Synthesis of Curved Polycyclic Arenes Embedded with Oxepine and Thiepine Using Ring Expansion Strategy
作者:Sheng Zhang、Hidenori Matsuyama、Itaru Nakamura、Masahiro Terada、Tienan Jin
DOI:10.1021/acs.orglett.3c01730
日期:2023.7.14
A tandem oxidative ring expansion of a six- to seven-membered ring was developed to construct a new class of negatively curved polycyclic arenes embedded with oxepine and thiepine, namely, dibenzo[b,f]phenanthro[9,10-d]oxepine (DBPO) and dibenzo[b,f]phenanthro[9,10-d]thiepine (DBPT), respectively. Mechanistic studies disclosed that an unexpected [4 + 2] cycloadduct formed between the alkene moiety
开发了六至七元环的串联氧化环扩展,以构建一类嵌入氧杂环己烷和硫杂环己烷的新型负弯曲多环芳烃,即二苯并[b,f]菲并[9,10- d ]氧杂环己烷( DBPO) 和二苯并[ b , f ]菲并[9,10- d ]硫杂苯 (DBPT) 分别。机理研究揭示了邻联苯连接的亚甲基呫吨的烯烃部分和邻四氢苯醌之间形成的意想不到的[4+2]环加合物充当自由基阳离子或阳离子等价物,促进FeCl 3介导的串联环膨胀过程。