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

Paul Demay-Drouhard; Ke Du; Kushal Samanta; Xintong Wan; Weiwei Yang; Rajavel Srinivasan; Andrew C-H Sue; Han Zuilhof

doi:10.1021/acs.orglett.9b01123

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

Org Lett. 2019 Jun 7;21(11):3976-3980. doi: 10.1021/acs.orglett.9b01123. Epub 2019 Apr 19.

Authors

Paul Demay-Drouhard^{1

2}, Ke Du¹, Kushal Samanta^{1

2}, Xintong Wan¹, Weiwei Yang¹, Rajavel Srinivasan¹, Andrew C-H Sue¹, Han Zuilhof^{1

2

3}

Affiliations

¹ 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.
² Laboratory of Organic Chemistry , Wageningen University , Stippeneng 4 , 6703 WE Wageningen , The Netherlands.
³ Department of Chemical and Materials Engineering , King Abdulaziz University , 21589 Jeddah , Saudi Arabia.

Abstract

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 of this macrocyclic scaffold. This paper describes a gram-scale synthesis of a C₅-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, BBr₃ demethylation activates another rim for similar functionalizations.