025

Язык: Английский

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Aryl-Radical-Initiated Z-Olefin Synthesis via Synergistic Palladium and Photocatalysis

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Фев. 7, 2025

We report a novel photocatalyzed selective functionalization of terminal olefins for the synthesis Z-olefins and cyclobutanes under mild conditions in excellent yields. A series Z-cinnamic acid derivatives, enamines, amide-containing were efficiently synthesized using this method. Mechanistic studies indicated that success reaction is based on triple radical relay strategy, anion-π interaction aryl halide activation generation, palladium controlling chemoselectivity radical, photocatalyst stereoselectivity via diradical species, respectively.

Язык: Английский

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Photoredox-catalyzed deoxygenative radical transformation of alcohols to sulfinamides

RSC Advances, Год журнала: 2025, Номер 15(6), С. 4532 - 4535

Опубликована: Янв. 1, 2025

Sulfinamides play a crucial role in organic synthesis and pharmaceuticals.

Язык: Английский

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Pulse radiolysis studies of open-formed diarylethenes in organic solvent: Does the radiochromism proceed in radical ions and triplet state?

Chemical Physics Letters, Год журнала: 2025, Номер unknown, С. 141945 - 141945

Опубликована: Фев. 1, 2025

Язык: Английский

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