12,15-dichloro[3.0]orthometacyclophane: A highly strained biphenylophane

被引：11

作者：

van Eis, MJ ^{[1
]}

de Kanter, FJJ ^{[1
]}

de Wolf, WH ^{[1
]}

Bickelhaupt, F ^{[1
]}

机构：

[1] Vrije Univ Amsterdam, Scheikundig Lab, NL-1081 HV Amsterdam, Netherlands

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 1998年 / 120卷 / 14期

关键词：

D O I：

10.1021/ja973876n

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The title compound, 3, in which two methylene groups of the parent compound 4 have been replaced by an ortho-substituted benzene ring, has been synthesized. It exists exclusively in the endo-conformation, in contrast to 4 for which the exo-conformation is preferred. High-level density functional calculations are presented for both compounds. They show that the endo-conformation of 3 is favored over the exo-conformation by 3.3 kcal mol(-1). The incorporation of a benzene ring in the bridge leads to a substantial increase of the strain energy (Delta SE = SE (3) - SE (4) = 4.7 kcal mol(-1)), making 3 the, thus far, smallest and most reactive, yet isolable, [n]metacyclophane.

引用

页码：3371 / 3375

页数：5