Enantioselective C(sp²)–C(sp³) Bond Construction by Ni Catalysis

Accounts of Chemical Research, Год журнала: 2024, Номер 57(5), С. 751 - 762

Опубликована: Фев. 12, 2024

ConspectusAfter decades of palladium dominating the realm transition-metal-catalyzed cross-coupling, recent years have witnessed exciting advances in development new nickel-catalyzed cross-coupling reactions to form C(sp3) centers. Nickel possesses distinct properties compared with palladium, such as facile single-electron transfer electrophiles and rapid C–C reductive elimination from NiIII. These properties, among others, make nickel particularly well-suited for (RCC) which two are coupled an exogenous reductant is used turn over metal catalyst. Ni-catalyzed RCCs use readily available stable starting materials exhibit good functional group tolerance, makes them appealing applications synthesis complex molecules. Building upon foundational work by groups Kumada, Durandetti, Weix, well advancements enantioselective redox-neutral cross-couplings led Fu co-workers, we initiated a program explore feasibility developing highly RCCs. Our research has also been driven keen interest unraveling factors contributing enantioinduction electrophile activation seek avenues advancing our understanding further these reactions.In first part this Account, organize reported methods on basis identity electrophiles, including benzylic chlorides, N-hydroxyphthalimide (NHP) esters, α-chloro esters nitriles. We highlight how selection specific chiral ligands plays pivotal role achieving high cross-selectivity enantioselectivity. In addition, show that reduction can be accomplished not only heterogeneous reductants, Mn0, but soluble organic tetrakis(dimethylamino)ethylene (TDAE), electrochemically. The homogeneous TDAE, suited studying mechanism transformation. Although Account primarily focuses RCCs, using trifluoroborate (BF3K) salts radical precursors dual-Ni/photoredox systems.At end summarize relevant mechanistic studies closely related asymmetric alkenylation developed laboratory provide context between others. discuss ligand influence rates mechanisms mode generation optimize yield RCC. endeavors offer insights intricate at play goal rate improve substrate scope anticipate share guidance field.

Язык: Английский

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Enantioselective Reductive Cross-Couplings of Olefins by Merging Electrochemistry with Nickel Catalysis

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(44), С. 23910 - 23917

Опубликована: Окт. 26, 2023

The merger of electrochemistry and transition metal catalysis has emerged as a powerful tool to join two electrophiles in an enantioselective manner. However, the development electroreductive cross-couplings olefins remains challenge. Inspired by advantages synergistic use with nickel catalysis, we present here Ni-catalyzed cross-coupling acrylates aryl halides alkyl bromides, which affords chiral α-aryl carbonyls good excellent enantioselectivity. Additionally, this catalytic reaction can be applied (hetero)aryl chlorides, is difficult achieve other methods. combination cyclic voltammetry analysis electrode potential studies suggests that NiI species activates oxidative addition bromides single-electron transfer.

Язык: Английский

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Recent advances in dual photoredox/nickel catalyzed alkene carbofunctionalised reactions

Chemical Communications, Год журнала: 2024, Номер 60(68), С. 8946 - 8977

Опубликована: Янв. 1, 2024

Alkene carbofunctionalization reactions have great potential for synthesizing complex molecules and constructing structures in natural products medicinal chemistry. Recently, dual photoredox/nickel catalysis has emerged as a novel strategy alkene carbofunctionalization. Nickel offers numerous advantages over other transition metals, such cost-effectiveness, abundance, low toxicity, moreover, it many oxidation states. catalysts exhibit excellent catalytic activity photoredox/transition metal catalysis, facilitating the formation of carbon-carbon or carbon-heteroatom bonds organic transformations. This review highlights latest advancements photoredox/nickel-catalyzed carbofunctionalizations includes literature published from 2020 to 2024.

