Photoinduced Copper‐Catalyzed Asymmetric Three‐Component Coupling of 1,3‐Dienes: An Alternative to Kharasch–Sosnovsky Reaction

Angewandte Chemie International Edition, Год журнала: 2021, Номер 60(42), С. 22956 - 22962

Опубликована: Авг. 18, 2021

Abstract Kharasch–Sosnovsky reaction is one of the most powerful methods for allylic oxidation alkenes. However, inherent radical mechanism and use peroxides as both oxidants oxygen nucleophiles render dearth universal catalytic systems highly enantioselective variants limited scope. Herein, an alternative to asymmetric that utilized a chiral copper catalyst purple‐LED irradiation enable three‐component coupling 1,3‐dienes, oxime esters, carboxylic acids reported. This protocol features mild conditions, remarkable scope functional group tolerance evidenced by >80 examples utility in late‐stage modification pharmaceuticals natural products. Detailed mechanistic studies provide evidences radical‐based pathway.

Язык: Английский

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Copper-photocatalyzed ATRA reactions: concepts, applications, and opportunities

Chemical Society Reviews, Год журнала: 2022, Номер 51(13), С. 5287 - 5299

Опубликована: Янв. 1, 2022

This review summarizes the different applications and underlying concepts that are applied for Cu( i )- or ii )-photocatalyzed difunctionalizations of alkenes.

Язык: Английский

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Photoinduced Pd-Catalyzed Enantioselective Carboamination of Dienes via Aliphatic C–H Bond Elaboration

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(17), С. 12053 - 12062

Опубликована: Апрель 16, 2024

Three-component diene carboaminations offer a potent means to access synthetically valuable allylic amines with rapid molecular complexity escalation. The existing literature primarily discloses racemic examples, necessitating the use of halides/pseudohalides as substrates. This paper introduces photoinduced Pd-catalyzed enantioselective three-component carboamination aryl-substituted 1,3-dienes, leveraging aliphatic C–H bonds for synthesis. reaction employs 10 mol % chiral palladium catalyst and an excess aryl bromide HAT reagent. approach yields diverse allylamines moderate excellent enantioselectivities. Notably, it stands first instance asymmetric reaction, directly utilizing abundant C(sp3)–H bearing partners, such toluene-type substrates, ethers, amines, esters, ketones. protocol exhibits versatility across encompassing aliphatic, aromatic, primary, secondary derivatives. method could serve versatile platform stereoselective incorporation various nucleophiles, dienes, partners.

Язык: Английский

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Cu-Catalyzed Asymmetric Dicarboxylation of 1,3-Dienes with CO₂

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(5), С. 2919 - 2927

Опубликована: Янв. 26, 2024

Dicarboxylic acids and derivatives are important building blocks in organic synthesis, biochemistry, the polymer industry. Although catalytic dicarboxylation with CO2 represents a straightforward sustainable route to dicarboxylic acids, it is still highly challenging limited generation of achiral or racemic acids. To date, asymmetric give chiral has not been reported. Herein, we report first 1,3-dienes via Cu catalysis. This strategy provides an efficient environmentally benign high regio-, chemo-, enantioselectivities. The copper self-relay catalysis, that is, Cu-catalyzed boracarboxylation carboxylated allyl boronic ester intermediates subsequent carboxylation C–B bonds dicarboxylates, key success this dicarboxylation. Moreover, protocol exhibits broad substrate scope, good functional group tolerance, easy product derivatizations, facile synthesis liquid crystalline polyester drug-like scaffolds.

Язык: Английский

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1,4‐Aminoarylation of Butadienes via Photoinduced Palladium Catalysis

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(14)

Опубликована: Фев. 9, 2024

Abstract A visible‐light‐induced, three‐component palladium‐catalyzed 1,4‐aminoarylation of butadienes with readily available aryl halides and aliphatic amines has been developed, affording allylamines excellent E ‐selectivity. The reaction exhibits exceptional control over chemo‐, regio‐, stereoselectivity, a broad substrate scope, high functional group compatibility, as demonstrated by the late‐stage functionalization bioactive molecules. Mechanistic investigations are consistent photoinduced radical Pd(0)‐Pd(I)‐Pd(II)‐Pd(0) Heck‐Tsuji–Trost allylation cascade.

