Functionalization at Will of Rim-Differentiated Pillar[5]arenes

• DOI: 10.1021/acs.orglett.9b01123
• Publication Date: 2019-04-19T14:52:55Z
• Authors: Paul Demay-Drouhard; Ke Du; Kushal Samanta; Xintong Wan; Weiwei Yang; Rajavel Srinivasan; Andrew C.-H. Sue; Han Zuilhof
• Keywords: Demethylation; Pillar; Surface Modification

The development of an efficient synthetic route toward rim-differentiated C5-symmetric pillar[5]arenes (P[5]s), whose two rims are decorated with different chemical functionalities, opens up successive transformations this macrocyclic scaffold. This paper describes a gram-scale synthesis penta-hydroxy P[5] precursor, and range highly reactions that allow functionalizing either rim at will via, e.g., sulfur(VI) fluoride exchange (SuFEx) reactions, esterifications, or Suzuki-Miyaura coupling. Afterward, BBr3 demethylation activates another for similar functionalizations.