Nickel-catalyzed formation of quaternary carbon centers using tertiary alkyl electrophiles

Chemical Society Reviews, Год журнала: 2021, Номер 50(6), С. 4162 - 4184

Опубликована: Янв. 1, 2021

This review provides a comprehensive summary of recent advances in nickel-catalyzed reactions employing tertiary alkyl electrophiles for the construction quaternary carbon centers.

Язык: Английский

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Transition-Metal-Catalyzed Functionalization of Alkynes with Organoboron Reagents: New Trends, Mechanistic Insights, and Applications

ACS Catalysis, Год журнала: 2021, Номер 11(12), С. 7513 - 7551

Опубликована: Июнь 9, 2021

Catalytic functionalization of alkynes with organoboron reagents provides a straightforward access to stereochemically defined multisubstituted alkenes, which are structural motifs commonly found in bioactive compounds and organic materials. Recent progress has substantially broadened the scope this field on several fronts. Strategies for regioselectivity control 1,2-migratory insertion across unsymmetrical internal alkynes, as well direct products anti-insertion stereochemistry, have been devised. The alkenyl-to-aryl 1,4-metal migration upon metal recently exploited powerful cascade sequences leading complex polycyclic scaffolds, including development enantioselective processes. Elegant enantiospecific dynamic kinetic resolution methods developed accessing chiral allenes from propargylic alcohol derivatives. Mechanistic manifolds emerged based single-electron transfer (SET) that provided fresh impetus alkyne 1,2-difunctionalization complementary stereoselectivity processes relying 1,2-insertion R–M species. Herein, we discuss most recent advances transition-metal-catalyzed using reagents, categorized according type mechanistic outcome. Emphasis is placed aspects, synthetic utility, limitations, challenges future research.

Язык: Английский

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Switchable 1,2-Rearrangement Enables Expedient Synthesis of Structurally Diverse Fluorine-Containing Scaffolds

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(26), С. 11626 - 11637

Опубликована: Май 23, 2022

Skeletal rearrangement that changes the connectivity of molecule via cleavage and reorganization carbon–carbon bonds is a fundamental powerful strategy in complex molecular assembly. Because lack effective methods to control migratory tendency different groups, achieving switchable selectivity skeletal has been long-standing quest. Metal-based dyotropic provides unique opportunity address this challenge. However, remains unexplored. Herein, we show such problem could be solved by modifying ligands on metal catalyst changing oxidation states aptitude thereby providing ligand-controlled, strategy. Experimental density functional theory calculation studies prove rational design. The occurs only when nickel(II) intermediate reduced more nucleophilic nickel(I) species, sterically hindered iPrPDI ligand facilitates 1,2-aryl/Ni rearrangement, while terpyridine promotes 1,2-acyl/Ni rearrangement. This method allows site-selective activation C–C applied for divergent synthesis four medicinally relevant fluorine-containing scaffolds from same starting material.

Язык: Английский

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Nickel‐Catalyzed Defluorinative Asymmetric Cyclization of Fluoroalkyl‐Substituted 1,6‐Enynes for the Synthesis of Seletracetam

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(46)

Опубликована: Сен. 23, 2022

Abstract The introduction of fluorine‐containing groups into organic molecules can significantly affect their physical and chemical properties has long been used as an effective strategy for drug discovery development. Consequently, the development catalytic asymmetric methods synthesis heterocycles is highly desirable sought after. Herein, we describe a nickel‐catalyzed defluorinative cyclization fluoroalkyl‐substituted 1,6‐enynes, providing expedient access to synthetically attractive 4‐fluorovinyl‐substituted 2‐pyrrolidones in good yields with remarkable high levels chemo‐, regio‐, enantioselectivities (90–99 % ee,>35 examples). This protocol features readily available starting materials excellent functional group compatibility, exhibits complementary regioselectivity. utility this was demonstrated enantioselective antiepileptic Seletracetam.

