一种用于定义双环环氧鎓离子分子内加成反应的结构/反应活性关系的实验和计算方法。
An experimental and computational approach to defining structure/reactivity relationships for intramolecular addition reactions to bicyclic epoxonium ions.
作者信息
Wan Shuangyi, Gunaydin Hakan, Houk K N, Floreancig Paul E
机构信息
Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095, USA.
出版信息
J Am Chem Soc. 2007 Jun 27;129(25):7915-23. doi: 10.1021/ja0709674. Epub 2007 Jun 5.
Abstract
In this manuscript we report that oxidative cleavage reactions can be used to form oxocarbenium ions that react with pendent epoxides to form bicyclic epoxonium ions as an entry to the formation of cyclic oligoether compounds. Bicyclic epoxonium ion structure was shown to have a dramatic impact on the ratio of exo- to endo-cyclization reactions, with bicyclo[4.1.0] intermediates showing a strong preference for endo-closures and bicyclo[3.1.0] intermediates showing a preference for exo-closures. Computational studies on the structures and energetics of the transition states using the B3LYP/6-31G(d) method provide substantial insight into the origins of this selectivity.
摘要
在本手稿中，我们报道了氧化裂解反应可用于形成氧鎓离子，该离子与侧链环氧化物反应形成双环环氧鎓离子，以此作为形成环状低聚醚化合物的途径。结果表明，双环环氧鎓离子结构对外型环化反应与内型环化反应的比例有显著影响，其中双环[4.1.0]中间体对内型闭环反应有强烈偏好，而双环[3.1.0]中间体对外型闭环反应有偏好。使用B3LYP/6-31G(d)方法对过渡态的结构和能量进行的计算研究，为这种选择性的起源提供了深入的见解。
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