Merging Photoinduced Electron Transfer with Hydrogen Atom Transfer: Formal β-C(sp³)–H Pyridination of Carbonyls

The Journal of Organic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Янв. 9, 2025

In this study, a novel approach that combines photoinduced electron transfer (ET) with hydrogen atom (HAT) has been introduced for the selective β-C(sp3)–H pyridination of carbonyl compounds. This method is notable its absence transition metals and ability to function under benign reaction conditions, resulting in range pyridinated derivatives consistently moderate good yields. The significance technique further underscored by potential late-stage functionalization pharmaceutically significant molecules. Mechanistic investigations confirmed proceeds via radical-mediated pathway.

Язык: Английский

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Visible-Light-Induced Divergent C–H Esterification/Alkylation of Quinoxalin-2(1H)-ones with Aldehydes under Mild Conditions

Organic Letters, Год журнала: 2025, Номер 27(10), С. 2526 - 2531

Опубликована: Март 5, 2025

Herein, we introduce an efficient and straightforward strategy for the selective C-H esterification alkylation of quinoxalin-2(1H)-ones with aldehydes. A key feature our study is ability to perform both using different types The reaction system highly compatible a range aldehydes, yielding C3-esterified C3-alkylated products in moderate-to-good yields. applicability this approach further enhanced by its scalability through continuous-flow synthesis, late-stage modification significant molecules, product derivatization. Our mechanistic investigations reveal radical relay mechanism, triggered hydrogen atom transfer process.

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 Enantioselective Tandem C–H Indolization toward Biindolyl Atropisomers: Reaction Development and Mechanistic Insight

ACS Catalysis, Год журнала: 2025, Номер 15(3), С. 1422 - 1430

Опубликована: Янв. 9, 2025

The electrochemical methods for asymmetric indolization are still elusive and pose a significant challenge. Taking advantage of 2-alkynylanilines as electrochemically compatible indolyl equivalents, we herein represent mild highly enantioselective electrocatalytic process tandem C–H to form 2,3′-biindolyl atropisomers along with hydrogen evolution reaction. Integrated experimental computational mechanistic studies revealed that sequential metalation/nucleophilic cyclization/reductive elimination/anodic oxidation sequence involving RhIII–RhI–RhIII catalytic cycle accounts the established transformation.

Язык: Английский

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Recent advances in electrochemical copper catalysis for modern organic synthesis

Beilstein Journal of Organic Chemistry, Год журнала: 2025, Номер 21, С. 155 - 178

Опубликована: Янв. 16, 2025

In recent decades, organic electrosynthesis has emerged as a practical, sustainable, and efficient approach that facilitates valuable transformations in synthetic chemistry. Combining electrochemistry with transition-metal catalysis is promising rapidly growing methodology for effectively forming challenging C-C C-heteroatom bonds complex molecules sustainable manner. this review, we summarize the advances combination of copper various transformations.

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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Asymmetric synthesis of metallocenes with planar and central chirality by rhodium-catalyzed desymmetrization reactions

Chemical Science, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

Metallocenes with planar and central chirality have emerged as a privileged skeleton for chiral ligand design, such ligands exhibited tremendous success in various asymmetric catalysis protocols. Herein, we report rhodium/chiral diene-catalyzed desymmetrization of 1,2-diformylmetallocenes aryl/alkenylboronic acids to give enantio-enriched formylmetallocenes, which are diastereoisomers Ugi-type products. This catalytic system also enables the kinetic resolution 2-substituted 1-formylferrocene selectivity factor (s) up 4331. Compared traditional synthesis methods, our method has following advantages: (1) opposite diastereoselectivity; (2) synthesis; (3) single-step construction chirality. The synthetic utility present is demonstrated by series phosphine ligands, including Josiphos- PPFA-type ligands.

Язык: Английский

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N-Heterocyclic Carbene-Catalyzed Chemo- and Enantioselective Three-Component Esterification/Amidation Relay for Access to Planar Chiral Ferrocene Derivatives

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 6130 - 6140

Опубликована: Апрель 1, 2025

Язык: Английский

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Electrooxidative iridium-catalyzed sp2 C−H activation-annulation leading to cationic π-extended heteroaromatics

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(17), С. 4849 - 4856

Опубликована: Янв. 1, 2024

An electrochemically driven, Cp*Ir( iii )-catalyzed method for alkenyl and aromatic C(sp 2 )–H activation coupling with alkynes the synthesis of biologically useful quaternary ammonium salts under mild conditions is demonstrated.

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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