Synthesis and Properties of Selectively Modifiable Cyclodextrin Analogues

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.

Name thesis:degree_name

Ph.D.

Level thesis:degree_level

Dissertation

Grantor

University of Illinois at Urbana-Champaign

Year dc:date

2015

Author dc:creator

• Bodine, Kyle D.

Contributors dc:contributor

• Mary S. Gin
• Gin, David Y.

• Chemistry, Organic

Language dc:language

eng

Identifier

(MiAaPQ)AAI3242796

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/87887