Conformational Isomerization as a Process to Determine Selectivity over Reaction Pathways: Effect of Alkene Rotation in Chain Walking via Cis Alkene Intermediates

研究成果: Article査読

抄録

In organic reactions, bond-forming and bond-cleaving processes are generally considered to be more important than other processes such as conformational isomerization. We report herein an example where a conformational isomerization process, propeller-like alkene rotation, is considered to determine the selectivity over the reaction pathways. The transition state with the highest energy barrier in some alkylpalladium isomerization (chain walking) events was theoretically indicated to correspond to alkene rotation, while transition states for bond-cleaving β-hydride elimination and bond-forming migratory insertion were not even observed. It was also suggested both theoretically and experimentally that the palladium chain walking over internal carbons in alkyl chains proceeds via cis alkene intermediates rather than thermodynamically more stable trans alkene intermediates, due to their relative difficulty to undergo alkene rotation.

本文言語English
ページ(範囲)4712-4721
ページ数10
ジャーナルJournal of Organic Chemistry
89
7
DOI
出版ステータスPublished - 2024 4月 5

ASJC Scopus subject areas

  • 有機化学

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