Nickel-Catalyzed Dicarbofunctionalization of Alkenes

ACS Catalysis, Год журнала: 2020, Номер 10(15), С. 8542 - 8556

Опубликована: Июль 2, 2020

1,2-Dicarbofunctionalization of alkenes has emerged as an efficient synthetic strategy for preparing substituted molecules by coupling readily available with electrophiles and/or nucleophiles. Nickel complexes serve effective catalysts owing to their tendency undergo facile oxidative addition and slow β-hydride elimination, capability access both two-electron radical pathways. Two-component alkene functionalization reactions have achieved high chemo-, regio-, stereoselectivities tethering one the partners substrate. Three-component reactions, however, often incorporate directing groups control selectivity. Only a few examples directing-group-free difunctionalizations unactivated been reported. Therefore, great opportunities exist development three-component difunctionalization broad substrate scopes tunable stereoselectivities.

Язык: Английский

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Homogeneous Gold-Catalyzed Oxidation Reactions

Chemical Reviews, Год журнала: 2021, Номер 121(14), С. 8979 - 9038

Опубликована: Фев. 16, 2021

Homogeneous gold catalysis has experienced extraordinary development since the dawn of this millennium. Oxidative is a vibrant and fertile subfield over years delivered diverse array versatile synthetic methods exceptional value to practices. This review aims cover topic in comprehensive manner. The discussions are organized by mechanistic aspects metal oxidation states further types oxidants or oxidizing functional groups. Synthetic applications oxidative also discussed.

Язык: Английский

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Enantioselective Three-Component Fluoroalkylarylation of Unactivated Olefins through Nickel-Catalyzed Cross-Electrophile Coupling

Journal of the American Chemical Society, Год журнала: 2020, Номер 142(21), С. 9604 - 9611

Опубликована: Май 11, 2020

A nickel-catalyzed, enantioselective, three-component fluoroalkylarylation of unactivated alkenes with aryl halides and perfluoroalkyl iodides has been described. This cross-electrophile coupling protocol utilizes a chiral nickel/BiOx system as well pendant chelating group to facilitate the challenging three-component, asymmetric difunctionalization alkenes, providing direct access valuable β-fluoroalkyl arylalkanes high efficiency excellent enantioselectivity. The mild conditions allow for broad substrate scope good functional toleration.

Язык: Английский

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Catalytic three-component dicarbofunctionalization reactions involving radical capture by nickel

Chemical Society Reviews, Год журнала: 2021, Номер 50(19), С. 10836 - 10856

Опубликована: Янв. 1, 2021

The catalytic dicarbofunctionalization of unsaturated π bonds represents a powerful platform for the rapid construction complex motifs. Despite remarkable progress, novel and efficient methods achieving such transformations under milder conditions with chemo-, regio-, stereoselectivity still remain significant challenge; thus, their development is highly desirable. Recently, merging nickel catalysis radical chemistry offers new benign unprecedented reactivity selectivity. In this review, we summarize recent advances in area by underpinning domino involving capture to provide clear overview reaction designs mechanistic scenarios.

Язык: Английский

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Nickel‐CatalyzedDicarbofunctionalization of Alkenes^†

Chinese Journal of Chemistry, Год журнала: 2020, Номер 38(11), С. 1371 - 1394

Опубликована: Июнь 16, 2020

As a straightforward strategy for rapidly increasing molecular complexity, dicarbofunctionalization of alkenes has attracted substantial interests organic synthesis, medicine chemistry, and materials science. Nickel‐catalyzed cascade dicarbofunctionalizations have been flourished in this area recently, nickel‐mediated radical pathways particularly offer new opportunities conjunctive cross‐couplings with alkyl coupling partners. Herein, we give comprehensive review nickel‐catalyzed through historical perspective, including intermolecular three‐component reactions intramolecular reactions. Among the discussed review, carbometallation/cross‐coupling process addition/cross‐coupling are two major alkenes. The oxidative cyclization 1,2‐metallate shift processes also selectively discussed. These methods overcome limitations associated using noble metals field, providing an efficient access to structurally diversified molecules.

Язык: Английский

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Electro-/photocatalytic alkene-derived radical cation chemistry: recent advances in synthetic applications

Chemical Society Reviews, Год журнала: 2022, Номер 51(16), С. 7206 - 7237

Опубликована: Янв. 1, 2022

This review covers the recent progress in electro-/photo-catalytic alkene-derived radical cation chemistry for organic synthesis, including synthetic strategies, plausible mechanisms and further research outlook.

Язык: Английский

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Ni-Catalyzed Ligand-Controlled Regiodivergent Reductive Dicarbofunctionalization of Alkenes

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(27), С. 10282 - 10291

Опубликована: Июнь 24, 2021

Transition-metal-catalyzed dicarbofunctionalization of alkenes involving intramolecular Heck cyclization followed by intermolecular cross-coupling has emerged as a powerful engine for building heterocycles with sterically congested quaternary carbon centers. However, only exo-cyclization/cross-coupling products can be obtained; endo-selective cyclization/cross-coupling not been reported yet and still poses formidable challenge. We herein report the first example catalyst-controlled regiodivergent synthesis five- six-membered benzo-fused lactams bearing all-carbon Using chiral Pyrox- or Phox-type bidentate ligand, 5-exo cyclization/cross-couplings proceed favorably to produce indole-2-ones in good yields excellent regioselectivity enantioselectivities (up 98% ee). When C6-carboxylic acid-modified 2,2′-bipyridine was used 3,4-dihydroquinolin-2-ones were obtained through 6-endo-selective processes. This transformation is modular tolerant variety functional groups. The ligand rather than substrate structures precisely dictates pattern. Moreover, synthetic value this protocol demonstrated preparation biologically relevant molecules structural scaffolds.

Язык: Английский

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Dual Nickel/Photoredox-Catalyzed Asymmetric Carbosulfonylation of Alkenes

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(23), С. 12532 - 12540

Опубликована: Май 30, 2023

An asymmetric three-component carbosulfonylation of alkenes is presented here. The reaction, involving the simultaneous formation a C-C and C-S bond across π-system, uses dual nickel/photoredox catalytic system to produce both β-aryl β-alkenyl sulfones in high yields with excellent levels stereocontrol (up 99:1 er). This protocol exhibits broad substrate scope functional group tolerance its synthetic potential has been demonstrated by successful applications toward pharmacologically relevant molecules. A array control experiments supports involvement secondary alkyl radical intermediate generated through addition sulfonyl double bond. Moreover, stoichiometric cross-over further suggest an underlying Ni(0)/Ni(I)/Ni(III) pathway operative these transformations.

Язык: Английский

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Recent advances in three-component difunctionalization ofgem-difluoroalkenes

Chemical Communications, Год журнала: 2020, Номер 56(72), С. 10442 - 10452

Опубликована: Янв. 1, 2020

Three-component difunctionalization ofgem-difluoroalkenesviathe generation and transformation of a α-fluoroalkylated carbanion, carbon–metal species, radical, carbocation intermediate.

Язык: Английский

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Electrochemistry and Photoredox Catalysis: A Comparative Evaluation in Organic Synthesis

Molecules, Год журнала: 2019, Номер 24(11), С. 2122 - 2122

Опубликована: Июнь 5, 2019

This review provides an overview of synthetic transformations that have been performed by both electro- and photoredox catalysis. Both toolboxes are evaluated compared in their ability to enable said transformations. Analogies distinctions formulated obtain a better understanding research areas. knowledge can be used conceptualize new methodological strategies for either approaches starting from the other. It was attempted extract key components as guidelines refine, complement innovate these two disciplines organic synthesis.

Язык: Английский

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