Enantioselective [3+2] Annulation of Aldimines with Alkynes by Scandium‐Catalyzed C−H Activation

Angewandte Chemie International Edition, Год журнала: 2025, Номер unknown

Опубликована: Янв. 3, 2025

Abstract The enantioselective [3+2] annulation of readily accessible aldimines with alkynes via C−H activation is, in principle, a straightforward and atom‐efficient route for synthesizing chiral 1‐aminoindenes, which are important components wide array natural products, bioactive molecules, functional materials. However, such asymmetric transformation has remained undeveloped to date due the lack suitable catalysts. Here, we report first time using half‐sandwich scandium This protocol enabled synthesis diverse multi‐substituted 1‐aminoindene derivatives 100 % atom‐efficiency, broad substrate scope, high regio‐ enantioselectivity. Density theory (DFT) analyses have revealed that noncovalent C−H⋅⋅⋅π interaction between tert ‐Bu substituent cyclopentadienyl (Cp) ligand phenyl ring an aromatic aldimine played role achieving level work not only offers efficient selective new family but also unprecedented insights into enantioselectivity control Cp‐ligated metal

Язык: Английский

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Copper-Mediated Enantioselective C–H Thiolation of Ferrocenes Enabled by the BINOL Ligand

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Янв. 30, 2025

Transition-metal-catalyzed enantioselective C-H activation has transformed the landscape of asymmetric synthesis, enabling efficient conversion bonds into C-C and carbon-heteroatom (C-X) bonds. However, formation C-S through thiolation remains underdeveloped due to challenges such as catalyst deactivation competitive coordination sulfur-containing compounds with chiral ligands. Herein, we report an unprecedented approach constructing sulfur-substituted planar ferrocenes (PCFs) copper-mediated enabled by only a 2.5 mol % 1,1'-bi-2,2'-naphthol (BINOL) ligand. A variety PCFs were obtained in good yields (up 83%) excellent enantioselectivity >99% ee). Mechanistic studies reveal that irreversible serves both stereo- rate-determining step can be achieved catalytic amounts Cu species. Furthermore, utility this protocol is illustrated gram-scale removal directing group, synthesis N,S-chiral ligands well rotaxanes. This significant advancement not expands tool kit for organosulfur but also highlights potential synthesis.

Язык: Английский

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Oxygen‐Linked Cyclopentadienyl Rhodium(III) Complexes‐Catalyzed Asymmetric C−H Arylation of Benzo[h]quinolines with 1‐Diazonaphthoquinones

Angewandte Chemie International Edition, Год журнала: 2021, Номер 60(28), С. 15510 - 15516

Опубликована: Апрель 16, 2021

Abstract Chiral cyclopentadienyl rhodium (CpRh) complex‐catalyzed asymmetric C−H functionalization reactions have witnessed a significant progress in organic synthesis. In sharp contrast, the reported chiral Cp ligands are limited to C‐linked and often synthetically challenging. To address these issues, we developed novel class of tunable bearing oxygen linkers, which were efficient catalysts for arylation benzo[ h ]quinolines with 1‐diazonaphthoquinones, affording axially heterobiaryls excellent yields enantioselectivity (up 99 % yield, 98.5:1.5 er). Mechanistic studies suggest that reaction is likely proceed by electrophilic activation, followed coupling cyclometalated rhodium(III) complex 1‐diazonaphthoquinones.

Язык: Английский

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Modular Access to Spiro-dihydroquinolines via Scandium-Catalyzed Dearomative Annulation of Quinolines with Alkynes

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(48), С. 20462 - 20471

Опубликована: Ноя. 23, 2021

The catalytic enantioselective construction of three-dimensional molecular architectures from planar aromatics such as quinolines is great interest and importance the viewpoint both organic synthesis drug discovery, but there still exist many challenges. Here, we report scandium-catalyzed asymmetric dearomative spiro-annulation with alkynes. This protocol offers an efficient selective route for spiro-dihydroquinoline derivatives containing a quaternary carbon stereocenter unprotected N–H group readily accessible diverse alkynes, featuring high yields, enantioselectivity, 100% atom-efficiency, broad substrate scope. Experimental density functional theory studies revealed that reaction proceeded through C–H activation 2-aryl substituent in quinoline by scandium alkyl (or amido) species followed alkyne insertion into Sc–aryl bond subsequent 1,2-addition resulting alkenyl to C═N unit moiety. work opens new avenue dearomatization quinolines, leading spiro were previously difficult access other means.

