Chemodivergent and Enantioselective Synthesis of Spirobi[dihydrophenalene] Structures

Organic Letters, Год журнала: 2025, Номер 27(3), С. 869 - 873

Опубликована: Янв. 10, 2025

The development and enantioselective synthesis of two types C2-symmetric spirobi[dihydrophenalene] structures is reported. reaction proceeds via rhodium-catalyzed 2-fold asymmetric conjugate arylation dienones followed by BF3·OEt2-promoted spirocyclization to give the enantiopure spiro products. Additive-dependent chemodivergent 3,3'-diarylated 2,2',3,3'-tetrahydro-1,1'-spirobi[phenalene]-9,9'-diols (3,3'-Ar2-SPHENOLs) corresponding diary ethers from same intermediate achieved. structural properties 3,3'-Ph2-SPHENOL are analyzed, its application in catalysis has been preliminarily demonstrated.

Язык: Английский

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Enantioselective synthesis of indenols via rhodium(III)–catalyzed C-H activation/annulation of ketones with alkynes

Science China Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Фев. 12, 2025

Язык: Английский

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Parametrization of κ²-N,O-Oxazoline Preligands for Enantioselective Cobaltaelectro-Catalyzed C–H Activations

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 4450 - 4459

Опубликована: Фев. 28, 2025

Enantioselective electrocatalyzed C–H activations have emerged as a transformative platform for the assembly of value-added chiral organic molecules. Despite recent progress, construction multiple C(sp3)-stereogenic centers via C(sp3)–C(sp3) bond formation has thus far proven to be elusive. In contrast, we herein report an annulative activation strategy, generating Fsp3-rich molecules with high levels diastereo- and enantioselectivity. κ2-N,O-oxazoline preligands were effectively employed in enantioselective cobalt(III)-catalyzed reactions. Using DFT-derived descriptors regression statistical modeling, performed parametrization study on modularity preligands. The resulted model describing ligands' selectivity characterized by key steric, electronic, interaction behaviors.

Язык: Английский

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Enantioselective C–H annulations enabled by either nickel- or cobalt-electrocatalysed C–H activation for catalyst-controlled chemodivergence

Nature Catalysis, Год журнала: 2025, Номер unknown

Опубликована: Март 7, 2025

Язык: Английский

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Electrochemical enabled cobalt catalyzed enantioselective C-H acyloxylation of aryl phosphamide with carboxylic acid

Green Chemistry, Год журнала: 2024, Номер 26(14), С. 8323 - 8329

Опубликована: Янв. 1, 2024

We described here the first example of cobalt-electro-catalyzed enantioselective C–H acyloxylation arylphosphinamides with carboxylic acids to generate P-stereogenic scaffolds.

Язык: Английский

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Electrochemical Enantioselective C–H Annulation by Achiral Rhodium(III)/Chiral Brønsted Base Domino Catalysis

ACS Catalysis, Год журнала: 2024, Номер 14(11), С. 8160 - 8167

Опубликована: Май 10, 2024

Rhodium(III)-catalyzed enantioselective C–H activation has emerged as a powerful tool for assembling enabling chiral molecules. However, this approach is significantly hampered by the cumbersome synthetic routes preparing rhodium catalysts. In sharp contrast, we herein report on an electrochemical domino catalysis system that exploits achiral Cp*-rhodium catalyst along with easily accessible Brønsted base activation/annulation reaction of alkenes benzoic acids. Our strategy offers environmentally benign and most user-friendly synthetically useful phthalides in good enantioselectivity, employing electricity sustainable oxidant.

Язык: Английский

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Electrocatalytic Cascade Selenylation/Cyclization/Deamination of 2-Hydroxyaryl Enaminones: Synthesis of 3-Selenylated Chromones under Mild Conditions

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(12), С. 8632 - 8640

Опубликована: Июнь 6, 2024

Herein, we disclosed a highly efficient pathway toward 3-selenylated chromone derivatives via electrocatalytic cascade selenylation/cyclization/deamination of 2-hydroxyaryl enaminones with diselenides. This method showed mild conditions, easy operation, wide substrate scope, and good functional group tolerance. Furthermore, this electrosynthesis strategy was amendable to scale-up the reaction. Additionally, preliminary experiments revealed that reaction probably proceeded cation instead radical pathway.

Язык: Английский

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Catalytic Asymmetric C–H Activation/Cyclization of Sulfoximines with Sulfoxonium Ylides by a Chiral η⁶-Benzene Ruthenium(II) Catalyst

ACS Catalysis, Год журнала: 2024, Номер unknown, С. 17398 - 17404

Опубликована: Ноя. 12, 2024

Chiral η6-benzene ruthenium(II) (BenRuII)-catalyzed asymmetric C–H activations are challenging and rarely seen in the literature. Herein, activation/cyclization of sulfoximines with sulfoxonium ylides catalyzed by chiral BenRuII catalyst derived from (S)-H8–BINOL is described. It provides efficient access to various sulfur-chiral 1,2-benzothiazine 1-oxides high yields enantioselectivities (up 99% yield 98% ee). Kinetic resolution racemic was also feasible. The reaction mechanism studied tool H/D exchange kinetic isotope effect. metallacycle revealing origin induction prepared, characterized, proved effective for model reaction. This work demonstrates great potential catalysts activation.

Язык: Английский

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N–N Atropisomer Synthesis via Electrolyte- and Base-Free Electrochemical Cobalt-Catalysed C–H Annulation

Green Chemistry, Год журнала: 2024, Номер 26(23), С. 11524 - 11530

Опубликована: Янв. 1, 2024

An exogenous electrolyte- and base-free electrochemical cobalt-catalysed atroposelective C–H annulation has been established to construct N–N axially chiral isoquinolinones in excellent enantioselectivities good yields.

Язык: Английский

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Metalla-Electrocatalyzed Alkyne Annulations via C–H Activations for Sustainable Heterocycle Syntheses

Chemical Communications, Год журнала: 2024, Номер unknown

Опубликована: Янв. 1, 2024

Herein, an overview of the evolution electrochemical C–H annulations with alkynes for construction heterocycles is provided, a topical focus on underlying mechanism manifolds.

Язык: Английский

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