One-pot Selective Formylation and Claisen Rearrangement on Calix[4]arenes

Abstract

A versatile synthon with formyl and allyl groups at the upper rim of calix[4]arene has been synthesized in two steps. Selective formylation of 25,27-diallyloxy-26,28-dihydroxycalix[4]arene, along with the Claisen rearrangement of the allyl groups, was achieved by reaction with hexamethylenetetraamine (hexamine) in glacial acetic acid. A control reaction of the dipropyl analogue shows that the selective formylation takes place independently of the Claisen rearrangement. The crystal structure of the dimethylacetal derivative of 5,17-diformyl-11,23-diallylcalix[4]arene is reported.