The Electronic Factor in Face Selection

这项来自有机动力学项目的资助资助了纽约州立大学石溪分校的William J. le Noble教授的工作，他通过使用各种取代的金刚烷-2- 1和相关化合物来研究pi-非对面层选择性的电子起源。具体项目有：(1)加成反应，包括二羟基化反应、Grob破碎反应、Michael加成反应和Claisen重排反应；(2)旨在区分Ahn、Cieplak和Felkin理论模型的研究；(3)通过在C6上扩展/还原一个亚甲基，研究更强的5-取代效应（n -氧化物和硼铵化合物），研究4,9-二取代效应，研究5,7-二取代效应，以及修饰C2上的三角中心，骨架和取代模式的变化。在这个项目中，William K. le Noble教授将研究在酮、亚胺和烯烃的键形成（和断开）过程中控制pi-非对面层选择性的电子效应。选择金刚烷框架以消除干扰的空间和构象影响。研究重点是标准加成反应，区分理论模型，并将探讨强取代基和结构刚度的影响。

This grant from the Organic Dynamics Program supports the work of Professor William J. le Noble at the State University of New York at Stony Brook to study the electronic origins of pi- diastereofacial selectivity by using various substituted adamantan-2-ones and related compounds. The specific projects are: (1) addition reactions, including dihydroxylation, Grob fragmentation, Michael addition, and Claisen rearrangement; (2) studies directed to differentiate between the theoretical models of Ahn, Cieplak, and Felkin; (3) changes in skeleton and substitution patterns by expanding/reducing adamantane by one methylene unit at C6, by studying more powerful 5-substituent effects (N-oxides and boron and ammonium compounds), by studying the 4,9-disubstitution effect, by studying the 5,7-disubstitution effect, and by modifying the trigonal center at C2. %%% In this project Professor William K. le Noble will study the electronic effects that govern pi-diastereofacial selectivities in bond making (and breaking) to (and from) ketones, imines, and olefins. The adamantane frame is selected to eliminate interfering steric and conformational effects. The study concentrates on standard addition reaction, differentiating between theoretical models, and will explore the influence of powerful substituents and structural rigidity.