A Platform for the Synthesis of Diverse Phosphonyl and Thiofunctionalized Sulfoxonium Ylides

Organic Letters, Journal Year: 2024, Volume and Issue: 26(27), P. 5811 - 5816

Published: June 28, 2024

A practical strategy for the construction of diverse phosphonyl and thiofunctionalized sulfoxonium ylides via controllable monofunctionalization hybrid I(III)/S(VI) is presented. This process allows efficient P–H insertion under Cu catalysis, enabling synthesis ylides, whereas reaction with sulfur-containing reagents including AgSCF3, KSC(S)OR, KSCN mild conditions resulted in α-trifluoromethylthiolation, dithiocarbanation, thiocyanation accordingly. Of note, wide substrate compatibility (108 examples), excellent efficiency (up to 99% yield), gram-scale experiments, various product derivatizations highlight synthetic utility this protocol.

Language: Английский

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Elemental Sulfur-Mediated Synthesis of Quinoxalines from Sulfoxonium Ylides

Organic Letters, Journal Year: 2023, Volume and Issue: 25(28), P. 5329 - 5332

Published: July 7, 2023

A novel straightforward and catalyst-free approach for synthesizing quinoxaline derivatives from sulfoxonium ylides o-phenylenediamines mediated by elemental sulfur has been described. Due to the simple mild reaction conditions, decorated with different functional groups furnished moderate high yields of were well tolerated. Finally, large-scale reactions, synthesis pyrazines, some bioactive compounds are used illustrate potential utility developed approach.

Language: Английский

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Nickel‐Catalyzed Reductive Amidation of Aryl Sulfonium Salts with Isocyanates for Amide Synthesis via C−S Bond Activation

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: unknown

Published: June 28, 2024

Abstract A nickel‐catalyzed reductive amidation of aryl sulfonium salts with isocyanates for amide synthesis via C−S bond cleavage was developed. The reactions proceeded smoothly at ambient temperature in the presence nickel catalyst and manganese metal DMF to give a variety amides moderate good yields wide functional group tolerance.

Language: Английский

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Annulative Coupling of Sulfoxonium Ylides with Aldehydes and Naphthols or Coumarins: Easy Access to Fused Dihydrofurans

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: 90(4), P. 1645 - 1655

Published: Jan. 17, 2025

We present a novel, metal- and additive-free method for the robust synthesis of dihydrofuran-fused naphthalenes coumarins. This approach utilizes annulative coupling sulfoxonium ylides with aldehydes, naphthols, or coumarins at ambient temperature. The exhibits broad substrate compatibility, accommodating various functional groups on naphthol coumarin derivatives resulting in good to high yields desired products. Additionally, we successfully scaled up reactions, synthesized were further converted other valuable bioactive molecules, validating viability our approach.

Language: Английский

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Perhaloacylation of α-Carbonyl Sulfoxonium Ylides

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 2, 2025

A mild and efficient protocol for the perhaloacylation of α-carbonyl sulfoxonium ylides has been developed. The commercially available perfluoro- perchloroacid anhydrides were used as acylating agents in catalyst- additive-free reactions to access α-carbonyl-α'-perhaloacyl high yields. reaction offers a simple method prepare valuable polyfluorinated organosulfur molecules.

Language: Английский

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Recent Developments in Stereoselective Reactions of Sulfoxonium Ylides

Molecules, Journal Year: 2025, Volume and Issue: 30(3), P. 655 - 655

Published: Feb. 1, 2025

This review probes the recent developments in stereoselective reactions within area of sulfoxonium ylide chemistry since early 2000s. An abundance research has been applied to its emergence 1960s. There a continued effort then with work traditional areas, such as epoxidation, aziridination and cyclopropanation. Efforts have also novel olefination insertion reactions, develop methodologies using organocatalysis transition metal catalysis. The growing interrupted Johnson–Corey–Chaykovsky is described, whereby unexpected cyclopropanation epoxidation developed. In general, most observed mechanistic pathway ylides formal cycloaddition: (2 + 1) (e.g., epoxides, cyclopropanes, aziridines), (3 oxetanes, azetidines), (4 indanones, indolines). involves formation zwitterionic intermediate through nucleophilic addition carbanion an electrophilic site. intramolecular cyclization occurs, constructing cyclic product. Insertion X–H bonds X = S, N or P) are observed, protonation followed by X, form inserted

Language: Английский

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Catalyst‐Free Direct Hydrocarbonation of Terminal Alkynes Toward E‐Alkene Substituted Stabilized Sulfoxonium Ylides

Advanced Science, Journal Year: 2025, Volume and Issue: unknown

Published: April 2, 2025

Amide and alkene moieties are frequently found in natural products privileged structures pharmaceuticals agrochemicals. Moreover, vinyl sulfoxonium ylide can be converted into a broad range of high-value compounds, thus they have been widely employed organic synthesis. However, the synthesis alkene-substituted amide-sulfoxonium ylides via intermolecular hydrocarbonation alkynes remains underexplored. This study describes development high-throughput approach to provide diverse functionalized E-alkene substituted (hetero)amide-sulfoxonium ylides. The reaction occurs under mild metal-free conditions, employing as highly effective nucleophiles, which participate Michael addition reactions with various alkynes, such esters, thioesters, ketones, amides, sulfones. low-cost, operationally simple has substrate scope, high functional group compatibility, excellent regio- stereoselectivity, making it suitable for transformation structurally complex molecules. Furthermore, obtained stabilized directly useful valuable 1,5-dicarbonyl thiabenzene 1-oxide compounds.

Language: Английский

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Divergent Access to α-Carbonyl-α′-vinyl Sulfoxonium Ylides and Polysubstituted Furans from β-Ketosulfoxonium Ylides and Ynone-Esters

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: April 28, 2025

Here, we describe the synthesis of novel α-carbonyl-α'-vinyl sulfoxonium ylides under ambient, catalyst-free, and additive-free conditions, demonstrating broad substrate scope scalability using β-ketosulfoxonium α-ynone-esters. Furthermore, these serve as versatile intermediates for highly substituted furans via Brønsted acid (p-TsOH) catalysis at 130 °C. This approach offers key advantages, including wide compatibility, divergent product formation from common precursors, gram-scale feasibility, good to excellent yields.

Language: Английский

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Straightforward access to α-thiocyanoketones and thiazoles from sulfoxonium ylides

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(68), P. 10247 - 10250

Published: Jan. 1, 2023

Efficient, versatile, and metal-free strategies for synthesizing α-thiocyanoketones thiazoles from β-ketosulfoxonium ylides ammonium thiocyanate have been described. Due to its simplicity, benign reaction conditions, excellent chemoselectivity, high yield, this method represents a unique approach divergent synthesis. Finally, the potential value of developed methods is demonstrated via large-scale reactions synthesis Fanetizole, an anti-inflammatory drug.

Language: Английский

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Synthesis of α-cyanato-α′-carbonyl sulfoxonium ylides in water

Green Chemistry, Journal Year: 2023, Volume and Issue: 25(18), P. 7068 - 7072

Published: Jan. 1, 2023

A new catalyst-, metal- and additive-free green strategy to synthesize bis-substituted sulfoxonium ylides is reported, which has good compatibility with various substituents generally excellent yields.

Language: Английский

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