Catalysis in the Excited State: Bringing Innate Transition Metal Photochemistry into Play

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 4665 - 4680

Опубликована: Март 5, 2025

Transition metal catalysis is an indispensable tool for organic synthesis that has been harnessed, modulated, and perfected many decades by careful selection of centers ligands, giving rise to synthetic methods with unparalleled efficiency chemoselectivity. Recent developments have demonstrated how light irradiation can also be recruited as a powerful dramatically alter the outcome catalytic reactions, providing access innovative pathways remarkable potential. In this context, adoption photochemical conditions mainstream strategy drive reactions unveiled exciting opportunities exploit rich excited-state framework transition metals applications. This Perspective examines advances in application complexes standalone photocatalysts, exploiting innate reactivity their excited states beyond common use photoredox catalysts. An account relevant examples dissected provide discussion on electronic reorganization, orbitals involved, associated different types states. analysis aims practitioners fundamental principles guiding strategies understand, design, apply light-activation homogeneous synthesis.

Язык: Английский

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Aryl-to-alkyl radical relay Heck reaction of amides with vinyl arenes

Chemical Science, Год журнала: 2023, Номер 14(13), С. 3580 - 3586

Опубликована: Янв. 1, 2023

Herein, a photo-induced palladium catalyzed aryl-to-alkyl radical relay Heck reaction at α-C(sp 3 )–H site of amide has been developed. This method is scalable and operationally simple. Mechanistic studies reveal the nature this transformation.

Язык: Английский

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Biomimetic Photoexcited Cobaloxime Catalysis in Organic Synthesis

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(33)

Опубликована: Май 22, 2024

Abstract Drawing inspiration from nature has long been a cornerstone of chemical innovation, with natural systems offering wealth untapped potential for discovery. In this minireview, we delve into the burgeoning field cobaloxime catalysis in organic synthesis, which mimics catalytic activity organometallic alkylcobalamine enzymes. Our focus lies on elucidating latest advancements area, as well delineating primary mechanistic pathways at play. By describing, and comparing these mechanisms, provide comprehensive overview current state‐of‐the‐art, while also shedding light key unresolved challenges that await further exploration.

Язык: Английский

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Photocatalyzed H₂-Acceptorless Dehydrogenative Borylation by Using Amine Borane

ACS Catalysis, Год журнала: 2024, Номер 14(11), С. 8666 - 8675

Опубликована: Май 20, 2024

Catalytic dehydrogenative borylation of alkenes is arguably the most straightforward approach for synthesizing alkenyl boronates, as it eliminates need alkene or boranes prefunctionalizion. While transition-metal catalysis has conventionally been employed this transformation, competitive side reactions including hydroborylation, overborylation, and regioisomer formation always exist. In study, we present a radical catalytic borylation, which involves synergistic merger photoredox/HAT/cobalt catalysis, thereby circumventing necessity noble metals, sacrificial hydrogen acceptors, high temperatures. This method employs stable cost-effective amine borane reagents feedstocks, resulting in sole byproduct H2. methodology facilitates conversion diverse array functionalized into valuable organoboron reagents. Furthermore, late-stage complex molecules demonstrates levels site selectivity.

Язык: Английский

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Decatungstate/Cobalt Dual Catalyzed Dehydrogenation of Ketones Enabled by Polarity-Matched Site-Selective Activation

ACS Catalysis, Год журнала: 2024, Номер 14(14), С. 11138 - 11146

Опубликована: Июль 11, 2024

Язык: Английский

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Selective N-α-C–H alkylation of cyclic tertiary amides via visible-light-mediated 1,5-hydrogen atom transfer

Organic Chemistry Frontiers, Год журнала: 2023, Номер 10(17), С. 4394 - 4399

Опубликована: Янв. 1, 2023

Herein, we report an effective C–H bond activation-alkylation strategy for 2-iodobenzoyl protected cyclic amines at the N -α-position through a visible-light mediated 1,5-hydrogen atom transfer (HAT) process.

Язык: Английский

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Direct C(sp3)-H functionalization with aryl and alkyl radicals as intermolecular hydrogen atom transfer (HAT) agents

Chemical Communications, Год журнала: 2024, Номер unknown

Опубликована: Янв. 1, 2024

Recent years have witnessed the emergence of direct intermolecular C(sp

Язык: Английский

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Cooperative Fe/Co-Catalyzed Remote Desaturation for the Synthesis of Unsaturated Amide Derivatives

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(7), С. 4985 - 4992

Опубликована: Фев. 6, 2024

Unsaturated amides represent common functional groups found in natural products and bioactive molecules serve as versatile synthetic building blocks. Here, we report an iron(II)/cobalt(II) dual catalytic system for the syntheses of distally unsaturated amide derivatives. The transformation proceeds through iron nitrenoid-mediated 1,5-hydrogen atom transfer (1,5-HAT) mechanism. Subsequently, radical intermediate undergoes hydrogen abstraction from vicinal methylene by a cobaloxime catalyst, efficiently yielding β,γ- or γ,δ-unsaturated derivatives under mild conditions. efficiency Co-mediated HAT can be tuned varying different auxiliaries, highlighting generality this protocol. Remarkably, desaturation protocol is also amenable to practical scalability, enabling synthesis carbamates ureas, which readily converted into various valuable molecules.

Язык: Английский

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Accessing Benzoazepine Derivatives via Photoinduced Radical Relay Formal [5 + 2] Reaction of Amide/Alkyne Enabled by Palladium Catalysis

Organic Letters, Год журнала: 2024, Номер 26(13), С. 2662 - 2667

Опубликована: Март 26, 2024

A novel class of alkyne-tethered amides facilitates an unprecedented photoinduced palladium-catalyzed radical relay formal [5 + 2] reaction. This innovative strategy allows for the rapid construction diverse fused benzoazepine structures, yielding structurally and compelling compounds. With a broad substrate scope excellent functional group tolerance, methodology synthesizes biologically active Notably, resulting tricyclic benzo[b]azepines offer diversification opportunities through simple transformations. DFT calculations elucidate seven-membered ring closure mechanism involving alkenyl Pd(I) rebound alongside concerted metalation–deprotonation (CMD) process.

Язык: Английский

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Transition-Metal-Catalyzed Remote C–H Bond Functionalization of Cyclic Amines

SynOpen, Год журнала: 2022, Номер 06(04), С. 286 - 305

Опубликована: Авг. 24, 2022

Abstract C–H bond functionalization is one of the most effective strategies for rapid synthesis cyclic amines containing substituents on ring, which are core structures many bioactive molecules. However, it much more challenging to perform this strategy remote bonds compared α-C–H amines. This graphical review aims provide a concise overview transition-metal-catalyzed methods Examples categorized and demonstrated according mechanistic pathways that initiate reactions amine substrates. Where relevant, selected substrate scope detailed reaction mechanisms given.

Язык: Английский

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