Visible-Light-Mediated Ruthenium-Catalyzed para-Selective Alkylation of Unprotected Anilines

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(11), P. 7310 - 7321

Published: May 15, 2023

Anilines are important moieties in organic chemistry, pharmaceuticals, and materials science. Although para-selective functionalization of anilides tertiary anilines is well established, unprotected have posed a challenge. Herein, we report visible-light-mediated Ru(II)-catalyzed para-alkylation anilines. The distinct Ru(II)–aniline complex enabled the reaction to proceed with extremely high efficiency (2 h) under mild conditions. good functional group tolerance allowed late-stage even aggregation-induced emission luminogen labeling natural products drugs. A mechanistic investigation suggests that crucial for both triggering controlling para-selectivity.

Language: Английский

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Regioselective [3+2]‐Spiroannulation and [4+n]‐Annulation Approaches through Activation of C−H Bond Facilitated by Ru(II) as Catalyst: Role of Solvent Selectivity

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(8), P. 1863 - 1876

Published: Feb. 21, 2024

Abstract Ru(II)‐catalyzed and solvent‐switched [3+2]‐spiroannulation [4+n] (n=1, 2, 3) annulations of 2‐aryl quinazolinone or 2‐aryl‐2,3‐dihydrophthalazine‐1,4‐diones with ynones alkynyl alcohol 1,3‐diynes under mild reaction conditions have been analyzed. These reactions take place in the presence appropriate solvent features a redox‐neutral pathway. Ynone serves as an ‘atypical one‐carbon unit’ [4+1] annulation generates tetrasubstituted carbon center bearing diverse heterocycles through [3+2] strategies. Post transformations synthesized spiro‐products augments potential developed methodology.

Language: Английский

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Palladium(II)-Catalyzed Intramolecular [2 + 2 + 2] Annulation of Indolyl 1,3-Diynes: Construction of Azepino-Fused Carbazoles

Organic Letters, Journal Year: 2023, Volume and Issue: 25(25), P. 4615 - 4620

Published: June 21, 2023

A novel palladium(II)-catalyzed intramolecular [2 + 2 2] annulation of indolyl 1,3-diynes is described in this contribution. variety azepino-fused carbazoles are obtained moderate to excellent yields. The key the success transformation use a carboxylic acid as an additive. This protocol features broad functional group tolerances, easy handling air, and 100% atom economy. Furthermore, scale-up reactions, late-stage derivatizations, photophysical property investigations highlight potential synthetic utility methodology.

Language: Английский

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Harnessing Dual Reactivity of N-Chloroamides for Cascade C–H Amidation/Chlorination of Indoles under Cobalt-Catalysis: Overriding Hofmann Rearrangement Pathway Leading to Aminocarbonylation

Organic Letters, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 27, 2024

Herein, we have developed a Cp*Co(III)-catalyzed cascade C-2 amidation/C-3 chlorination of indoles by leveraging the dual functionality

Language: Английский

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Deciphering the Origin of Regioselectivity in Ru(II)-Catalyzed C–H Annulation of N-Chlorobenzamides with 1,3-Diynes

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(10), P. 6838 - 6846

Published: May 3, 2024

Understanding the reaction mechanism and origin of regioselectivity in transition metal-catalyzed C–H activation/annulation reactions with 1,3-diynes has remained an intriguing challenge. In this article, to establish decipher regioselectivity, we report a detailed computational density functional theory-based mechanistic investigation on recently developed Ru(II)-catalyzed [4 + 2] annulation N-chlorobenzamides for synthesis 3-alkynylated isoquinolone derivatives. Our calculations reveal redox-neutral pathway reaction. The stepwise analysis channels indicates migratory insertion step concerted reductive elimination/oxidative addition Ru(p-cymene) moiety form N–C bond leading product be selectivity- rate-determining steps, respectively. Finally, distortion/interaction using activation-strain model suggests steric effect as determining factor observed formation product. Overall, computationally obtained key insights into catalytic can used guide rationally design develop novel transformation strategies heterocycle synthesis.

Language: Английский

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Regioselective Cobalt(II) Catalyzed C–H Functionalization and [3 + 2] Annulation of N-Arylguanidines with 1,3-Diynes

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(11), P. 7376 - 7393

Published: May 15, 2024

8-Quinolinyl directed

Language: Английский

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DFT studies on the reaction mechanism of Ru(II)-catalyzed the C H activation of aromatic amide and alkylation of non-active olefins

Computational and Theoretical Chemistry, Journal Year: 2023, Volume and Issue: 1229, P. 114339 - 114339

Published: Sept. 29, 2023

Language: Английский

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Ru(II)-Catalyzed C(sp²)–H Activation Annulation: Synthesis of Fluorescent Benzoisoquinolonyl Acetate/Peptides from N-Arylamides and Ethyne at Room Temperature

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(11), P. 7485 - 7494

Published: May 15, 2024

Benzoisoquinolones are aryl ring extended isoquinolinone derivatives, which constituents of alkaloid natural products. This report describes the synthesis novel benzoisoquinolone amino acid/peptide derivatives from respective

Language: Английский

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Ru(II)-Catalyzed Redox-Neutral C–H Olefination and Tandem Cyclization with Vinyl Sulfones: Leveraging Sulfinate Anion as a Leaving Group for the Synthesis of 3-Methyleneisoindolin-1-ones

Organic Letters, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 2, 2024

We developed a Ru(II)-catalyzed redox-neutral C–H olefination of N-methoxybenzamides with vinyl sulfones. The reaction is operationally simple and conducted at ambient temperature does not require silver additives or external oxidants, making it suitable for late-stage functionalization. Notably, we leveraged the leaving group ability sulfinate anion to synthesize 3-methyleneisoindolin-1-ones through tandem olefination/cyclization/elimination sequence temperature. Moreover, successfully demonstrated synthetic versatility 3-methyleneisoindolin-1-one construction an isoindolobenzazepine core.

Language: Английский

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Theoretical Investigation of Cp*CO(III)-Mediated Regioselective [4 + 2]-Annulation of N-Chlorobenzamide with Vinyl Acetate for the Synthesis of Isoquinolone

Heterocycles, Journal Year: 2023, Volume and Issue: 106(8), P. 1385 - 1385

Published: Jan. 1, 2023

The mechanism is investigated for regioselective [4 + 2]-annulation of N-chlorobenzamide catalyzed by Cp*Co(III).The CoCp*(OAc)2-mediated ortho-cobaltation via acetate-aided N-H and C-H deprotonation furnishes a five-membered intermediate, which coordinative inserted into alkene giving seven-membered cobaltacycle.The reductive elimination oxidative addition CoCp*(I) species afford six-membered ring.The recovery CoCp*(III) assisted one AcOH vinyl acetate with OAc group available to cleavage as ligand.Two ligands are both supplied ketone COMe difficult break.The acetate-assisted tautomerization produces isoquinolin-1(2H)-one.The 3-acetylisoquinolin-1(2H)-one given dehydrooxidation.The promotion Cp*Co(III) lies in the barrier decrease most steps especially deprotonation.AcOH functions protonation Cl, N sources CoCp*(III).These results supported Multiwfn analysis on FMO specific TSs MBO value vital bonding, breaking.As common heterocyclic skeletons, isoquinolones present various natural products pharmaceuticals.Their derivatives exhibit broad medicinal properties, including antitumor, antiobesity, antiviral, other effects. 1,2Hence, development practical efficient synthetic protocol construction their analogues continuous need chemists.4][5] In recent years, some novel protocols have constantly emerged such Rh(III)-catalyzed 1385

Language: Английский

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