Comparison of Phosphonium and Sulfoxonium Ylides in Ru(II)-Catalyzed Dehydrogenative Annulations: A Density Functional Theory Study

Molecules, Journal Year: 2025, Volume and Issue: 30(9), P. 1883 - 1883

Published: April 23, 2025

Density functional theory calculations have been performed to explore the detailed mechanism of a ruthenium-catalyzed dehydrogenative annulation between α-carbonyl phosphonium ylide (A) and sulfoxonium (B). The proposed catalytic cycles consist several elementary steps in succession, namely C–H activation A, insertion B, reductive elimination, protodemetallation, an intramolecular Wittig reaction, which is rate-limiting, with free energy barrier 31.7 kcal/mol. As A B are both capable being substrate carbene precursor, there potentially four competing pathways including homo-coupling reactions. Further demonstrate that more reactive step than while opposite conclusion true for step, can successfully explain fact solely observed product originated from use as precursor. Molecular electrostatic potential, charge decomposition, electron density difference analyses were understand distinct behaviors two ylides nature key ruthenium–carbene intermediate.

Language: Английский

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

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: April 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.

Language: Английский

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Quinazolinone-to-Isoquinoline Metamorphosis by Ruthenium-Catalyzed [4+2] Annulation with Sulfoxonium Ylides

Organic Letters, Journal Year: 2024, Volume and Issue: 26(50), P. 10951 - 10957

Published: Dec. 10, 2024

Molecular editing of quinazolinones to isoquinolines by a novel ruthenium-catalyzed [4+2] annulation with sulfoxonium ylides has been developed. The method permits the precise and rapid assembly multisubstituted aminoisoquinolines, class heterocycles that play privileged role in organic synthesis pharmaceutical development. This new catalytic process exhibits programmability, including directed C–H acetylation, nucleophilic cyclization, alcoholysis. Remarkably, various 2-arylquinazolinones could be employed excellent yields broad functional group tolerance. heterocycle-to-heterocycle protocol is compatible green chemistry using an EtOH solvent releasing H2O dimethyl sulfoxide as byproducts.

Language: Английский

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Maleimide-Dependent Rh(III)-Catalyzed Site-Selective Mono and Dual C–H Functionalization of 2-Arylbenzo[d]thiazole and Oxazole Derivatives

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 3, 2024

The site-selective functionalization of aromatic compounds via C–H activation has emerged as a popular tool in organic synthesis. In this study, we report regioselective coupling maleimide to 2-arylbenzo[d]thiazoles the presence rhodium(III) catalyst. Depending upon nature substituent (R2-group) present substrate, either mono- or bis-1,4-addition products were observed methodology. case R2 = aryl, cyclohexyl, and tert-butyl, mono was observed, whereas substituents, such methyl, ethyl, benzyl, methyl thiophene, provided bis major products. Similar selectivity also 2-arylbenzo[d]oxazoles.

Language: Английский

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