Metal Assisted Ionization in Carbenoids and Chiroptical Properties of Acyclic Dienes

有机动力学计划中的这项拨款支持佛罗里达州立大学哈里·沃尔博斯基博士的研究，该研究旨在结构和机械有机化学的两个领域的研究。第一个调查将提供有关烷基锂与卤化、饱和和不饱和有机化合物反应的详细途径的信息。第二个目的是为了更好地了解测定无环二烯结构的方法。这个项目将研究类卡宾，即在同一个碳原子上拥有金属和卤素的中间体。这些中间体可能会坍塌形成卡宾，或者它们可能会发生双亲反应。(1)金属(2)卤素和(3)亲核试剂的变化的影响有待研究。由于在后一种情况下，金属化试剂在第二步中也用作亲核试剂，因此将使用混合有机硫化物。这项研究的第二部分将研究非环二烯的手性。例如，5-X-和5-X-7-Y-金刚烷基乙醛(和金刚烷基亚甲基丙烯)将被研究，因为金刚烷基体系有一个内置的参照物，可以直接比较赤道取代基X和Y对pi-pi-star棉花效应的影响。这样得到的数据应该允许在其他未定义的系统中进行构型和构象分配。

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.