Metal Assisted Ionization in Carbenoids and Chiroptical Properties of Acyclic Dienes

类胡萝卜素中的金属辅助电离和无环二烯的手性光学性质

• 批准号: 8815521
• 负责人: Harry Walborsky
• 金额: $ 26.94万
• 依托单位: Florida State University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1989
• 资助国家: 美国
• 起止时间: 1989-02-01 至 1993-01-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=8815521&HistoricalAwards=false
• 关键词: Metal; Assisted; Ionization; Carbenoids; Chiroptical

This grant in the Organic Dynamics Program supports research of Dr. Harry Walborsky, Florida State University, which is aimed at two areas of research in structural and mechanistic organic chemistry. The first investigation will provide information about the detailed pathway of the reaction of alkyllithiums with halogenated, saturated and unsaturated organic compounds. The second is aimed at a better understanding of methods for determing the structure of acyclic dienes. This project will investigate carbenoids, intermediates which possess a metal and a halogen on the same carbon atom. These intermediates may collapse to form carbenes or they may undergo ambiphilic reactions. The effect of variation in (1) metal (2) halogen and (3) nucleophile is to be studied. Since in the latter case, the metalating agent also serves as the nucleophile in a second step, mixed organolithiums will be used. A second part of the study will investigate chiroptical properties of acyclic dienes. For example, the 5-X- and 5-X-7-Y-adamantylideneacetaldehyde (and adamantylidenepropene) will be studied since the adamantyl system has a built-in reference which enables direct comparison of the effect of equatorial substituents X vs. Y on the pi-pi-star Cotton effects. The data so derived should allow configurational and conformational assignments to be made in otherwise undefined systems.

有机动力学计划的这项拨款支持以下研究： 哈利·沃尔博斯基博士，佛罗里达州立大学， 在两个研究领域，结构和机械有机 化学. 第一次调查将提供信息 关于烷基锂反应的详细途径 卤代的、饱和的和不饱和的有机化合物。 第二个目的是更好地理解 确定无环二烯的结构。 本项目将研究类卡宾， 在同一碳原子上具有金属和卤素。 这些 中间体可能坍塌形成卡宾，或者它们可能经历 两亲性反应 （1）金属的变化影响 (2)卤素和（3）亲核试剂。 因为在 在后一种情况下，金属化剂也用作 在第二步中，混合的有机锂将被 采用 研究的第二部分将调查手光学 无环二烯的性质。 例如，5-X-和 5-X-7-Y-亚金刚烷基乙醛（和亚金刚烷基丙烯） 将进行研究，因为金刚烷系统具有内置的 可以直接比较的参考 π-π-星星上的赤道取代基X与Y 方面的影响. 由此得出的数据应允许配置和 构象分配，否则未定义 系统.