Synthesis and Properties of Selectively Modifiable Cyclodextrin Analogues

221 p.Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 2006.Cyclodextrins (CDs) are amphiphilic carbohydrate based macrocycles that have been under-utilized in supramolecular chemistry due to difficulties surrounding the selective functionalization of the hydroxyl groups on the macrocycle. A novel strategy for the synthesis of CD analogues is described which involves the use of [3+2] Huisgen cycloadditions between azide and alkyne functionalities to form the macrocycles from linear precursors. This strategy is used in the synthesis of a trisaccharide cyclodimer which was shown to complex a fluorescent dye 8-anilino-1-naphthalene sulfonate with an association constant of 38 +/- 10 M-1. In addition, the synthesis of a monosaccharide cyclotrimer and a disaccharide cyclodimer is presented that were demonstrated to complex 2,4-hexadiyne-1,6-diol with association constants of 8.8 +/- 1.5 M -1 and 10.4 +/- 1.1 M-1, respectively. Alternate synthetic routes which incorporate selectively installed orthogonal protecting groups are discussed for each of the three types of CD analogues. Efforts toward the synthesis of a gated molecular pore are also detailed.U of I OnlyRestricted to the U of I community idenfinitely during batch ingest of legacy ETD