General Regio- and Diastereoselective Allylic C–H Oxygenation of Internal Alkenes

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(27), P. 18218 - 18223

Published: June 26, 2024

Branched allylic esters and carboxylates are fundamental motifs prevalent in natural products drug molecules. The direct C-H oxygenation of internal alkenes represents one the most straightforward approaches, bypassing requirement for an leaving group as classical Tsuji-Trost reaction. However, current methods suffer from limited scope─often accompanied by selectivity issues─thus hampering further development. Herein we report a photocatalytic platform general solution to these problems, enabling coupling diverse with carboxylic acids, alcohols, other

Language: Английский

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Dynamic Kinetic Activation of Aziridines Enables Radical-Polar Crossover (4 + 3) Cycloaddition with 1,3-Dienes

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 10, 2025

The cycloaddition of aziridines with unsaturated compounds is a valuable method for synthesizing nitrogen heterocycles. However, this process predominantly substrate-controlled, posing significant challenges in regulating the regioselectivity C–N bond cleavage. In study, we report nickel-catalyzed dynamic kinetic activation strategy that enables catalyst-controlled aziridines. Various types aziridines, including 2-phenyl, 2-carbonyl, 2-alkyl, and disubstituted consistently cleave their more sterically hindered bonds to generate 1,3-radical anion intermediates. These intermediates participate highly regioselective 1,4-Heck/allylic substitution cascade aromatic branched 1,3-dienes, resulting radical-polar crossover (4 + 3) produces seven-membered azepine products. This approach not only complements traditional dipolar cycloaddition, which typically act as zwitterionic 1,3-dipoles, but also introduces an unusual mode 1,3-dienes. Experimental investigations density functional theory (DFT) calculations provide insight into reaction mechanism.

Language: Английский

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Photoinduced Pd-Catalyzed Formal Asymmetric Allylic Substitution of Piperidine Scaffolds

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 4384 - 4393

Published: Feb. 26, 2025

Language: Английский

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Functionalization of 1,3‐Butadiene Derivatives under Photo/Electrocatalysis

European Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 27(28)

Published: May 20, 2024

Abstract In recent years, the functionalization of 1,3‐butadiene has become an attractive strategy for constructing allyl compounds with molecular and structural complexity, current research focuses on synthetic chemistry organic synthesis. Compared traditional synthesis method, methods promoted by photochemistry or electrochemistry represent environmentally friendly mild strategy. this review, reactions under photochemical/electrochemical processes in years are reviewed according to classification systems, particular emphasis corresponding reaction mechanism, which lays a foundation further exploration new catalytic methods.

Language: Английский

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Excited Pd-catalyzed dearomative 1,4-dicarbofunctionalization of nonactivated aromatic rings

Organic Chemistry Frontiers, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

1,4-difunctionalization of nonactivated arenes has been accomplished by the excited-palladium catalysis via radical generation a cyclohexadienyl-Pd( ii ) intermediate.

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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Cu(II)/Photoredox-Catalyzed Aminoacylation of Vinyl Bromides

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

Published: March 24, 2025

A novel C–C coupling reaction of vinyl bromides with carboxamides has been developed through Cu(OAc)2/photocatalysis. This process features regioselective carboxamido carbon-vinylation under mild conditions. Mechanistic studies suggest that the formation an acyl-Cu(I) intermediate plays a crucial role regard to enabling this transformation.

Language: Английский

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Controllable Radical Reactions of 1,3-Dienes with Light

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 7749 - 7779

Published: April 25, 2025

Language: Английский

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Divergent and Enantioselective Synthesis of Three Types of Chiral Polycyclic N-Heterocycles via Copper-Catalyzed Dearomative Cyclization

ACS Central Science, Journal Year: 2025, Volume and Issue: unknown

Published: May 2, 2025

Language: Английский

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Enantioselective 1,2-Carboamination of 1,3-Dienes with N-Hydroxyphthalimide (NHP) Esters Enabled by a Photoinduced Pd Catalysis

Organic Letters, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 3, 2024

Herein, a photoinduced, Pd-catalyzed direct 1,2-carboamination of conjugated 1,3-dienes has been successfully achieved. Sequential regioselective C-C bond and enantioselective C-N formation allows rapid assembly wide range value-added chiral allylic amines from readily available

Language: Английский

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