Cation Radicals in Solution

这项研究是由合成有机 Nathan L博士研究的化学计划。保尔德 德克萨斯大学化学系， 奥斯汀这项工作将开发新的温和反应， 复杂的环状结构 这些结构存在于许多 用于农业和医药的物质。 该研究继续了空穴催化 周环反应，用于合成目的和获得 对结构和反应路径的基本理解 有机阳离子自由基。 空穴催化的Diels-Alder 反应（DA）已经经历了广泛的发展， 最近在倍半萜烯的合成中举例说明 天然产物（-）-β-芹烯。 更机械的， 立体化学和动力学研究， 周环反应计划，以回答更多 与反应音乐会有关的决定性基本问题， 角色选择性，以及直接性与间接性。 一个新的和 在净DA意义上间接增加的强大方法， 高度受阻的二烯已经被开发并将被精制， 延伸，并在化合物的合成中说明， drimane系列 空穴催化直接Diels-Alder 应用（例如B-芹烯）强调了 二烯/富电子烯烃形式。 一个新的和非常有前途的 反应中实现Diels-Alder环加成的策略 二烯/二烯形式，其仍然产生高度 已经观察到不同的烯烃官能度， 将被开发。 新开发的空穴催化 乙烯基环丁烷重排可用于实现净 Diels-Alder加成 空穴催化的乙烯基环丁烷 反应也将广泛发展， 机械感和综合感。

This research is being funded by the Synthetic Organic Chemistry Program for the research of Dr. Nathan L. Bauld of the Department of Chemistry at the University of Texas at Austin. The work will develop new mild reactions for forming complex ring structures. These structures are found in many of the substances used in agriculture and medicine. The research continues the development of hole-catalyzed pericyclic reactions, both for synthetic purposes and to gain fundamental understanding of the structures and reaction paths of organic cation radicals. The hole-catalyzed Diels-Alder reaction (DA) has undergone extensive development and has recently been exemplified in the synthesis of the sesquiterpene natural product (-)-B-selinene. Further mechanistic, stereochemical, and kinetic studies of this and other pericyclic reactions are planned in order to answer more decisively fundamental questions relating to reaction concert, role selectivity, and directness vs. indirectness. A new and powerful methodology for indirect addition in a net DA sense to highly hindered dienes has been developed and will be refined, extended, and illustrated in the synthesis of compounds in the drimane series. Previous hole-catalyzed direct Diels-Alder applications (e.g. B-selinene) have emphasized the diene/electron rich alkene format. A new and very promising strategy for effecting Diels-Alder cycloadditions in the diene/diene format, which nevertheless produces highly differentiated alkene functionalities, has been observed and will be developed. The newly developed hole-catalyzed vinylcyclobutane rearrangement can be used to achieve net Diels-Alder addition. The hole-catalyzed vinylcyclobutane reaction will also be developed extensively in both a mechanistic and synthetic sense.