Nickel-catalysed enantioselective alkene dicarbofunctionalization enabled by photochemical aliphatic C–H bond activation

Nature Catalysis, Год журнала: 2024, Номер 7(6), С. 655 - 665

Опубликована: Апрель 29, 2024

Abstract The development of novel strategies to rapidly construct complex chiral molecules from readily available feedstocks is a long-term pursuit in the chemistry community. Radical-mediated alkene difunctionalizations represent an excellent platform towards this goal. However, asymmetric versions remain highly challenging, and more importantly, examples featuring simple hydrocarbons as reaction partners are elusive. Here we report three-component dicarbofunctionalization capitalizing on direct activation C( sp 3 )–H bonds through combination photocatalysed hydrogen atom transfer nickel catalysis. This protocol provides efficient for installing two vicinal carbon–carbon across alkenes atom-economic fashion, providing wide array high-value α-aryl/alkenyl carbonyls phosphonates, well 1,1-diarylalkanes ubiquitous alkane, ether alcohol feedstocks. method exhibits operational simplicity, broad substrate scope regioselectivity, chemoselectivity enantioselectivity. compatibility with bioactive motifs expedient synthesis pharmaceutically relevant highlight synthetic potential protocol.

Язык: Английский

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Desymmetrization–Addition Reaction of Cyclopropenes to Imines via Synergistic Photoredox and Cobalt Catalysis

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(28), С. 18892 - 18898

Опубликована: Июль 5, 2024

Herein, we designed a reaction for the desymmetrization-addition of cyclopropenes to imines by leveraging synergy between photoredox and asymmetric cobalt catalysis. This protocol facilitated synthesis series chiral functionalized cyclopropanes with high yield, enantioselectivity, diastereoselectivity (44 examples, up 93% yield >99% ee). A possible mechanism involving cyclopropene desymmetrization Co-H species imine addition Co-alkyl was proposed. study provides novel route important extends frontier metallaphotoredox

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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Electrochemical chemo- and regioselective arylalkylation, dialkylation and hydro(deutero)alkylation of 1,3-enynes

Nature Synthesis, Год журнала: 2023, Номер 2(11), С. 1068 - 1081

Опубликована: Июнь 22, 2023

Язык: Английский

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Group 14 Elements Hetero‐Difunctionalizations via Nickel‐Catalyzed Electroreductive Cross‐Coupling

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(33)

Опубликована: Июнь 13, 2023

Abstract The difunctionalization of unsaturated bonds plays a vital role in the enrichment molecular complexity. While various catalytic methods for alkene and alkyne have been developed recent years, hetero‐functionalization introduction two different atoms has less explored. This is mainly due to challenges associated with achieving high chemo‐, regio‐, stereoselectivity, especially when adding similar from same group across bonds. In this study, we describe nickel‐catalyzed, three‐component reductive protocol 14 element hetero‐difunctionalization 1,3‐enynes using electrochemistry. new method mild, selective, general, allowing silyl‐, germanyl‐, stannyl‐alkylation enynes. Various chlorosilanes as well chlorogermans, chlorostannanes can be successfully used combination aryl/alkyl‐substituted primary, secondary, tertiary alkyl bromides electroreductive coupling.

Язык: Английский

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Rapid Synthesis of β-Chiral Sulfones by Ni-Organophotocatalyzed Enantioselective Sulfonylalkenylation of Alkenes

JACS Au, Год журнала: 2023, Номер 3(5), С. 1321 - 1327

Опубликована: Апрель 27, 2023

β-Chiral sulfones are substructures widespread in drug molecules and bioactive targets serve as important chiral synthons organic synthesis yet challenging to access. Herein, a three-component strategy enabled by visible-light- Ni-catalyzed sulfonylalkenylation of styrenes for the enantioenriched β-chiral has been developed. This dual-catalysis allows one-step skeletal assembly along with control enantioselectivity presence ligand, providing an efficient straightforward access β-alkenyl from easily available simple starting materials. Mechanistic investigations reveal that reaction undergoes chemoselective radical addition over two alkenes followed Ni-intercepted asymmetric Csp3-Csp2 coupling alkenyl halides.

Язык: Английский

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Ni- and Pd-Catalyzed Enantioselective 1,2-Dicarbofunctionalization of Alkenes

Synthesis, Год журнала: 2023, Номер 56(01), С. 1 - 15

Опубликована: Июнь 12, 2023

Abstract Catalytic enantioselective 1,2-dicarbofunctionalization (1,2-DCF) of alkenes is a powerful transformation growing importance in organic synthesis for constructing chiral building blocks, bioactive molecules, and agrochemicals. Both two- three-component context, this family reactions generates densely functionalized, structurally complex products single step. Across several distinct mechanistic pathways at play these transformations with nickel or palladium catalysts, stereocontrol can be obtained through tailored ligands. In Review we discuss the various strategies, mechanisms, catalysts that have been applied to achieve enantioinduction alkene 1,2-DCF. 1 Introduction 2 Two-Component Enantioselective 1,2-DCF via Migratory Insertion 3 Radical Capture 4 Three-Component 5 6 Miscellaneous Mechanisms 7 Conclusion

Язык: Английский

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Selective Hydrofunctionalization of Alkenyl Fluorides Enabled by Nickel-Catalyzed Hydrogen Atoms and Group Transfer: Reaction Development and Mechanistic Study

Journal of the American Chemical Society, Год журнала: 2024, Номер unknown

Опубликована: Апрель 15, 2024

Due to the unique effect of fluorine atoms, efficient construction high-value alkyl fluorides has attracted significant interest in modern drug development. However, enantioselective catalytic strategies for assembly highly functionalized chiral C(sp

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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Enantioconvergent Reductive C(sp)−C(sp³) Cross‐Coupling to Access Chiral α‐Alkynyl Phosphonates Under Dual Nickel/Photoredox Catalysis

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(18)

Опубликована: Март 8, 2023

Transition-metal-catalyzed asymmetric carbon-carbon bond formation to forge phosphonates with an α-chiral carbon center through C(sp3 )-C(sp3 ) and C(sp2 couplings has been successful. However, the enantioselective C(sp)-C(sp3 coupling not yet disclosed. Reported herein is unprecedented enantioconvergent cross-coupling of alkynyl bromides α-bromo deliver chiral α-alkynyl phosphonates.

Язык: Английский

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