open access

https://hdl.handle.net/2115/91058

Reactive orbital energy theory serving a theoretical foundation for the electronic theory of organic chemistry

英語

the electronic theory of organic chemistry

2023-01-15

John Wiley & Sons

Journal of computational chemistry

44(2)

93-104

It is established that the reactive orbital energy theory (ROET) theoretically reproduces the rule-based electronic theory diagrams of organic chemistry by a comparative study on the charge transfer natures of typical organic carbon-carbon and carbon-heteroatom bond formation reactions: aldol, Mannich, alpha-aminooxylation, and isogyric reactions. The ROET, which is an expansion of the reaction electronic theories (e.g., the frontier orbital theory) in terms of orbital energies, elucidates the reactive orbitals driving reactions and the charge transferability indices of the reactions. Performing the ROET analyses of these reactions shows that the charge transfer directions given in the rule-based diagrams of the electronic theory are reproduced even for the functional groups of charge transfer destinations in all but only two processes for 38 reaction processes. The ROET analyses also make clear the detailed orbital-based pictures of these bond formation reactions: that is, the use of the out-of-plane antibonding pi orbitals in acidic conditions (enol-mode) and in-plane antibonding pi orbitals in basic conditions (enolate-mode), which explain the experimentally assumed mechanisms such as the pi-bond formations in acidic conditions and sigma-bond formations at alpha-carbons in basic conditions. Furthermore, the ROET analyses explicate that the methyl group initially accepts electrons and then donates them to the bond formations in the target reactions. It is, consequently, suggested that the ROET serves a theoretical foundation for the electronic theory of organic chemistry.

学術雑誌論文

Accepted Manuscript

This is the peer reviewed version of the following article: Tsuneda, T., Sumitomo, H., Hasebe, M., Tsutsumi, T., Taketsugu, T., J. Comput. Chem. 2023, 44(2), 93. which has been published in final form at https://doi.org/10.1002/jcc.27017. 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.

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