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 antibonding π orbitals in acidic conditions (enol-mode) and in-plane antibonding π orbitals in basic conditions (enolate-mode), which explain the experimentally assumed mechanisms such as the π-bond formations in acidic conditions and σ-bond formations at α-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.

中文翻译：

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反应轨道能理论为有机化学电子理论奠定了理论基础

通过对典型有机碳-碳和碳-杂原子键形成反应的电荷转移性质的比较研究，确定反应轨道能量理论 (ROET) 在理论上再现了基于规则的有机化学电子理论图：aldol，Mannich , α-氨基氧基化和等回反应。ROET 是反应电子理论（例如，前沿轨道理论）在轨道能量方面的扩展，阐明了驱动反应的反应轨道和反应的电荷可转移性指数。对这些反应进行 ROET 分析表明，基于规则的电子理论图中给出的电荷转移方向即使对于 38 个反应过程中的电荷转移目的地的官能团也可以再现，但只有两个过程。ROET 分析还明确了这些键形成反应的基于轨道的详细图片：即在酸性条件（烯醇模式）和面内反键 π中使用面外反键 π轨道碱性条件下的轨道（烯醇化模式），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碳的σ键形成。此外，ROET 分析表明甲基最初接受电子，然后将其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。