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

这项研究得到了有机和大分子化学计划的支持。它将开发一种可能非常普遍的方法来研究多环结构。它们存在于现代医学和农业中使用的许多复杂分子中。本研究将使锰基氧化自由基环化成为合成高功能化环和多环化合物的一种可靠、通用的方法。研究计划将重点关注以下问题：(1)发起群体的范围；(2)可耐受的双键取代模式类型以及是否形成了内环自由基或外环自由基；(3)可成形的圆环尺寸；(4)双键上可耐受的官能团；(5)在分子中其他地方可以耐受的官能团；(6)芳构化反应的范围；(7)添加剂对反应性质的影响；(8) Mn(OAc)3.2H2O和/或Cu(OAc)2氧化终止的范围和限制。H2O、LiCl和LiX；(9)第二环或第三环形成的范围和限制。

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.