Synthesis of calix[4]arene triflates and their unusual chemical reactivity in palladium-catalyzed reactions

The formation of p-tert-butylcalix[4]arene mono-, bis-, tris-, and tetrakistriflates 3, 2, 4, and 5, respectively, and their respective reactions, under typical Pd-catalyzed carbonylative, Suzuki-Miyaura coupling, or deoxygenation conditions are described. A novel, nonsolvent-derived 1:1 clathrate (6) of benzophenone and 3 was formed from the palladium-catalyzed carbonylative reaction of phenylboronic acid and 2. The X-ray crystal structure of this first nonsolvent-derived clathrate of a calix[4]arene derivative is reported. Another 1:1 clathrate of triethylamine and 3 was formed during the attempted Pd-catalyzed deoxygenation of 2.