在这项研究中,我们探索了赫德-克莱森重排的立体选择性,关注两个吸电子基团和八个不同取代基的影响。利用科廷-哈米特原理,我们对反应进行了能量计算,产品,和过渡状态使用M062X/def2TZVPP复合模型。我们的分析表明,动力学因素主要决定了反应平衡。我们研究的一个关键方面是舒宾的能量分解分析在优化过渡态中的应用,强调静电相互作用在确定立体选择性中的重要作用。我们进一步将每个过渡态分解为四个片段:吸电子基团($CO_2Et$,$CN$),赫德集团($H$),各种取代基($CH_3$,$Et$,$SProp$,$TBut$,$IsoBut$,$NH_2Ph$,$NO_2Ph$,$Ph$),和中央碎片。这种碎裂方法能够深入分析群偶极矩,提供对静电力的见解。我们的发现揭示了赫德-克莱森重排中驱动立体选择性的复杂机制,并增强了对分子相互作用的理解。为有机合成提供有价值的启示。
In this study, we explore the stereoselectivity of Hurd-Claisen Rearrangements, focusing on the influence of two electron-withdrawing groups and eight diverse substituents. Utilizing the Curtin-Hammett principle, we performed energy calculations for reactions, products, and transition states using the M062X/def2TZVPP compound model. Our analysis reveals that kinetic factors predominantly dictate the reaction equilibrium. A key aspect of our research is the application of Shubin\'s energy decomposition analysis to optimized transition states, highlighting the significant role of electrostatic interactions in determining stereoselectivity. We further dissected each transition state into four fragments: the electron-withdrawing groups ($CO_2Et$, $CN$), the Hurd group ($H$), various substituents ($CH_3$, $Et$, $SProp$, $TBut$, $IsoBut$, $NH_2Ph$, $NO_2Ph$, $Ph$), and the central fragment. This fragmentation approach enabled an in-depth analysis of group dipole moments, providing insights into the electrostatic forces at play. Our findings shed light on the intricate mechanisms driving stereoselectivity in Hurd-Claisen Rearrangements and enhance the understanding of molecular interactions, offering valuable implications for organic synthesis.