The Electronic Factor in Face Selection

人脸选择中的电子因素

• 批准号: 9310712
• 负责人: William le Noble
• 金额: $ 32万
• 依托单位: SUNY at Stony Brook
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1993
• 资助国家: 美国
• 起止时间: 1993-07-01 至 1997-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9310712&HistoricalAwards=false
• 关键词: Electronic; Factor; Face; Selection

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.

有机动力学计划的这笔资助支持纽约州立大学石溪分校的 William J. le Noble 教授的工作，通过使用各种取代的金刚烷-2-酮和相关化合物来研究 pi-非对映选择性的电子起源。具体项目有：（1）加成反应，包括二羟基化、Grob碎裂、Michael加成、Claisen重排等； (2) 旨在区分 Ahn、Cieplak 和 Felkin 的理论模型的研究； (3)通过在C6处增加/减少1个亚甲基单元的金刚烷、通过研究更强大的5-取代基效应(N-氧化物和硼和铵化合物)、通过研究4,9-二取代效应、通过研究5,7-二取代效应以及通过修改C2处的三角中心来改变骨架和取代模式。 %%% 在这个项目中，William K. le Noble 教授将研究控制酮、亚胺和烯烃成键（和断裂）的 π-非立体面选择性的电子效应。选择金刚烷框架是为了消除干扰空间和构象效应。该研究集中于标准加成反应，区分理论模型，并将探讨强取代基和结构刚性的影响。