Recent Advances in Visible Light Induced Palladium Catalysis

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(9)

Published: Nov. 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.

Language: Английский

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

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 4665 - 4680

Published: March 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.

Language: Английский

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Merging of Light/Dark Palladium Catalytic Cycles Enables Multicomponent Tandem Alkyl Heck/Tsuji–Trost Homologative Amination Reaction toward Allylic Amines

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(33), P. 18497 - 18505

Published: Aug. 9, 2023

A visible light-induced palladium-catalyzed homologative three-component synthesis of allylic amines has been developed. This protocol proceeds

Language: 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, Journal Year: 2024, Volume and Issue: 63(26)

Published: April 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.

Language: Английский

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Escape from Hydrofunctionalization: Palladium Hydride‐Enabled Difunctionalization of Conjugated Dienes and Enynes

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(47)

Published: Oct. 3, 2023

Abstract Palladium hydrides are traditionally employed in hydrofunctionalization (i.e. monofunctionalization) of conjugated dienes and enynes, owning to its facile protic hydropalladation electron‐rich (or neutral) unsaturated bonds. Herein, we report a mild PdH‐catalyzed difunctionalization enynes. This protocol is enabled by the chemoselectivity switch initial step achieved visible light enhancement hydricity PdH species. method allows for cascade annulation enynes with various easily available abundant substrates, such as acrylic acids, amides, Baylis–Hillman adducts, toward wide range alkenyl or alkynyl lactones, lactams, tetrahydrofurans. also provides an easy access complex spiro‐fused tricyclic frameworks.

Language: Английский

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Reductive Cross-Coupling of Olefins via a Radical Pathway

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(46), P. 25098 - 25102

Published: Nov. 10, 2023

Olefins are widely available at low costs, which explains the usefulness of developing new methods for their functionalization. Here we report a simple protocol that uses photoredox catalyst and an inexpensive thiol to stitch together two olefins, forming C-C bond. Specifically, electron-poor olefin is reduced by generate, upon protonation, carbon radical, then captured neutral olefin. This intermolecular cross-coupling process provides tool rapidly synthesizing sp3-dense molecules from olefins using unconventional disconnection.

Language: Английский

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Reversible Radical Addition Guides Selective Photocatalytic Intermolecular Thiol‐Yne‐Ene Molecular Assembly

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(13)

Published: Jan. 19, 2024

Abstract In modern organic chemistry, harnessing the power of multicomponent radical reactions presents both significant challenges and extraordinary potential. This article delves into this scientific frontier by addressing critical issue controlling selectivity in such complex processes. We introduce a novel approach that revolves around reversible addition thiyl radicals to multiple bonds, reshaping landscape reactions. The key lies intricate interplay between reversibility energy landscapes governing C−C bond formation thiol‐yne‐ene developed not only allows prioritize cascade, dominating over alternative reactions, but also extends scope coupling products obtained from alkenes alkynes various structures electron density distributions, regardless their relative polarity difference, opening doors more versatile synthetic possibilities. present study, we provide powerful tool for atom‐economical C−S formation, paving way efficient synthesis molecules. Carrying out our experimental computational studies, elucidated fundamental mechanisms underlying cascades, knowledge can be broadly applied field chemistry.

Language: Английский

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Unveiling Heavier Dihydropyridine Chalcogenol Esters in Metallaphotoredox Catalyst-Enabled Regioselective Hydrothio(seleno)carbonylation

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 23, 2025

Herein, aromaticity-driven thio(seleno)ester group transfer from novel 1,4-dihydropyridine thio(seleno)esters to alkene feedstocks is disclosed by merging palladium and photoredox catalysis. In this process, photoactivation of dihydropyridine integrated with regioselective hydrometalation alkenes, avoiding photoinduced Pd-C bond homolysis organopalladium intermediates. Additionally, a hydroselenocarbonylation an accomplished for the first time using bench-stable selenoester reagent. The activation mode thioesters has been illustrated detailed mechanistic studies, spectroscopic analysis, intermediate trapping, isotope labeling experiments.

Language: Английский

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Illuminating Palladium Catalysis

Accounts of Chemical Research, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 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

Language: Английский

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Mononuclear palladium(I) and palladium(III) coordination compounds

Coordination Chemistry Reviews, Journal Year: 2025, Volume and Issue: 535, P. 216605 - 216605

Published: March 17, 2025

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