Tetraheterodecalin Podands, Their Linkers, and Resulting Macrocycles: A Hoard of Constitutionally and Stereochemically Dynamic Systems

Discoveries involving the formation, structure, and behavior of an exciting class of compounds, 1,3,5,7‐ cis ‐tetraheterodecalins, are reviewed. These compounds are rich in free electrons and exhibit concave structures. The tetraoxa‐ and dioxadiaza‐ members of this class of compounds comprise the underframe of various podand structures, which, along with suitable polyhetero linkers, constitute the building blocks of an entire series of unique classes of macro‐ and gigantocyclic compounds, capable of cation inclusion and catalytic behavior. In the works presented here, a recurring theme is the pursuit of a fundamental understanding and judicious utilization of the dynamic chemical and stereochemical features of compounds derived from 1,3,5,7‐ cis ‐tetraheterodecalins, most of which are members of dynamic combinatorial libraries (DCLs).