Язык: Английский

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Pyrazolyl-pyrimidine porous-organic-polymer supported single-site nickel composites as efficient catalysts for the synthesis of substituted pyrimidines

Chemical Engineering Journal, Год журнала: 2023, Номер 474, С. 145642 - 145642

Опубликована: Авг. 25, 2023

Язык: Английский

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Recent Advances in Cyclization Reactions of 1,6‐Enynes

Advanced Synthesis & Catalysis, Год журнала: 2024, Номер 366(6), С. 1220 - 1268

Опубликована: Янв. 22, 2024

Abstract Elaborated molecular architectures, specifically those bearing one or more carbon stereocenters, stand as an important class of carbocyclic and heterocyclic frameworks because they are frequently occurring core structures in numerous natural products biologically active pharmaceutical molecules. Over the past few decades, development versatile synthetic approaches via cascade cyclization reactions 1,6‐enynes for construction a series fused spiro compounds has been focus great deal research initiatives. These synthesis strategies peculiarly fascinating context assembly wide array molecules, products, agrochemicals, functional materials. In this review, recent developments transformations with diverse coupling reagents summarized since 2018, which could be divided into five categories: 1) Introduction; 2) Transition metal catalyzed 1,6‐enynes; 3) Metal‐free 4) Visible‐light‐induced 5) Electrocatalytic 1,6‐enynes.

Язык: Английский

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Nickel-catalyzed switchable arylative/endo-cyclization of 1,6-enynes

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Апрель 4, 2024

Abstract Carbo- and heterocycles are frequently used as crucial scaffolds in natural products, fine chemicals, biologically pharmaceutically active compounds. Transition-metal-catalyzed cyclization of 1,6-enynes has emerged a powerful strategy for constructing functionalized carbo- heterocycles. Despite significant progress, the regioselectivity alkyne functionalization is entirely substrate-dependent. And only exo -cyclization/cross-coupling products can be obtained, while endo -selective cyclization/cross-coupling remains elusive still poses formidable challenge. In this study, we disclose nickel-catalyzed switchable arylation/cyclization which nature ligand dictates arylation, electrophilic trapping reagents determine selectivity mode. Specifically, using commercially available 1,10-phenanthroline facilitates trans -arylation/cyclization to obtain seven-membered ring 2-naphthyl-substituted bisbox promotes cis access six-membered products. Diastereoselective cyclizations have also been developed synthesis enantioenriched piperidines azepanes, core structural elements pharmaceuticals possessing important biological activities. Furthermore, experimental density functional theory studies reveal that arylation process controlled by steric hindrance ligand; reaction mechanism involves -cyclization followed Dowd-Beckwith-type expansion form

Язык: Английский

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Nickel‐Catalyzed Arylative Cyclizations of Alkyne‐ and Allene‐Tethered Electrophiles using Arylboron Reagents

Chemistry - A European Journal, Год журнала: 2022, Номер 28(18)

Опубликована: Янв. 5, 2022

The use of arylboron reagents in metal-catalyzed domino addition-cyclization reactions is a well-established strategy for the preparation diverse, highly functionalized carbo- and heterocyclic products. Although rhodium- palladium-based catalysts have been commonly used these reactions, more recent work has demonstrated nickel catalysis also effective, many cases offering unique reactivity access to products that might otherwise not be readily available. This review gives an overview nickel-catalyzed arylative cyclizations alkyne- allene-tethered electrophiles using reagents. scope discussed detail, general mechanistic concepts underpinning processes are described.

Язык: Английский

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Enantioselective Ni/N-Heterocyclic Carbene-Catalyzed Redox-Economical Coupling of Aldehydes, Alkynes, and Enones for Rapid Construction of Acyclic All-Carbon Quaternary Stereocenters

Journal of the American Chemical Society, Год журнала: 2021, Номер 144(1), С. 130 - 136

Опубликована: Дек. 23, 2021

Acyclic quaternary carbon stereocenters exist widely in natural products and bioactive molecules, but their enantioselective construction remains a prominent challenge. In particular, multicomponent couplings of simple precursors to acyclic all-carbon are very rare. We describe herein an N-heterocyclic carbene (NHC)-Ni catalyzed redox-economical three-component reaction aldehydes, alkynes, enones that proceeds highly chemo-, regio-, manner. A wide variety valuable α-quaternary chiral ketones were synthesized single step with 100% atom economy. This through the formation transient cyclic enolate followed by aldol reaction/ring-opening sequence. The strategy is expected inspire new efficient approaches generate other stereocenters.

Язык: Английский

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Enantioselective difunctionalization of alkenes by a palladium-catalyzed Heck/borylation sequence

Chemical Science, Год журнала: 2022, Номер 13(7), С. 2021 - 2025

Опубликована: Янв. 1, 2022

A palladium catalyzed enantioselective Heck/borylation reaction of alkene-tethered aryl iodides was realized, delivering a variety 2,3-dihydrobenzofuranyl boronic esters in high yield with excellent enantioselectivity.

Язык: Английский

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