Mn(III) Based Oxidative Free Radical Cyclizations (Chemistry)

这项研究得到了有机化学和高分子化学项目的支持。它将为进入多环结构的潜在的非常一般的路线开发方法。在现代医学和农业中使用的许多复杂分子中都有这些。这项研究将发展基于锰(III)的氧化自由基环化反应成为一种可靠和通用的方法来合成高官能化的环和多环化合物。研究计划将集中于以下问题：(1)引发基团的范围；(2)可以容忍的双键取代模式的类型以及是否形成环内或环外自由基；(3)可以形成的环大小；(4)双键上可以容忍的官能团；(5)分子中其他地方可以容忍的官能团；(6)芳构化反应的范围；(7)添加剂对反应性质的影响；(8)用Mn(OAc)3.2H2O和/或Cu(OAc)2.H2O、LiCl和Lix氧化终止的范围和限制；(9)形成第二环或第三环的范围和限制。

This research is being supported by the Organic and Macromolecular Chemistry Program. It will develop the methodology for a potentially very general route into polycyclic structures. These are found in many of the complex molecules used in modern medicine and agriculture. This research will develop the manganese (III) based oxidative free radical cyclization into a reliable and versatile method for the synthesis of highly functionalized cyclic and polycyclic compounds. The research program will focus on the following questions: (1) the scope of initiating groups; (2) the type of double bond substitution patterns that can be tolerated and whether endocyclic or exocyclic radicals are formed; (3) the ring sizes that can be formed; (4) the functional groups that can be tolerated on the double bond; (5) the functional groups that can be tolerated elsewhere in the molecule; (6) the scope of the aromatization reaction; (7) the effect of additives on the nature of the reaction; (8) the scope and limitations of the oxidative termination with Mn(OAc)3.2H2O and/or Cu(OAc)2.H2O, LiCl and LiX; and (9) the scope and limitations for the formation of a second or third ring.