Date of Award


Document Type


Degree Name

Doctor of Philosophy (PhD)



First Advisor

Severin T. Schneebeli


Chirality is a key principle in organic chemistry. All chiral compounds are non-superimposable mirror images of each other and therefore lack an improper axis of rotation (Sn). These mirror images often have identical properties in an achiral environment, however when two chiral molecules interact, they produce different shapes and properties. Nature, to this extent takes advantage of this aspect through unique formation of shape defined biological macromolecules that are tailored to carry out various life processes. This level of shape control is only made possible because of natural chiral monomers such as amino acids or glycosides that make up such macromolecules. Under new methods such as Chirality Assisted Synthesis (CAS), shape and size-controlled polymers and macromolecules can be realized through the use of chiral monomers to make well defined macromolecules. Because chirality dictates shape, and shape defines function in reference to macromolecules, controlling the chirality of monomers, while concurrently dictating shape and size can lead to the potential of biomimetic methodologies and cage like structures.

Accessing shape defined monomers can be difficult especially when in reference to chiral compounds. The unique structure of enantiopure tribenzotriquinacenes show promise in the formation of well-defined cage like structures through utilization of CAS methodology. Synthesis of functionalized tribenzotriquinacenes along with development of an enantioselective electrophilic aromatic nitration method was attempted. Further exploration into the effectiveness of through-space enantioselective nitrations found a dependence on solvent temperature, and the auxiliary that is used. Synthetic difficulties, results, modifications and processes toward a generalized method are presented herein.

In addition, controlling the size of polymers has always been a difficult synthetic challenge. Overall selectivity toward one product over another is determined via a variety of chemical properties. However, the formation of sequence and size defined polymers are a prominent aspect of natural polymers. The size selective synthesis, of unique ABAB sequenced polymers was attempted using an iterative exponential growth method. The ability to scale up these processes and create monodisperse oligoethers is also presented and described herein.



Number of Pages

225 p.

Included in

Chemistry Commons