Electronically Driven Stereogenesis

有机动力学计划将支持教授威廉J。 勒诺布尔的研究“电子驱动的立体发生”， 纽约州立大学化学系， 斯托尼布鲁克。 他将探索化学键的形成 在三角形碳和键断裂在四碳， 在具有最多的表面选择性的一侧上是有利的 富电子σ键在反周面位置。 在这个项目中，勒诺布尔教授正在研究三个主要的 研究领域，将利用独特的优势， 2，5-二取代金刚烷作为探针研究 非对映体选择中的立体电子效应。 一 研究领域将涉及审查一个简单的 根据键形成的规则（加成反应： 亲电加成，亲核加成，周环加成 反应等）在三角碳和键断裂 （脱羧、断裂、溶剂分解等）在 四碳出现在具有最多 富电子键反周面。 的刚性 金刚石骨架保证了没有旋转运动 掩盖了构象中观察到的面选择 不确定性 研究的另一个领域涉及 手性，第三个领域涉及的动力学研究， 2-和5-甲苯磺酰基金刚烷的溶剂分解。

The Organic Dynamics Program will support Professor William J. le Noble's study of "Electronically Driven Stereogenesis" in the Chemistry Department at the State University of New York at Stony Brook. He will explore the principle that bond formation at trigonal carbon and bond cleavage at tetragonal carbon are favored in face selectivity on that side which has the most electron-rich sigma bond in the antiperiplanar position. In this project, Professor le Noble is pursuing three major areas of research that will exploit unique advantages of 2,5-disubstituted adamantanes as probes to study stereoelectronic effects in diastereofacial selection. One area of study will involve examination of the scope of a simple rule according to which bond formation (addition reactions: electrophilic addition, nucleophilic addition, pericyclic reactions, etc.) at trigonal carbon and bond cleavage (decarboxylation, fragmentation, solvolysis, etc.) at tetragonal carbon occur at that face which has the most electron rich bond antiperiplanar. The rigidity of the adamantane skeleton guarantees that no rotational motion will shroud the observed face selection in conformational uncertainty. Another area of study deals with the transfer of chirality, and the third area deals with the kinetic studies of solvolysis of 2- and 5-tosyl adamantanes.