Molecular Mechanisms of Regio-and Stereoselections in the Reactions of Charcogen Coumpounds

随着化学家的兴趣扩展到更高原子序数的元素的化学，出现了许多不能用主要针对第一行元素发展的价概念来解释的情况。在这项研究中，我们彻底重新研究了现有的反应性理论，并提出了一个新的理论处理的反应性。我们已经定义了每个反应物分子的反应轨道，这些反应物分子积极参与与试剂形成新键，并位于反应位点周围。通过这种方式，我们能够估计反应位点的局部供电子和接受电子的电势，使得比较不同分子的反应性变得可行。为了证明这一理论的适用性，并进一步明确生碳化合物与周围有其它元素的化合物之间的区别，我们将这一理论应用于碳π共轭物种中的取代基效应，其中有大量的 ...更多信息 实验数据是可用的。结果表明，与现有理论相比，我们的新理论对实验观测的解释更令人满意。我们还将该理论应用于烯丙基化合物的反应，获得了成功的结果。为了揭示硒化合物σ迁移重排中不对称诱导反应的分子机理和控制反应路径的因素，我们进行了从头计算.对甲基锂与含二茂铁基的恶唑啉的反应进行了计算，阐明了锂优先加到氮中心的原因。在实验方面，我们首次合成了光学活性的[R，S ; R，S] -和[S，R ; S，R]-双[2- [1-（2-甲氧基苯基）-2-甲基-3-氧代-2-（二甲基氨基）乙基]二茂铁基]二硒醚并已证明不对称硒氧化物消除和不对称[2，为了研究过渡金属配合物的不对称催化反应，我们合成了一系列含二茂铁基的碳精化合物。研究表明，通过使用具有手性配体的Rh（I）络合物，酮的硅氢加成以高产率得到手性醇。少

As the interests of chemists expands to chemistry of the elements with higher atomic numbers, there appear many cases which cannot be interpreted by the valence concept that has been developed mainly for the first row elements. In this research, we have thoroughly reinvestigated the presenting reactivity theories and proposed a novel theoretical treatment of reactivity. We have defined the reactive orbital for each reactant molecule that participates actively in the formation of new bonds with a reagent, being localized around the reaction sites. In this way, we are able to estimate the local electron-donating and accepting potentials of the reaction sites, making it feasible to compare the reactivity of different molecules. With a view to proving the applicability of this theory and to making clearer the difference between charcogen componds and compounds with other elements around, we have applied the theory to the subsituent effects in the carbon pi conjugated species in which ample … More experimental data are available. It has been demonstrated that our new theory interprets the experimental observations much more satisfactorily compared with the existing theories. We have also applied the theory to the reaction of allylic compounds, obtaining successful results. To disclose the molecular mechanism and the factors controlling the reaction path for an asymmetric induction in sigmatropic rearrangements of selenium compounds, we have carried out ab initio MO calculations. Calculation have also been carried out on the reaction between methkyllithium and oxazolines having a ferrocenyl group, elucidating the reason why lithium adds preferentially to the nitrogen center. The results of these works are being prepared for publishing.On the experimental side, we have synthesized for the first time optically active [R,S ; R,S] - and [S,R ; S,R]-Bis [2- [1- (dimethyamino) ethyl] ferrocenyl] Diselenides and have demonstrated asymmetric selenoxide elimination and asymmetric [2,3] sigmatropic rearrangement take place very efficiently.To study asymmetric catalytic reacttions by the use of transition metal complexes, we have synthesized a variety of charcogen compounds having ferrocenyl groups. It was been shown hydrosilylation of ketones by using Rh (I) complexes having chiral ligands gives chiral alcohols at high yields. Less