Cation Radical Explorations

9312460将研究阳离子自由基西格玛键上的三电子SN2取代的一般性、范围和局限性。这项研究将：(1)扩大可用于实际取代反应的亲核试剂的种类；(2)研究控制三电子SN2反应区域化学的因素；(3)探索各种环丙烷阳离子自由基的电子结构以测试结构/活性关系；(4)测试简单的烷基取代的环丙烷阳离子自由基以及不含环丙烷环的阳离子自由基上的取代反应的可行性。来自有机动力学项目的这笔赠款支持罗切斯特大学约瑟夫·P·迪诺琴佐教授的工作。我们将研究富电子分子与环丙烷阳离子自由基的反应。后一种是三碳循环，其中一个电子被移除。这项研究将包括考虑富电子分子攻击环丙烷阳离子自由基的位置，以及将反应扩展到环丙烷阳离子自由基以外的物种。这些反应将有可能制造出更大的感兴趣的分子。该反应的研究也将提供重要的理论见解，因为它是一个常见的两电子取代反应的三电子类似物。***

9312460 Dinnocenzo The generality, scope, and limitations of three-electron SN2 substitutions on cation radical sigma bonds will be studied. The study will: (1) extend the variety of nucleophiles that can be used in practical substitution reactions, (2) investigate the factors that control the regiochemistry of three-electron SN2 reactions, (3) probe the electronic structures of various cyclopropane cation radicals to test structure/reactivity relationships, and (4) test the viability of substitution reactions on simple, alkyl- substituted cyclopropane cation radicals and, in addition, cation radicals which do not contain a cyclopropane ring. %%% This grant from the Organic Dynamics Program supports the work of Professor Joseph P. Dinnocenzo at the University of Rochester. The reactions of electron-rich molecules with cyclopropane cation radicals will be studied. The latter species are three-carbon cycles in which one electron has been removed. The study will include consideration of where the electron-rich molecule attacks the cyclopropane cation radical and extension of the reaction to species other than the cyclopropane cation radical. These reactions will have the potential to make larger molecules that are of interest. The reaction to be studied will provide important theoretical insight as well, since it is the three-electron analog of a common two-electron substitution reaction. ***