Cited by Solvent-Controlled Enantioselective Allylic C–H Alkylation of 2,5-Dihydrofuran via Synergistic Palladium/Nickel Catalysis

Kelvin Pak Shing Cheung, Vladimir Gevorgyan

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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Allylic C–H oxygenation of unactivated internal olefins by the Cu/azodiformate catalyst system DOI

Le Wang,

Yuan She,

Jie Xiao

и другие.

Nature Communications, Год журнала: 2025, Номер 16(1)

Опубликована: Янв. 20, 2025

Язык: Английский

Процитировано

Pd-Catalyzed Allylic Substitution of Azo-Ene Adducts Enables Net Allylic C–H Alkylation of Allylic Alcohols DOI

Yusuke Kuroda, Takashi Chiba,

Moe Kawajiri

и другие.

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Фев. 3, 2025

We present a protocol for regioselective allylic C-H alkylation of alcohols, consisting sequential azo-ene reaction and attendant Pd-catalyzed substitution with Grignard reagents. Notable features this work include: (1) C(sp3)-C(sp3) bond formation is achieved under Pd-catalysis, (2) the proceeds retention configuration at electrophilic carbon as well olefin geometry.

Язык: Английский

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Harnessing Visible/UV Light for the Activation and/or Functionalization of C−H Bonds: Metal‐ and Photocatalyst‐Free Approach DOI

Jitender Bariwal, Erik V. Van der Eycken

The Chemical Record, Год журнала: 2025, Номер unknown

Опубликована: Март 12, 2025

Abstract Photosynthesis in plants has inspired photochemical reactions organic chemistry. Synthetic chemists always seek cost‐effective, operationally simple, averting the use of toxic and difficult‐to‐remove metallic catalysts, atom economical, high product purity reactions. In last few decades, light as a catalyst increased exponentially literature exploded with examples, particularly by using expensive metal complexes, photosensitizers like dyes, hypervalent iodine, or inorganic semiconductors. this report, we have selected interesting examples performed without any photosensitizers. These inherent potential reactants to utilize energy initiate chemical Our main emphasis is highlight structural features that can absorb form an electron donor‐acceptor (EDA) complex during reaction reaction. Considering degree variability reactions, utmost care been taken present most accurate conditions. A short introductory section on will act anchor revolve around discussed explain underlying principle mechanism.

Язык: Английский

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Solvent-Controlled Enantioselective Allylic C–H Alkylation of 2,5-Dihydrofuran via Synergistic Palladium/Nickel Catalysis DOI

Fule Wu,

Hongkai Wang,

Zhenwei Wu

и другие.

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

Опубликована: Май 1, 2025

Enantioenriched, substituted tetrahydrofuran skeletons extensively occur in natural products, bioactive targets, and organic frameworks. The rapid diverse synthesis of these molecules is highly desired yet challenging. Herein, we present a practical synthetic strategy for asymmetric allylic C-H bond functionalization oxyheterocyclic alkenes by making use the synergistic catalysis achiral Pd complex chiral N,N'-dioxide-Ni(II) catalyst. Notably, chemodivergent alkylated products hydroalkylated was readily achieved good outcomes via regulation solvents. Furthermore, post-transformation functionalized 2,5-dihydrofurans provides an innovative route to access skeleton compounds containing multiple stereocenters.

Язык: Английский

Процитировано