Physical Sciences and Mathematics Commons^™

Fragmentation, Rearrangement, And C-H Insertion: Reactions Of Vinyl Cations Derived From Diazo Carbonyls, Sarah Elizabeth Cleary

Graduate College Dissertations and Theses

Many commercialized medicinal compounds are analogs of chemicals isolated from sources found in nature (also called natural products). However, the natural sources of these chemicals, such as plants, fungi, or insects, only offer small quantities of these bioactive agents. Thus, it is typically desirable to find ways to synthesize these products and their analogs in large quantities using cost-effective methods that also minimize the impact on the environment. It is also important to develop strategies that expedite the process of modifying the natural products, which allows medicinal chemists to determine which functional groups are enhancing or deleterious to the bioactivity. …

Unprecedented Reactivity And Applications Of 1-Aza-2-Azoniaallene Salts, Ramya Srinivasan

Graduate College Dissertations and Theses

1-Aza-2-azoniaallene salts, derived by oxidation of substituted hydrazones, are highly reactive cationic heteroallenes. These species participate in several mechanistically distinct reactions including: (1) intramolecular [3+2] cycloadditions, (2) polar [4 +2] cycloadditions, (3) stereospecific C-H aminations, (4) electrophilic aromatic substitutions, and (5) chloroamination reactions. We have shown that this versatile reactivity is governed by the length of the tether and nature of the π-system.

A novel intramolecular electrophilic aromatic substitution reaction is observed when the tether length separating the 1-aza-2-azoniaallene salt and a pendant aryl ring is three methylene units to generate alkylaryl azo products. Variations in the electronics and sterics …

The Synthesis Of Highly Substituted Aromatics And The Reaction Of Alkene Pi Systems With Vinyl Cations, Nicholas Jarrod Dodge

Graduate College Dissertations and Theses

Aldol cyclotrimerizations have been used to achieve the rational chemical synthesis of both fullerenes and fullerene fragments in the past. Under certain conditions this reaction produces the corresponding cyclotetramer which has sometimes been regarded as an undesired byproduct. This work details efforts to synthesize and use these cyclotetramers toward a synthesis of a C240 fullerene fragment. One principal focus in this work is tridecacyclene, a cyclic tetramer of acenaphthylene given its name by our group for its thirteen rings. Relatively low yields for the synthesis of tridecacyclene and its derivatives drove us to investigate the mechanism of its formation and …