Troger’s base (TB) is a curved, chiral molecule possessing aromatic rings oriented at approximately 90° and two stereogenic amine nitrogens.  Recent interest in TB arises from its use as a scaffold for the construction of supramolecular assemblies.  Notable among these applications, TB has been used in designing chiral molecular clefts, as a ligand platform for the assembly of coordination cages and for the fabrication of polymer materials possessing persistent voids for the separation of gases.  Our research has been directed at finding solutions to gaps in TB synthetic strategies.  The classic, one-step TB synthesis works well for p-substituted anilines bearing electron-donating groups, but limits available substitution patterns as well as access to strategically useful halogenated derivatives.  We have developed a four-step TB synthesis, which allows for the preparation of several heretofore inaccessible derivatives.  A second problem involves a general, scalable resolution of TB derivatives, which is required for the preparation of homochiral molecules containing several TB fragments.  A general method for the gram-scale resolution of both symmetric 2,8-disubstituted and unsymmetric 2-substituted TB has been developed.  Yields of 63-91% are possible via a crystallization induced asymmetric transformation (CIAT).  Among the TB derivatives resolved are four synthetically useful iodo- and bromo- derivatives.

Troger’s base: A versatile platform for supramolecular chemistry

255th National Meeting (2018)

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