Demay-Drouhard Paul, Du Ke, Samanta Kushal, Wan Xintong, Yang Weiwei, Srinivasan Rajavel, Sue Andrew C-H, Zuilhof Han
Institute for Molecular Design and Synthesis, School of Pharmaceutical Science & Technology , Tianjin University , 92 Weijin Road, Nankai District , Tianjin , 300072 , People's Republic of China.
Laboratory of Organic Chemistry , Wageningen University , Stippeneng 4 , 6703 WE Wageningen , The Netherlands.
Org Lett. 2019 Jun 7;21(11):3976-3980. doi: 10.1021/acs.orglett.9b01123. Epub 2019 Apr 19.
The development of an efficient synthetic route toward rim-differentiated C-symmetric pillar[5]arenes (P[5]s), whose two rims are decorated with different chemical functionalities, opens up successive transformations of this macrocyclic scaffold. This paper describes a gram-scale synthesis of a C-symmetric penta-hydroxy P[5] precursor, and a range of highly efficient reactions that allow functionalizing either rim at will via, e.g., sulfur(VI) fluoride exchange (SuFEx) reactions, esterifications, or Suzuki-Miyaura coupling. Afterward, BBr demethylation activates another rim for similar functionalizations.
一种向边缘差异化的 C 对称柱[5]芳烃(P[5])发展的高效合成路线,其两个边缘带有不同的化学官能团,开启了这种大环支架的连续转化。本文描述了一种克级规模合成 C 对称五羟基 P[5]前体的方法,以及一系列高效反应,这些反应允许通过例如六价硫氟交换(SuFEx)反应、酯化反应或铃木-宫浦偶联反应随意对任一边缘进行功能化。之后,BBr 脱甲基反应激活另一个边缘以进行类似的功能化。