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

The formation of p-tert-butylcalix[4]arene mono-, bis-, tris-, and tetrakis triflates 3, 2, 4, and 5, respectively, and their respective reactions, und er typical Pd-catalyzed carbonylative, Suzuki-Miyaura coupling, or deoxygen ation conditions are described. A novel, nonsolvent-derived 1:1 clathrate ( 6) of benzophenone and 3 was formed from the palladium-catalyzed carbonylat ive reaction of phenylboronic acid and 2. The X-ray crystal structure of th is first nonsolvent-derived clathrate of a calix[4]arene derivative is repo rted. Another 1:1 clathrate of triethylamine and 3 was formed during the at tempted Pd-catalyzed deoxygenation of 2.