Nickel-Catalyzed Enantioselective Electrochemical Reductive Cross-Coupling of Aryl Aziridines with Alkenyl Bromides

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(11), С. 6270 - 6279

Опубликована: Март 7, 2023

An electrochemically driven nickel-catalyzed enantioselective reductive cross-coupling of aryl aziridines with alkenyl bromides has been developed, affording enantioenriched β-aryl homoallylic amines excellent E-selectivity. This electroreductive strategy proceeds in the absence heterogeneous metal reductants and sacrificial anodes by employing constant current electrolysis an undivided cell triethylamine as a terminal reductant. The reaction features mild conditions, remarkable stereocontrol, broad substrate scope, functional group compatibility, which was illustrated late-stage functionalization bioactive molecules. Mechanistic studies indicate that this transformation conforms stereoconvergent mechanism aziridine is activated through nucleophilic halide ring-opening process.

Язык: Английский

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Highly selective synthesis of all-carbon tetrasubstituted alkenes by deoxygenative alkenylation of carboxylic acids

Nature Communications, Год журнала: 2022, Номер 13(1)

Опубликована: Фев. 4, 2022

Abstract The synthesis of all-carbon tetrasubstituted olefins under mild reaction conditions is challenging because the inevitable issues including significant steric hindrance and uncontrolled Z/E stereoselectivity. In this paper, we report alkenes from readily available carboxylic acids alkenyl triflates with synergistic catalysis cyclo-octa-1,5-diene(tetramethyl-1,4-benzoquinone)nickel visible light an air atmosphere, thus avoiding need for a glovebox or Schlenk line. A wide range aromatic cyclic acyclic undergo C-C coupling process smoothly, forming structurally diverse stereospecifically in moderate to good yields. practicality method further illustrated by late-stage modification complex molecules, one pot gram-scale applications. This important step towards valuable utilization acids, it also simplifies experimental operation metallophotoredox moisture sensitive nickel(0) catalysis.

Язык: Английский

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Photoinduced Cobalt-Catalyzed Desymmetrization of Dialdehydes to Access Axial Chirality

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(12), С. 6944 - 6952

Опубликована: Март 15, 2023

Enantioselective metallaphotoredox catalysis, which combines photoredox catalysis and asymmetric transition-metal has become an effective approach to achieve stereoconvergence under mild conditions. Although many impressive synthetic approaches have been developed access central chirality, the construction of axial chirality by still remains underexplored. Herein, we report two visible light-induced cobalt-catalyzed reductive couplings biaryl dialdehydes synthesize axially chiral aldehydes (60 examples, up 98% yield, >19:1 dr, >99% ee). This protocol shows good functional group tolerance, broad substrate scope, excellent diastereo- enantioselectivity.

Язык: Английский

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Modular and Facile Access to Chiral α-Aryl Phosphates via Dual Nickel- and Photoredox-Catalyzed Reductive Cross-Coupling

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(9), С. 3989 - 3997

Опубликована: Фев. 22, 2022

Chiral phosphine-containing skeletons are important motifs in bioactive natural products, pharmaceuticals, chiral catalysts, and ligands. Herein, we report a general modular platform to access α-aryl phosphorus compounds via Ni/photoredox-catalyzed enantioconvergent reductive cross-coupling between α-bromophosphates aryl iodides. This dual catalytic regime exhibited high efficiency good functional group compacity. A wide variety of substrates bearing diverse set groups could be converted into phosphates excellent yields enantioselectivities. The utility the method was also demonstrated by development new phosphine ligand synthesis enzyme inhibitor derivatives. detailed mechanistic studies supported radical chain process revealed unique distinction compared with traditional cross-coupling.

Язык: Английский

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Carbon-centered radical capture at nickel(II) complexes: Spectroscopic evidence, rates, and selectivity

Chem, Год журнала: 2023, Номер 9(5), С. 1295 - 1308

Опубликована: Март 13, 2023

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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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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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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Metallaphotoredox catalysis for multicomponent coupling reactions

Green Chemistry, Год журнала: 2021, Номер 23(15), С. 5379 - 5393

Опубликована: Янв. 1, 2021

The key advances in the field of metallaphotoredox-catalyzed multicomponent couplings recent years are highlighted this review. To better meet needs modern chemistry, further research outlooks were also proposed.

Язык: Английский

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Three-component 1,2-dicarbofunctionalization of alkenes involving alkyl radicals

Chemical Communications, Год журнала: 2021, Номер 58(6), С. 730 - 746

Опубликована: Дек. 8, 2021

This article provides a comprehensive perspective on three-component 1,2-dicarbofunctionalization of alkenes involving alkyl radicals, which generated from structurally diverse electrophilic and nucleophilic precursors under mild conditions.

Язык: Английский

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