Synthesis and Reactions of C₄-Symmetric 1,3,5,7(1,3)-Tetrabenzenacyclooctaphane Tetraazide and Tetraamine Derivatives: Toward the Synthesis of Nitrogen-Embedded Zigzag Hydrocarbon Belts

Abstract

Starting from readily available tetratriflated resorcin[4]­arene derivatives, C 4-symmetric 1,3,5,7­(1,3)-tetra­benzenacyclo­octaphane tetra­amines were synthesized conveniently by means of Pd-catalyzed C–N bond coupling reaction with diphenyl­methanimine followed by hydrolysis. Subsequent Sandmeyer reaction and sulfonylation reaction efficiently afforded the corresponding tetraazide and tetrasulfonamide products, respectively. Upon treatment with PhI­(OAc)2, tetrasulfonamides underwent facile oxidative transannular cyclization reaction to produce mono- and dispiro macrocyclic compounds selectively rather than N4-octahydrobelt­[8]­arenes. Conformational structures of resulting macrocycles are presented, and the reaction mechanism is discussed.