Coupling of Sulfoxonium Ylides with Arynes: A Direct Synthesis of Pro-Chiral Aryl Ketosulfoxonium Ylides and Its Application in the Preparation of α-Aryl Ketones

Organic Letters, Journal Year: 2018, Volume and Issue: 20(22), P. 7206 - 7211

Published: Oct. 26, 2018

A general, mild, and versatile synthesis of the challenging α-aryl-β-ketosulfoxonium ylides has been developed for first time, substituting traditional methods starting from diazo compounds. The arylation easily accessible β-ketosulfoxonium using aryne chemistry allowed preparation a large scope pro-chiral in very good yields (40 examples; up to 85%). As applications, these were smoothly converted into α-aryl ketones after desulfurization (up 98%) as well other important derivatives.

Language: Английский

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Chemospecific Cyclizations of α‐Carbonyl Sulfoxonium Ylides on Aryls and Heteroaryls

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 58(45), P. 16198 - 16202

Published: Sept. 11, 2019

The functionalization of aryl and heteroaryls using α-carbonyl sulfoxonium ylides without the help a directing group has remained so far neglected area, despite advantageous safety profile ylides. Described herein are cyclizations onto benzenes, benzofurans N-p-toluenesulfonyl indoles in presence base HFIP, whereas pyrroles N-methyl undergo cyclization an iridium catalyst. Significantly, these two sets conditions chemospecific for each groups substrates.

Language: Английский

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Iridium(III)-Catalyzed Tandem Annulation Synthesis of Pyrazolo[1,2-α]cinnolines from Pyrazolones and Sulfoxonium Ylides

The Journal of Organic Chemistry, Journal Year: 2018, Volume and Issue: 84(1), P. 409 - 416

Published: Dec. 6, 2018

A highly efficient iridium-catalyzed cascade annulation of pyrazolones and sulfoxonium ylides to access various pyrazolo[1,2-α]cinnoline derivatives has been achieved. This novel approach expanded the application scope coupling partners ylides. The control experiments were performed give insight into mechanism this reaction.

Language: Английский

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Copper-Catalyzed Annulation or Homocoupling of Sulfoxonium Ylides: Synthesis of 2,3-Diaroylquinolines or α,α,β-Tricarbonyl Sulfoxonium Ylides

Organic Letters, Journal Year: 2020, Volume and Issue: 22(4), P. 1504 - 1509

Published: Feb. 11, 2020

An unprecedented copper-catalyzed reaction of sulfoxonium ylides and anthranils is reported that enables an easy access to 2,3-diaroylquinolines through a [4+1+1] annulation. Copper-catalyzed homocoupling provided α,α,β-tricarbonyl ylides, which provides strategy extend the carbon chain C–C bond formation. The utility products as well mechanistic details process are presented.

Language: Английский

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Thioether-Directed C4-Selective C–H Acylmethylation of Indoles Using α-Carbonyl Sulfoxonium Ylides

Organic Letters, Journal Year: 2020, Volume and Issue: 22(12), P. 4806 - 4811

Published: June 1, 2020

Site-selective direct functionalization of an indole benzenoid core has been a great challenge due to its inherently poor reactivity. We herein demonstrate iridium-catalyzed C4-selective acylmethylation indoles using α-carbonyl sulfoxonium ylides as carbene precursors. This method exhibits high efficiency and broad functional group compatibility. The directing was easily removed or converted other functionalities after the catalysis. potential synthetic utility coupling products highlighted by constructing medium-sized polycyclic indoles.

Language: Английский

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Rh(III)-Catalyzed Reaction of α-Carbonyl Sulfoxonium Ylides and Alkenes: Synthesis of Indanones via [4 + 1] Cycloaddition

Organic Letters, Journal Year: 2020, Volume and Issue: 22(4), P. 1375 - 1379

Published: Feb. 3, 2020

The synthesis of indanone derivatives by the Rh(III)-catalyzed reaction α-carbonyl sulfoxonium ylides with activated alkenes is reported. shows a high tolerance for functional groups and furnishes variety substituted via formal [4 + 1] cycloaddition. Highly stable were used as substrates in this C-H functionalization, their bifunctional character could be effectively exploited using Rh(III) catalysis sequential double C-C bond formation. Based on mechanistic studies including deuterium-labeling experiments, proposed to proceed follows: oxidative alkenylation β-hydride elimination, readdition H-Rh species, 1,2-carbon shift elimination DMSO, protonation.

Language: Английский

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Application of Sulfoxonium Ylides or Iodonium Ylides in Rhodium‐Catalyzed Synthesis of Phenanthrenes

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(8), P. 1744 - 1750

Published: Feb. 22, 2024

Abstract The transmetalation triggered rhodium‐catalyzed C−H bond activation and tandem annulation of 2‐biphenylboronic acids with sulfoxonium ylides or iodonium has been developed. Various products phenanthrenes were constructed under redox‐neutral conditions in 34–86% yields. Several mechanism exploration experiments derivatization reactions conducted sequence to gain a deeper understanding the process potential this transformation. It offers an alternative approach for synthesis phenanthrene derivatives.

Language: Английский

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Ruthenium(II)‐Catalyzed Homocoupling of Weakly Coordinating Sulfoxonium Ylides via C−H Activation/Annulations: Synthesis of Functionalized Isocoumarins

Advanced Synthesis & Catalysis, Journal Year: 2019, Volume and Issue: 361(22), P. 5191 - 5197

Published: Sept. 30, 2019

Abstract Homocoupling of weakly coordinating sulfoxonium ylides was accomplished via ruthenium (II) catalyzed C−H activation process. This strategy provides a convenient, efficient and step‐economic method to access 3‐substituted isocoumarins with good functional group tolerance. The ylide acts both as the convenient aromatic substrate acylmethylation reagent in this transformation. Moreover, products could be transformed diverse valuable derivatives. magnified image

Language: Английский

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Palladium-Catalyzed Synthesis of Bis-Substituted Sulfoxonium Ylides

Organic Letters, Journal Year: 2018, Volume and Issue: 21(1), P. 296 - 299

Published: Dec. 20, 2018

The lack of general access to bis-substituted sulfoxonium ylides is addressed by developing a palladium-catalyzed C–H cross-coupling α-ester with (hetero)aryl iodides, bromides, and triflates. Three different catalysts have been evaluated. This method amenable the late-stage functionalization active pharmaceutical ingredients.

Language: Английский

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α-Imino Iridium Carbenes from Imidoyl Sulfoxonium Ylides: Application in the One-Step Synthesis of Indoles

The Journal of Organic Chemistry, Journal Year: 2020, Volume and Issue: 85(11), P. 7433 - 7445

Published: April 28, 2020

Imidoyl sulfoxonium ylides are presented for the first time as potential precursors to generate α-imino metal-carbene intermediates and applied in direct C-H functionalization reactions catalyzed by [Ir(cod)Cl]2 (4 mol %) provide 2-substituted indoles (up 70% yield) just one step. This class of sulfur ylide is successfully obtained from imidoyl chloride dimethylsulfoxonium methylide (23 new examples 45-85% or imino group formation corresponding β-keto anilines presence TiCl4 a Lewis acid (9 33-94% yield).

Language: Английский

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