利用亲核取代反应来理解一个远程烷基或烷氧基取代基如何影响八元环氧鎓离子的构象。
Using nucleophilic substitution reactions to understand how a remote alkyl or alkoxy substituent influences the conformation of eight-membered ring oxocarbenium ions.
作者信息
Chamberland Stephen, Woerpel K A
机构信息
Department of Chemistry, University of California-Irvine, Irvine, California 92697-2025, USA.
出版信息
Org Lett. 2004 Dec 9;6(25):4739-41. doi: 10.1021/ol047998d.
[reaction: see text] A remote alkoxy substituent strongly stabilizes one particular conformer of an eight-membered ring oxocarbenium ion by a through-space electrostatic effect. X-ray crystallographic analysis of a crystalline derivative proves that kinetically controlled nucleophilic substitution favors the 1,4-trans product. Nucleophilic substitution of the corresponding alkyl-substituted acetate, however, is unselective. A computational model has been developed and experimentally validated to predict the low-energy conformers of C3-, C4-, or C5-alkyl- or alkoxy-substituted eight-membered ring oxocarbenium ions.
[反应：见正文] 一个远程烷氧基取代基通过空间静电效应强烈稳定八元环氧鎓离子的一种特定构象异构体。一种晶体衍生物的X射线晶体学分析证明，动力学控制的亲核取代有利于1,4-反式产物。然而，相应的烷基取代乙酸酯的亲核取代是无选择性的。已开发并通过实验验证了一种计算模型，以预测C3-、C4-或C5-烷基或烷氧基取代的八元环氧鎓离子的低能量构象异构体。
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