Insights into the multifaceted applications of vinyl sulfoxonium ylides

Chemical Communications, Год журнала: 2023, Номер 59(83), С. 12411 - 12422

Опубликована: Янв. 1, 2023

Sulfoxonium ylides are important synthetic precursors in various organic transformations. Their potential was well explored the synthesis of bioactive natural products and pharmaceuticals. Vinyl sulfoxonium ylide is a stabilized containing an electron-deficient alkene at ylidic carbon. Similar to α-keto ylides, these reagents can generate vinyl carbenes presence metals under suitable conditions. These be used for transformations such as X-H (X = C, N, O, S) insertions, annulations, rearrangement reactions. Due dipole structure ylide, it undergo electrophilic addition with electrophiles α-position. synthons aromatic heteroaromatic compound syntheses. Moreover, their stability convenient handling make them replacements thermally less stable diazo compounds. Herein, we provide overview early efforts this area, particular emphasis on our own recent development ylide-mediated absence metal catalysis, also give personal perspectives challenges future scope improving application ylides.

Язык: Английский

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Metal-free cascade O–H double insertion between I^(III)/S^(VI)-ylides, carboxylic acids, and alcohols: modular access to unsymmetrical α,α-O,O-substituted ketones

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(11), С. 3234 - 3241

Опубликована: Янв. 1, 2024

Herein, we present a cascade O–H double insertion reaction between I (III) /S (VI) -ylides, carboxylic acids, and alcohols under metal-free conditions, enabling the modular synthesis of unsymmetrical α,α- O , -substituted ketones.

Язык: Английский

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

Organic Letters, Год журнала: 2024, Номер 26(27), С. 5811 - 5816

Опубликована: Июнь 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.

Язык: Английский

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Stereoselective Three-Component Carbocyclization of 1,7-Enynes with Sulfoxonium Ylides and Water under Photoredox Catalysis

Organic Letters, Год журнала: 2024, Номер 26(31), С. 6736 - 6741

Опубликована: Июль 29, 2024

A visible-light-induced photoredox three-component carbocyclization reaction of 1,7-enynes with sulfoxonium ylides and water is reported. The protocol provides a facile entry to structurally valuable highly functionalized cyclopenta[c]quinoline scaffolds in chemoselective stereoselective manner. Salient features this method include redox-neutral conditions, no requirement base or other additive, good functional-group tolerance.

Язык: Английский

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Divergent Approach to Highly Substituted Arenes via [3 + 3] Annulation of Vinyl Sulfoxonium Ylides with Ynones

Organic Letters, Год журнала: 2023, Номер 25(50), С. 8992 - 8996

Опубликована: Дек. 12, 2023

Herein, we report the divergent benzannulation for highly substituted arenes using vinyl sulfoxonium ylides and ynones. The addition of ynone at γ-position leads to dienyl ylide that can undergo selective annulation under different conditions give m-terphenyls parabens. Moreover, control experiments quantum chemical calculations reveal two distinct reaction mechanisms both annulations.

Язык: Английский

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Visible-Light-Induced photoredox aerobic coupling of sulfonium ylides and amines leading to E-selective formation of 2-amino-2-butene-1,4-diones

Organic Chemistry Frontiers, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

A novel visible-light-induced photoredox three-component aerobic coupling reaction of sulfoxonium ylides and amines is reported.

Язык: Английский

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Synthesis of Multisubstituted Arylnitriles via Tf₂O-Mediated Benzannulation of Enaminones with Acylacetonitriles

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Март 3, 2025

A novel and efficient method for the synthesis of multisubstituted arylnitriles via Tf2O-mediated [3 + 2 1] benzannulation enaminones acylacetonitriles has been developed. This reaction proceeds under mild conditions with excellent functional group compatibility. Mechanistic studies have revealed that cyclization involves two consecutive nucleophilic additions, followed by a cascade Knoevenagel condensation aromatization. Additionally, trifluoromethanesulfonate 6 identified as crucial intermediate in this process.

Язык: Английский

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Divergent Construction of α,α-Difunctionalized Ketones via [1,2]-Sigmatropic Rearrangement/Alkylation-Hydroxylation/Dialkylation of I^(III)/S^(VI) Ylides

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Апрель 1, 2025

The rare [1,2]-sigmatropic rearrangement of sulfoxonium-iodonium hybrid ylides is described, which enables the efficient sulfoxidation/sulfonylation-alkylation I(III)/S(VI) with 1,3-dicarbonyls. By slight modification reaction conditions, controllable alkylation-hydroxylation and dialkylation were achieved. This strategy affords a diverse array α,α-difunctionalized ketones in moderate to good yields, demonstrating broad substrate scope. These findings provide an important advancement sulfoxonium highlight divergent reactivity ylides.

Язык: Английский

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

Advanced Science, Год журнала: 2025, Номер unknown

Опубликована: Апрель 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.

Язык: Английский

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Synthesis and Applications of π-Conjugation-Extended Vinyl Sulfoxonium Ylides

Organic Letters, Год журнала: 2023, Номер 25(43), С. 7906 - 7910

Опубликована: Окт. 24, 2023

Herein, we report the synthesis of π-conjugation-extended vinyl sulfoxonium ylides from ylide and electron-deficient alkynes. The new dienoate are used in various transformations, such as X-H (X = S, O) insertion, halogenation, carbene-mediated transformation, radical-mediated reductions to obtain a variety conjugated dienoates.

Язык: Английский

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