Cross-Electrophile Coupling: Principles, Methods, and Applications in Synthesis

Chemical Reviews, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 26, 2024

Cross-electrophile coupling (XEC), defined by us as the cross-coupling of two different σ-electrophiles that is driven catalyst reduction, has seen rapid progression in recent years. As such, this review aims to summarize field from its beginnings up until mid-2023 and provide comprehensive coverage on synthetic methods current state mechanistic understanding. Chapters are split type bond formed, which include C(sp

Language: Английский

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Halogen‐Atom Transfer Enabled Catalytic Enantioselective Coupling to Chiral Trifluoromethylated Alkynes via Dual Nickel and Photocatalysis

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(28)

Published: April 15, 2024

With halogen-atom transfer as an effective tool, a novel catalytic enantioselective protocol to generate chiral trifluoromethylated alkynes has been established by cooperative photoredox and nickel catalysis system, providing straightforward modular route access this type of product in good yields enantioselectivities. The process is essential for the reaction strategy offers another promising way utilize alkyl halides with highly negative reduction potentials. It firstly expands nickel-catalyzed asymmetric reductive cross-couplings organohalides from traditional single-electron transfer.

Language: Английский

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Deoxygenative Transformation of Alcohols via Phosphoranyl Radical from Exogenous Radical Addition

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(17)

Published: Feb. 15, 2024

Abstract A general approach to the direct deoxygenative transformation of primary, secondary, and tertiary alcohols has been developed. It undergoes through phosphoranyl radical intermediates generated by addition exogenous iodine trivalent alkoxylphosphanes. Since these alkoxylphosphanes are readily in situ obtained from commercially available, inexpensive chlorodiphenylphosphine, a diverse range with various functional groups can be utilized proceed cross‐couplings alkenes or aryl iodides. The selective polyhydroxy substrates rapid synthesis complex organic molecules also demonstrated this method.

Language: Английский

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Deacylative arylation and alkynylation of unstrained ketones

Science Advances, Journal Year: 2024, Volume and Issue: 10(17)

Published: April 26, 2024

Ketones are ubiquitous in bioactive natural products, pharmaceuticals, chemical feedstocks, and synthetic intermediates. Hence, deacylative coupling reactions enable the versatile elaboration of a plethora chemicals to access complex drug candidates products. Here, we present arylation alkynylation strategies for synthesis wide range alkyl-tethered arenes alkynes from cyclic ketones methyl under dual nickel/photoredox catalysis. This reaction begins by generating pre-aromatic intermediate (PAI) through condensation ketone

Language: Английский

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Dual Nickel- and Photoredox-Catalyzed Asymmetric Reductive Cross-Couplings: Just a Change of the Reduction System?

Accounts of Chemical Research, Journal Year: 2024, Volume and Issue: 57(14), P. 1997 - 2011

Published: July 4, 2024

ConspectusIn recent years, nickel-catalyzed asymmetric coupling reactions have emerged as efficient methods for constructing chiral C(sp

Language: Английский

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Ni-catalyzed enantioconvergent deoxygenative reductive cross-coupling of unactivated alkyl alcohols and aryl bromides

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: March 28, 2024

Abstract Transition metal-catalyzed enantioconvergent cross-coupling of an alkyl precursor presents a promising method for producing enantioenriched C(sp 3 ) molecules. Because alcohol is ubiquitous and abundant family feedstock in nature, the direct reductive coupling aryl halide enables efficient access to valuable compounds. Although several strategies have been developed overcome high bond dissociation energy C − O bond, asymmetric pattern remains unknown. In this report, we describe realization deoxygenative unactivated (β-hydroxy ketone) bromide presence NHC activating agent. The approach can accommodate substituents various sizes functional groups, its synthetic potency demonstrated through gram scale reaction derivatizations into other compound families. Finally, apply our convergent synthesis four β-aryl ketones that are natural products or bioactive

Language: Английский

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Photocatalytic C–P bond formation based on the reaction of carbon-centered radicals with phosphides

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(17), P. 4882 - 4894

Published: Jan. 1, 2024

This review focuses on the synthesis of C–P bonds using carbon-centered radicals with phosphorous compounds different valence states (P III , P V 4 ) under photocatalysis.

Language: Английский

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Direct Synthesis of β-Amino Boronates via Amide α-C–H Bond Activation and C(sp³)–C(sp³) Coupling under Dual Ni/Photoredox Catalysis

ACS Catalysis, Journal Year: 2023, Volume and Issue: 14(1), P. 547 - 553

Published: Dec. 26, 2023

Direct transformations of readily available amines or amides via C–H bond functionalization could provide a fast route for accessing complex molecules. While various groups have been successfully incorporated into the α position nitrogen atom with photoredox system activation, couplings functionalized alkyl halides are still very challenging. Herein, we report direct and convenient protocol β-amino boronates through C(sp3)–C(sp3) coupling α-bromoboronates. The mild conditions allow good functional group tolerance broad scope. application method in late-stage modification molecules further demonstrates its great potential organic synthesis. Mechanistic studies were also conducted, catalytic cycle is proposed.

Language: Английский

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Dual Nickel- and Photoredox-Catalyzed Asymmetric Reductive Cross-Coupling To Access Chiral Secondary Benzylic Alcohols

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(22), P. 16134 - 16144

Published: Feb. 8, 2024

Transition-metal-catalyzed asymmetric cross-coupling represents a powerful strategy for C-C bond formation and the synthesis of enantiomerically pure molecules. Here, we report dual nickel/photoredox-catalyzed enantioselective reductive aryl halides with α-bromobenzoates, readily generated from aliphatic aldehydes, to provide diverse chiral secondary benzylic alcohols that are important motifs in bioactive natural products pharmaceuticals. This catalytic system features mild conditions, good functional group tolerance, broad substrate scope, excellent enantiocontrol, avoidance stoichiometric metal reductants, presenting great potential late-stage functionalization complex

Language: Английский

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Visible Light Catalyzed Reductive Cross‐Coupling of α‐CF₃‐alkyl Bromide and Alkynyl Bromide^†

Chinese Journal of Chemistry, Journal Year: 2024, Volume and Issue: 42(20), P. 2479 - 2484

Published: June 21, 2024

Comprehensive Summary Traditional reduction coupling reactions of two bromides typically rely on transition metal catalysis. Here, we introduce the development a visible‐light catalytic direct reaction between α ‐CF 3 ‐alkyl and alkynyl to access valuable organic frameworks. Our research confirms excellent compatibility this with various functional groups, which could be used modify substrate biologically active molecular fragments. Mechanistic investigations, including control experiments, fluorescence quenching studies, light‐switching have provided insights into mechanism. This study paves way for application catalysis in diverse synthetic transformations, offering sustainable efficient approach synthesis.

Language: Английский

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