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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Photoexcited Copper-Catalyzed Enantioselective Allylic C(sp³)–H Acyloxylation of Acyclic Internal Alkenes

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(39), С. 27196 - 27203

Опубликована: Сен. 17, 2024

The functionalization of C-H bonds streamlines the synthesis complex molecules by eliminating need for substrate preactivation. Traditionally, Kharasch-Sosnovsky reaction, which directly oxidizes allylic into esters under copper catalysis, has been hampered long reaction times, limited scope, and low enantioselectivity with acyclic olefins. Herein, we present a novel, visible light-driven, copper-catalyzed asymmetric that overcomes these challenges. This method expands scope to include internal alkenes improves conditions using eco-friendly light catalysis. It enhances radical reactivity achieves superior regioselectivity in producing acyloxylation products. breakthrough significantly advances direct techniques, offering more efficient sustainable approach synthesizing chiral molecules.

Язык: Английский

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A Photo- and Cobalt-Catalyzed Highly Selective and Divergent Hydrofunctionalization of 1,3-Dienes with Phenols

Chemical Science, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

An applicable cobalt-hydride-mediated selective, divergent hydroetherification and sequential hydroetherification/hydroarylation of 1,3-dienes with simple phenol feedstocks under a photoredox cobalt catalytic system have been developed. A variety allyl aryl ethers value-added chroman derivatives can be obtained in good to excellent yields stereoselectivity. This method not only obviates the need for extra hydrosilanes stoichiometric oxidants, thereby offering exceedingly mild conditions alkene hydroetherification, but also represents first case CoH-HAT-catalyzed double hydrofunctionalization alkenes sole nucleophile. The continuous selective bond-forming expands applications cobalt-hydride MHAT reaction provides novel approach design synthesis heterocyclic molecules.

Язык: Английский

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Photoinduced Pd‐Catalyzed Direct Sulfonylation of Allylic C–H Bonds

Angewandte Chemie International Edition, Год журнала: 2024, Номер 64(1)

Опубликована: Сен. 17, 2024

Allylic sulfones are valuable motifs due to their medicinal and biological significance versatile chemical reactivities. While direct allylic C-H sulfonylation represents a straightforward desirable approach, these methods primarily restricted terminal alkenes, leaving the engagement of internal counterparts formidable challenge. Herein we report photocatalytic approach that accommodates both cyclic acyclic alkenes with diverse substitution patterns electronic properties. Importantly, obtained can be readily diversified into wide range products, thus enabling formal alkene transposition all-carbon quaternary center formation through sequential functionalization.

Язык: Английский

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Palladium-catalyzed allylic C-H alkylation of terminal olefins with 3-carboxamide oxindoles

Organic & Biomolecular Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

A novel palladium-catalyzed allylic C-H alkylation of terminal olefins with 3-carboxamide oxindoles is described. variety new 3-carboxamide-3-allylation an all-carbon quaternary center were obtained in moderate to good yields (up 99%). In addition, the asymmetric version this reaction was also explored, providing enantioselectivity.

Язык: Английский

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

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

Опубликована: Янв. 20, 2025

Язык: Английский

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

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

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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Palladium-Catalyzed Transfer Iodination from Aryl Iodides to Nonactivated C(sp³)–H Bonds

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

Опубликована: Апрель 4, 2025

We report a new strategy for the catalytic iodination of nonactivated C(sp3)-H bonds. The method merges concepts shuttle and light-enabled palladium catalysis to employ aryl iodides as both hydrogen atom transfer reagents iodine donors. A noncanonical Pd0/PdI cycle is harnessed from C(sp2) bond under mild conditions, which tolerate sensitive functional groups. This mechanism also applied implement thiolation that exploits reversible steps system.

Язык: Английский

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

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

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