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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Divergent Synthesis of Dihydrofuran and Dienol Scaffolds via Pd-Catalyzed Decarboxylative Carbene Cross-Coupling

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Апрель 24, 2025

Herein, we report a novel ligand-switchable Pd-catalyzed carbene coupling reaction employing vinylethylene carbonates and sulfoxonium ylides. By proper choice of ligands, the chemoselectivity process could be efficiently regulated, allowing for availability dihydrofuran or dienol scaffolds. This method features mild conditions, broad scope, remarkable synthetic utility. Compound 6f can effectively stimulate secretion GLP-1, providing promising insight into development small-molecule agonists GLP-1 receptor.

Язык: Английский

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Palladium-Catalyzed Synthesis of α-Carbonyl-α′-(hetero)aryl Sulfoxonium Ylides: Scope and Insight into the Mechanism

The Journal of Organic Chemistry, Год журнала: 2019, Номер 85(2), С. 1126 - 1137

Опубликована: Дек. 6, 2019

Despite recent advances, a general method for the synthesis of α-carbonyl-α′-(hetero)aryl sulfoxonium ylides is needed to benefit more greatly from potential safety advantages offered by these compounds over parent diazo compounds. Herein, we report palladium-catalyzed cross-coupling aryl bromides and triflates with α-carbonyl ylides. We also use this modification an active pharmaceutical ingredient key precursor antagonists neurokinin-1 receptor. In addition, mechanism reaction was inferred several observations. Thus, oxidative addition complex [(XPhos)PhPdBr] its dimer were observed 31P{1H} NMR, complexes shown be catalytically kinetically competent. Moreover, resulting transmetalation [(XPhos)ArPdBr] (Ar = p-CF3–C6H4) model ylide mass spectrometry. Finally, partial rate law suggests that subsequent deprotonation are rate-determining in catalytic cycle.

Язык: Английский

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Pd/C-Catalyzed Carbonylative Synthesis of α-Carbonyl-α′-Amide Sulfoxonium Ylides from Azides

The Journal of Organic Chemistry, Год журнала: 2020, Номер 85(8), С. 5733 - 5740

Опубликована: Март 25, 2020

The synthesis of α-carbonyl-α′-amide sulfoxonium ylides by Pd/C-catalyzed carbonylative transformation azides with α-carbonyl has been studied. This method offers a direct approach to produce synthetically useful in high efficiency. By using readily available substrates, 39 examples products were prepared good yields outstanding functional group compatibility. An example converting the obtained ylide into corresponding 1,3-dicarbonyl compound given as well.

Язык: Английский

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Copper-catalyzed N–H insertion reactions from sulfoxonium ylides

Tetrahedron, Год журнала: 2020, Номер 76(51), С. 131313 - 131313

Опубликована: Май 29, 2020

Язык: Английский

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