Intermolecular vs. Intramolecular carbene reactions of a cage-functionalized cyclopentylcarbene
作者:Alan P. Marchand、Kaipenchery A. Kumar、Kata Mlinarić-Majerski、Jelena Veljković
DOI:10.1016/s0040-4020(98)00909-0
日期:1998.12
yield) via intramolecular C-H insertion along with other reaction products. By way of contrast, photodecomposition of 11 afforded a mixture of isomeric azines, 21a–21d, as the major reaction product. No intramolecular carbene trapping products were obtained when 9 was generated via reaction of 12 with n-BuLi.
通过使用不同的前体在不同条件下生成的五环[5.4.0.0 2,6 .0 3,10 .0 5,9 ]十一碳八亚基(即,PCU-8-亚烷基,9)的卡宾反应结果[即,(i)PCU-8-对甲苯磺酰P的钠盐(8),(ii)PCU-8-重氮嗪(11)和(iii)8,8-二溴-PCU (12)]报告。由8热生成的PCU-8-卡宾(9)通过分子内CH插入以及其他反应产物提供了均戊四烯(17,收率9.6%)。相比之下,光分解为11给出了主要反应产物异丁嗪21a-21d的混合物。当通过12与正丁基锂的反应生成9时,没有获得分子内卡宾捕获产物。