微扰分子轨道法在有机化学中的应用

The Application of The PMO Theory in Organic Chemistry

经Dewar,Hoffmann,Epiotis,Houk,Wolfe和Kost等理论化学家的努力,PMO理论已经成为研究影响分子构型、构象和(立体专一性和区域专一性)反应产物的结构因素的一个有效的手段。Epiotis的非键轨道作用理论已经使有机化学家认识到,一个拥挤的构象或过渡态不一定是一个能量上不利的状态。π轨道作用的分析表明,共轭基团间的作用在本质上是相斥的,全平面构象不是共轭效应最大的构象。WSW-like法不仅为定量PMO法提供了一组完整的、具有正确集据数的轨道基组,而且它还成功地将轨道作用能转化为原子作用能。

The progress in the PMO theory made by Dewar, Hoffmann, Epiotis, Houk, Wolfe and Kost et al, is reviewed. The various PMO methods have been used as the useful instrument for analyzing the effects of the orbital interactions on the molecular geometry and on the sterospecific and re-giospecific reactions, such as 1,2 - asymmetric addition to carbon - oxygen double bond of ketone and various cycloaddition reactions. Epiotis' Non - Bonded Orbital interaction theory has made organic chemist to understand that a crowded geometry is not mere aberration of an order dominated by 'steric effect'. The PMO analysis for the Ttorbital interaction shows that the interaction between the conjugated groups is repulsive in nature. Our WSW - like procedure provides for the quantitative PMO analysis a set of complete fragment MOs basis, and it has succeed in transforming the orbital interaction energy into the atomic interacion energy.