Reactive orbital energy theory serving a theoretical foundation for the electronic theory of organic chemistry
Reactive orbital energy theory serving a theoretical foundation for the electronic theory of organic chemistry
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反应轨道能量理论为有机化学电子理论奠定了理论基础
DOI：
10.1002/jcc.27017
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发表时间：
2022
影响因子：
3
通讯作者：
Taketsugu Tetsuya
中科院分区：
文献类型：
--
作者：
Tsuneda Takao;Sumitomo Hiroki;Hasebe Masatoshi;Tsutsumi Takuro;Taketsugu Tetsuya
通过对典型的有机碳-碳键和碳-杂原子键形成反应：羟醛缩合反应、Mannich反应、α-氨氧基化反应和等旋反应的电荷转移性质的比较研究，证实了反应轨道能量理论（ROET）在理论上再现了有机化学中基于规则的电子理论图. ROET是反应电子理论的扩展（例如，前线轨道理论）阐明了驱动反应的反应轨道和反应的电荷转移指数。对这些反应进行ROET分析表明，在电子理论的基于规则的图中给出的电荷转移方向即使对于38个反应过程中的所有过程中的电荷转移目的地的官能团也是重现的，但只有两个过程。ROET分析还清楚地显示了这些成键反应的详细轨道图像：即在酸性条件下使用面外反键π轨道（烯醇模式）和在碱性条件下使用面内反键π轨道（烯醇模式），这解释了实验假设的机制，例如酸性条件下的π键形成和碱性条件下α碳上的σ键形成。此外，ROET分析表明，甲基基团最初接受电子，然后将它们提供给目标反应中的键形成。因此，建议ROET为有机化学的电子理论提供理论基础。
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,α‐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 antibondingπorbitals in acidic conditions (enol‐mode) and in‐plane antibondingπorbitals in basic conditions (enolate‐mode), which explain the experimentally assumed mechanisms such as theπ‐bond formations in acidic conditions andσ‐bond formations atα‐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.
影响因子：
5.5
作者：
M. Hasebe;Takuro Tsutsumi;T. Taketsugu;T. Tsuneda
通讯作者：
T. Tsuneda
影响因子：
4.4
作者：
Tawada, Y;Tsuneda, T;Hirao, K
通讯作者：
Hirao, K