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

Wei Zhou,

Lei Zhang, Dan-Yang Liu

et al.

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

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

Wei Zhou,

Lei Zhang, Dan-Yang Liu

et al.

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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