open access

https://hdl.handle.net/2115/97801

Unraveling Reaction Path Bifurcation: Insights Into Electron Movement via Natural Reaction Orbitals

英語

substituent effect

2025-04

John Wiley & Sons

Journal of Computational Chemistry

46(10)

e70101

This study investigates the Beckmann rearrangement of 1-phenyl-2-propanone oxime derivatives, focusing on the reaction path bifurcation behavior from the perspective of electron movement. The previous work reported that electron-withdrawing substit-uents drove the reaction toward the rearrangement pathway, while electron-donating substituents favored the fragmentation pathway. Through natural reaction orbital (NRO) analysis, this research demonstrates how electrons move at critical branching points, specifically in the directions of the intrinsic reaction coordinate (IRC) and the projected vibrational mode associated with the branching behavior. The NRO approach, which complements traditional IRC and ab initio molecular dynamics methods, not only provides valuable quantitative insights for predicting product distributions but also aids in the strategic design of substitu-ents for desired products. These findings extend our understanding of reaction mechanisms and byproduct formation, offering fresh perspectives on complex chemical transformations.

学術雑誌論文

Accepted Manuscript

This is the peer reviewed version of the following article:Tatsuhiro Nakanishi, Takuro Tsutsumi, Yuriko Ono, Kazuki Sada, Tetsuya Taketsugu, J. Comput. Chem. 2025, 46(10), e70101, which has been published in final form at [Link to final article using https://doi.org/10.1002/jcc.70101. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions. This article may not be enhanced, enriched or otherwise transformed into a derivative work, without express permission from Wiley or by statutory rights under applicable legislation. Copyright notices must not be removed, obscured or modified. The article must be linked to Wiley’s version of record on Wiley Online Library and any embedding, framing or otherwise making available the article or pages thereof by third parties from platforms, services and websites other than Wiley Online Library must be prohibited.

0192-8651

1096-987X

AA00257341