Язык: Английский

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Photocatalytic Enantioselective Hydrosulfonylation of α,β‐Unsaturated Carbonyls with Sulfonyl Chlorides

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(46)

Опубликована: Окт. 2, 2023

This research explores the enantioselective hydrosulfonylation of various α,β-unsaturated carbonyl compounds via use visible light and redox-active chiral Ni-catalysis, facilitating synthesis enantioenriched α-chiral sulfones with remarkable enantioselectivity (exceeding 99 % ee). A significant challenge entails enhancing reactivity between metal-coordinated moderate electrophilic sulfonyl radicals, aiming to minimize background reactions. The success our approach stems from two distinctive attributes: 1) Cl-atom abstraction employed for radical generation chlorides, 2) single-electron reduction produce a key enolate Ni-complex. latter process appears enhance feasibility radical's addition electron-rich radical. An in-depth investigation into reaction mechanism, supported by both experimental observations theoretical analysis, offers insight intricate process. Moreover, versatility methodology is highlighted through its successful application in late-stage functionalization complex bioactive molecules, demonstrating practicality as strategy producing sulfones.

Язык: Английский

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Palladium-Catalyzed Enantioselective Multicomponent Cross-Coupling of Trisubstituted Olefins

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(24), С. 16892 - 16901

Опубликована: Июнь 6, 2024

The development of a catalytic method for stereogenic carbon center formation holds immense significance in organic synthesis. Transition-metal-catalyzed cross-coupling reaction has been regarded as straightforward and efficient tool stereoselectively forging C–C bond. Nevertheless, the creation acyclic all-carbon quaternary-containing vicinal stereocenters remains notoriously challenging within domain chemistry despite their prominence various bioactive small molecules. Herein, we describe palladium-catalyzed asymmetric multicomponent trisubstituted alkene with aryl diazonium salts arylboronic acids to realize tertiary-quaternary centers high regio-, distereo-, enantioselectivity. Specifically, precise manipulation stereoconfiguration alkenes enables divergent stereoselective reaction, thus allowing facile construction all four enantiomers. Harnessing ligand-swap strategy involving chiral bisoxazoline an achiral fumarate individually accelerates enantioselective migratory insertion reductive elimination step process, supported by density functional theory (DFT) calculations, obviating requirement neighboring directing group internal olefin skeleton.

Язык: Английский

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Enantioselective Ni‐Catalyzed Three‐Component Dicarbofunctionalization of Alkenes

ChemCatChem, Год журнала: 2023, Номер 15(18)

Опубликована: Авг. 3, 2023

Abstract Asymmetric multicomponent reactions are considered as efficient protocols for constructing complex chiral molecules because of their step‐ and atom‐economy. Nickel‐catalyzed asymmetric three‐component dicarbofunctionalization alkenes has been well developed in recent years, which is used the area total synthesis natural products late‐stage modification drugs rapid incorporation sp 3 ‐enriched carbon centers. In this concept, significant breakthroughs field summarized, together with related mechanisms. Moreover, remaining challenges potential opportunities also highlighted.

Язык: Английский

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Photoinduced decatungstate-catalyzed C(sp³)–H thioetherification by sulfinate salts

Organic & Biomolecular Chemistry, Год журнала: 2024, Номер 22(17), С. 3420 - 3424

Опубликована: Янв. 1, 2024

A visible light photoinduced decatungstate-catalyzed C(sp 3 )–H thioetherification of hydrocarbons by sodium sulfite is herein reported.

Язык: Английский

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Ni-catalyzed reductive alkylgermylation of activated alkenes: Modular access to polyfunctionalized alkyl germanes

Chem Catalysis, Год журнала: 2023, Номер 3(12), С. 100819 - 100819

Опубликована: Ноя. 22, 2023

Язык: Английский

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SO2-Insertion induced enantioselective oxysulfonylation to access β-chiral sulfones with quaternary carbon stereocenters

Science China Chemistry, Год журнала: 2023, Номер 67(3), С. 908 - 913

Опубликована: Дек. 5, 2023

Язык: Английский

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Regio- and Stereoselective Intermolecular 1,2-Difunctionalization of Terminal Alkynes: An Approach to Access (Z)-β-Amidovinylsulfones

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(5), С. 2873 - 2884

Опубликована: Фев. 14, 2024

We have developed the first I2/base-catalyzed regio- and stereoselective intermolecular β-amidosulfonylation of terminal alkynes using sodium sulfinates quinoxalinone derivatives. The present methodology is compatible with a broad spectrum various heterocyclic amides, alkynes, sulfinates. It provides rapid access to valuable (Z)-β-amidovinyl sulfones at mild conditions. Moreover, synthetic application this was demonstrated by late-stage functionalization numerous bioactive molecules.

Язык: Английский

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