Recent Advances in Visible Light Induced Palladium Catalysis

Angewandte Chemie International Edition, Год журнала: 2023, Номер 63(9)

Опубликована: Ноя. 14, 2023

Visible light-induced Pd catalysis has emerged as a promising subfield of photocatalysis. The hybrid nature radical species enabled wide array radical-based transformations otherwise challenging or unknown via conventional chemistry. In parallel to the ongoing pursuit alternative, readily available precursors, notable discoveries have demonstrated that photoexcitation can alter not only oxidative addition but also other elementary steps. This Minireview highlights recent progress in this area.

Язык: Английский

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Recent advances in C(sp³)–N bond formation via metallaphoto-redox catalysis

Chemical Communications, Год журнала: 2024, Номер 60(50), С. 6340 - 6361

Опубликована: Янв. 1, 2024

In this review, the state-of-the-art advances in radical-involved C(sp 3 )–N bond formation via metallaphotoredox catalysis have been highlighted, which are organized according to different catalytic modes, reaction types, and substrate classes.

Язык: Английский

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Catalytic Asymmetric Cascade Dearomatization of Indoles via a Photoinduced Pd‐Catalyzed 1,2‐Bisfunctionalization of Butadienes

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(26)

Опубликована: Апрель 20, 2024

Photoinduced Pd-catalyzed bisfunctionalization of butadienes with a readily available organic halide and nucleophile represents an emerging attractive method to assemble versatile alkenes bearing various functional groups at the allylic position. However, enantiocontrol and/or diastereocontrol in C-C or C-X bond-formation step have not been solved due open-shell process. Herein, we present cascade asymmetric dearomatization reaction indoles via photoexcited 1,2-biscarbonfunctionalization 1,3-butadienes, wherein control on both electrophile part is achieved for first time photoinduced butadienes. This delivers structurally novel chiral spiroindolenines two contiguous stereogenic centers high diastereomeric ratios (up >20 : 1 dr) good excellent enantiomeric 97 3 er). Experimental computational studies mechanism confirmed radical pathway involving excited-state palladium catalysis. The alignment non-covalent interactions between substrate catalyst were found be essential stereocontrol.

Язык: Английский

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Illuminating Palladium Catalysis

Accounts of Chemical Research, Год журнала: 2025, Номер unknown

Опубликована: Фев. 26, 2025

ConspectusThe past decade has witnessed significant advancements of visible-light-induced photocatalysis, establishing it as a powerful and versatile tool in organic synthesis. The major focus this field centered on the development methodologies that either rely solely photocatalysts or combine photocatalysis with other catalytic methods, such transition metal catalysis, to address broader more diverse array transformations. Within rapidly evolving area, subfield we refer garnered attention due its growing impact mechanistic uniqueness. A distinguishing feature is dual functionality single complex, which not only acts photocatalyst initiate photochemical processes but also functions traditional catalyst, facilitating key bond-breaking bond-forming events. As such, an exogenous required photocatalysis. However, implications harnessing both excited- ground-state reactivities complex can extend beyond simplification. One most compelling aspects area photoexcited complexes exhibit unique inaccessible through conventional thermal photocatalytic approaches. These distinct be leveraged accomplish novel transformations by engaging entirely different substrate pool unlocking new known substrates.In 2016, our group pioneered use phosphine-ligated palladium catalysts upon visible-light irradiation engage substrates radical reactions. In initial discovery, showed photoexcitation redirect well-established oxidative addition Pd(0) into aryl iodides toward unprecedented process, generating hybrid Pd(I) species. We subsequently extended strategy formation alkyl radicals from halides. reactive intermediates have been harnessed wide variety transformations, including desaturation, Heck reactions, alkene difunctionalization cascades, among others.Seeking further expand avenue, achieved first example asymmetric context allylic C–H amination, where catalyst now plays triple duty additionally controlling stereochemical outcome reaction. parallel reaction established diazo compounds, strained molecules, electron-deficient alkenes serve precursors halides redox-active esters. Notably, engagement made possible photoinduced hydricity enhancement Pd–H species, representing mode reactivity.This Account presents discovery organized type explored. Given rapid progress field, anticipate will provide readers guiding principles inspiration for designing developing efficient

Язык: Английский

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Direct Alkylation of Glycine Derivatives via Photoinduced Palladium Catalysis, Utilizing Intermolecular Hydrogen Atom Transfer Mediated by Alkyl Radicals

ACS Catalysis, Год журнала: 2023, Номер 13(24), С. 15652 - 15662

Опубликована: Ноя. 21, 2023

Unveiling the alkyl/Pd hybrid species is a unique sp3-C-centered radical for facilitating intermolecular hydrogen atom transfer (HAT) in development of direct alkylation glycine derivatives. This transformative reaction proceeds smoothly under simple and mild conditions, exhibiting impressive versatility terms substrate scope encompassing both derivatives alkyl bromides while showcasing remarkable tolerance toward diverse functional groups. To shed light on underlying mechanism, extensive investigations involving control experiments, deuterium labeling, clocking, kinetic studies have been conducted. The collected data consistently support pathway formation Pd(I)/alkyl followed by HAT elimination steps that lead to situ imine intermediates, ultimately culminating final stage through addition.

Язык: Английский

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Mechanistic insights into excited-state palladium catalysis for C–S bond formations and dehydrogenative sulfonylation of amines

Nature Communications, Год журнала: 2023, Номер 14(1)

Опубликована: Окт. 19, 2023

Photocatalytic selective C(sp3)-H activation/cross-coupling reactions are appealing in organic synthesis. In this manuscript, we describe the development of photoexcited-state Pd-catalyzed dehydrogenative β-sulfonylation using amines and aryl sulfonyl chlorides via intermolecular hydrogen atom transfer C-S cross-coupling processes at room temperature. The transformation can be achieved by direct generation two distinct Pd-radical hybrid species their capability to promote different reactivities from Pd(0) chlorides, allowing for efficient conversion readily available into stable sulfonyl-substituted enamines in-depth experimental, computational, transient optical spectroscopic study catalytic applications a functionalization event provide evidence both static dynamic quenching, as well inner-sphere outer-sphere mechanisms.

Язык: Английский

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Metallaphotoredox catalysis for sp3 C–H functionalizations through single-electron transfer

Nature Catalysis, Год журнала: 2024, Номер 7(9), С. 963 - 976

Опубликована: Сен. 24, 2024

Язык: Английский

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Photoredox Promoted Barbier-Type Reaction of Alkyl Iodides with N-Alkyl and N-Aryl Imines

The Journal of Organic Chemistry, Год журнала: 2023, Номер 88(2), С. 1260 - 1269

Опубликована: Янв. 6, 2023

The reaction of organozinc reagents with unactivated imines is accelerated when performed in the presence a photocatalyst under blue light irradiation. Coordination between Lewis acidic zinc iodide and imine key factor responsible for efficiency. method can be carried out using alkyl iodides Barbier conditions.

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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Copper(I)-based metal-metal-to-ligand charge transfer excited state with halogen-atom transfer photo-reactivity and photocatalysis

Chem, Год журнала: 2024, Номер 10(9), С. 2807 - 2828

Опубликована: Июнь 5, 2024

Язык: Английский

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