The Trouble with Five: New Synthetic Strategies toward C₅ -Symmetric Pillar[5]arenes and Beyond

Abstract

Rim-differentiated pillar[5]arenes (P[5]s) are intriguing macrocyclic molecular platforms with C ₅-symmetry, but their conventional statistical syntheses suffer from low yields and laborious separation. Our group recently reported a ‘pre-oriented’ protocol that results in highly selective production of C ₅-symmetric P[5]s among four constitutional isomers. Subsequently, we devised a more general divergent synthetic route starting with a common P[5] precursor with rim differentiation, followed by a series of high-yielding reactions that permit successive transformations of both rims freely. As a result, a variety of rim-differentiated P[5]s can be made to order in gram-scale quantities. This total solution not only populates the list of C ₅-symmetric P[5]s, but also enables further design and synthesis of assorted five-fold organic building blocks towards complex supramolecular architectures.

Key words

five-fold symmetry - C ₅-axis - pillar[5]arenes - rim differentiation - regioselectivity - macrocycles

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