Язык: Английский

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Binaphthyl Scaffold: A Class of Versatile Structure in Asymmetric C–H Functionalization

ACS Catalysis, Год журнала: 2022, Номер 12(15), С. 9359 - 9396

Опубликована: Июль 18, 2022

Over the past decades, transition metal-catalyzed enantioselective C–H functionalization has emerged as a straightforward and powerful tool for rapid access to chiral molecules. The enormous advances achieved in this emerging area largely rely on development of ligands that can enable both high levels enantiocontrol efficiency. Chiral bearing binaphthyl scaffolds have been proven be versatile asymmetric due their availability, unique stereochemical features, ease fine-tuning steric electronic properties. In Review, we summarized advance applications basis scaffold functionalization.

Язык: Английский

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Access to Planar Chiral Ferrocenes via N-Heterocyclic Carbene-Catalyzed Enantioselective Desymmetrization Reactions

ACS Catalysis, Год журнала: 2022, Номер 12(4), С. 2706 - 2713

Опубликована: Фев. 9, 2022

Ferrocene-derived dicarbaldehydes bearing pro-chiral planes are desymmetrized under the catalysis of chiral N-heterocyclic carbene organic catalysts. The reaction features selective activation and one aldehyde moieties ferrocene derivative while leaving other unit untouched. Our affords enantiomerically enriched planar products obtained that amenable for further transformations. Preliminary application studies show encouraging results when our explored in chemical synthesis antimicrobial utilities pesticide development.

Язык: Английский

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Coordination-assisted, transition-metal-catalyzed enantioselective desymmetric C–H functionalization

Organic Chemistry Frontiers, Год журнала: 2022, Номер 9(5), С. 1458 - 1484

Опубликована: Янв. 1, 2022

Recent advances in transition-metal-catalyzed enantioselective desymmetric C–H functionalization are summarized.

Язык: Английский

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Copper-catalyzed asymmetric C(sp2)–H arylation for the synthesis of P- and axially chiral phosphorus compounds

Nature Communications, Год журнала: 2023, Номер 14(1)

Опубликована: Апрель 20, 2023

Transition metal-catalyzed C-H bond functionalization is an important method in organic synthesis, but the development of methods that are lower cost and have a less environmental impact desirable. Here, Cu-catalyzed asymmetric C(sp

Язык: Английский

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Copper/BINOL-Catalyzed Enantioselective C–H Functionalization toward Planar Chiral Ferrocenes Under Mild Conditions

ACS Catalysis, Год журнала: 2024, Номер 14(6), С. 4030 - 4039

Опубликована: Фев. 28, 2024

Copper-catalyzed enantioselective C–H activation proceeding through an inner-sphere mechanism remains a huge challenge. Herein, copper-catalyzed alkynylation with terminal alkynes assisted by 8-aminoquinoline using readily available (S)-BINOL as the chiral ligand was disclosed. The reaction proceeded under mild conditions catalytic amount of copper salt, providing range ferrocenes in good yields and enantioselectivities (0 °C, up to 77% yield 94% ee). alteration stoichiometric chemical oxidant renewable electricity is also feasible at ambient temperature, demonstrating robustness this copper/BINOL catalysis. Notably, first cupraelectrocatalyzed reaction. Gram-scale synthesis, versatile transformations, application resulting oxazoline–olefin asymmetric synthesis highlight utility protocols.

Язык: Английский

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Iridium-Catalyzed Regiodivergent Atroposelective C–H Alkylation of Heterobiaryls with Alkenes

ACS Catalysis, Год журнала: 2024, Номер 14(9), С. 7243 - 7255

Опубликована: Апрель 24, 2024

The atroposelective direct C–H alkylation of heterobiaryls with simple alkenes represents a challenging and underexplored frontier. Herein we report an iridium(I)-catalyzed regiodivergent enantioselective 1-arylisoquinolines or 2-arylpyridines alkenes. By utilizing cationic iridium catalyst different types chiral bidentate phosphine ligands, both linear- branched-selective alkylations were achieved high regioselectivities enantioselectivities. With this atom-economic ligand-enabled protocol, series axially nitrogen-containing synthesized good efficiency enantioselectivity. For the linear-selective involving styrene moiety, computational investigations illuminated that regioselectivity is established during migratory insertion step into Ir–C bond. Both experimental density functional theory (DFT) studies concerning substituent effects moiety also conducted. These results suggest primacy role resonance effect relative to field-inductive in determining transformation.

Язык: Английский

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