Stable Ion and Electrophilic Chemistry of the Sterically Crowded Stilbene 1,1′-Bi(benzocyclobutenylidene) and Its Derivatives
作者:Kenneth K. Laali、Takao Okazaki、Scott D. Bunge、Dieter Lenoir
DOI:10.1021/jo800175d
日期:2008.6.1
Generation and NMR studies of novel carbocations and carboxonium ions are reported from sterically hindered stilbene 1,1′-bi(benzocyclobutenylidene) 1, its dimethoxy derivative 5, and from their skeletally rearranged derivatives, namely, the spirocyclic ketone 6, diastereomeric alcohols 7 and isomeric diols 8. Quenching experiments on the carbocations under various conditions resulted in the formation/isolation
据报道,位阻二苯乙烯1,1'-双(苯并环丁烯基)1,其二甲氧基衍生物5以及其骨架重排的衍生物即螺环酮6,非对映异构醇7和异构二醇8。在各种条件下对碳正离子进行猝灭实验导致了几种新型共价加合物的形成/分离。二醇8的酸催化异构化产生显着的二聚分子,其结构通过X射线分析证实。受阻苯乙烯1和5与Br的反应经由NMR实验检查了2 / CDCl 3。GIAO-DFT和NICS还通过计算研究了实验观察到的碳正离子。