Язык: Английский

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Photoinduced, Palladium-Catalyzed Enantioselective 1,2-Alkylsulfonylation of 1,3-Dienes

ACS Catalysis, Год журнала: 2024, Номер 14(5), С. 3725 - 3732

Опубликована: Фев. 21, 2024

The chiral allylic sulfonylated group is a unique structural motif embedded in range of natural products and pharmaceuticals. Notably, the synthesis structurally diverse derivatives via alkylsulfonylation 1,3-dienes remains underexplored because its inherent challenges stereocontrol regioselectivity. Herein, photoinduced, palladium-catalyzed enantioselective 1,2-alkylsulfonylation conjugated described. A wide variety alkyl bromides, 1,3-dienes, sodium sulfinates could be facilely coupled to generate value-added with high enantioselectivity. Finally, utility this difunctionalization protocol was demonstrated pharmaceutical analogue synthesis.

Язык: Английский

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Recent advances in transition-metal-free trifluoromethylation with Togni's reagents

Organic Chemistry Frontiers, Год журнала: 2021, Номер 9(4), С. 1152 - 1164

Опубликована: Дек. 16, 2021

Transition-metal-free trifluoromethylations have attracted significant research interest driven by the increasing importance of CF 3 -containing compounds.

Язык: Английский

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Photoredox-Catalyzed and Copper(II) Salt-Assisted Radical Addition/Hydroxylation Reaction of Alkenes, Sulfur Ylides, and Water

ACS Catalysis, Год журнала: 2022, Номер 12(6), С. 3279 - 3285

Опубликована: Фев. 25, 2022

A visible light-driven photoredox-catalyzed and copper(II)-assisted three-component radical addition/hydroxylation reaction of alkenes, sulfur ylides, water is reported. This process shows broad substrate scope high functional group tolerance, with respect to both readily available ylides providing high-yielding practical access valuable γ-hydroxy carbonyl compounds. Key the success controlled generation α-carbonyl carbon radicals from via sulfonium salts by a visible-light-driven proton-coupled electron transfer (PCET) strategy in mixture 2,2,2-trifluoroethanol/CH2Cl2. Addition Cu(TFA)2·H2O helps accelerate radical-cation crossover improve efficiency. Mechanistic studies suggest that hydroxy moiety products stems water. study also builds up platform for further investigation into synthetic chemistry ylides.

Язык: Английский

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Copper-Catalyzed Three-Component Photo-ATRA-Type Reaction for Asymmetric Intermolecular C–O Coupling

ACS Catalysis, Год журнала: 2022, Номер 12(17), С. 10925 - 10937

Опубликована: Авг. 22, 2022

Atom transfer radical addition (ATRA) reaction of alkenes has had a significant impact on the field difunctionalization alkenes. Particularly, in three-component photo-ATRA-type processes, rich chemical space and structural diversity could be achieved by smart combination redox-active precursors third coupling components (e.g., halides, C-, N-, O-nucleophiles) under mild conditions. However, inherent complicated mechanisms involving chain or outer-sphere SET incipient intermediates have led to dearth general catalytic methods for highly enantioselective variants, especially those regarding asymmetric intermolecular C–O bond formation. Here, we report visible-light-induced copper-catalyzed with oxime esters carboxylic acids. In this process, cross-coupling between sp3-hybridized carbon radicals acids was enabled formation an aryl π-bond-engaged [σ + π]-copper complex. This working hypothesis renders naphthyl extended conjugation suitable substrates allows good stereocontrol. exhibits broad substrate scope high functional group tolerance respect each component, giving desired products generally yields enantioselectivity (>70 examples; up 97% ee). Preliminary experimental computational studies are also performed gain insight into mechanism stereoregulatory elements. finding provides promising platform development other benzylic-type radical-based reactions.

Язык: Английский

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Emerging Trends in Copper-Promoted Radical-Involved C–O Bond Formations

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(32), С. 17527 - 17550

Опубликована: Авг. 2, 2023

The C–O bond is ubiquitous in biologically active molecules, pharmaceutical agents, and functional materials, thereby making it an important group. Consequently, the development of bond-forming reactions using catalytic strategies has become increasingly research topic organic synthesis because more conventional methods involving strong base acid have many limitations. In contrast to ionic-pathway-based methods, copper-promoted radical-mediated formation experiencing a surge interest owing renaissance free-radical chemistry photoredox catalysis. This Perspective highlights appraises state-of-the-art techniques this burgeoning field. contents are organized according different reaction types working models.

Язык: Английский

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