This dissertation is separated into two parts according to the two major distinct research projects. In Part I, the full account of synthetic studies toward C10-functionalized lycopodium alkaloids is described. In Part II, the detailed discussion on the exploration of the Pummerer cyclization methodology and its application to the total...
The photoelectron spectra of a series of ketone
compounds have been investigated in the gas phase. Core
ionization energies were measured to probe the effects of
molecular size and connectivity number on core ionization
energies.
It was found that core ionization energies roughly
decrease with increasing connectivity number as expected....
The regiodivergent O- to C- or N-carboxyl transfer of pyrazolyl carbonates is described, with DMAP giving preferential N-carboxylation and triazolinylidenes promoting selective C-carboxylation (both with up to >99 : 1 regioselectivity). An enantioselective O- to C-carboxyl variant using NHC catalysis is demonstrated (up to 92% ee), while mechanistic and DFT studies outline...
A spectrometer, here denoted a Simple, Low-power, Inexpensive. Microcontroller-based or SLIM spectrometer. was developed that exploits the small size and low cost of solid-state electronic devices. This approach results in customizable spectrometers that are considerably less expensive and smaller than traditional instrumentation. The performance of the SLIM spectrometer was evaluated...
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LIST OF APPENDICES
Appendix Page
A Supplemental information for the SLIM spectrometer
Part I describes the synthesis of bis(fac-S)((tris)2-aminoethanethiolatoiron( III))iron(III) chloride. The compound was first discovered during an attempt to prepare a ternary complex of iron, thiolate and pi-acid ligand. The compound is a reasonably air-stable iron(III)-thiolate that contains a linear tri-iron cluster with each iron bridged to the adjacent iron by...
The first part of this manuscript is about the total synthesis of the Arundo donax bis(indole) natural products. The A. donax alkaloids were prepared using the first example of an ynindole Diels–Alder reaction. Each were then separated, isolated, and determined to have stable enantiomeric conformations at room temperature (Chen, J.;...
Many pesticides, polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers
(PBDEs), and polycyclic aromatic hydrocarbons are persistent, bio-accumulative, and
toxic. These semi-volatile organic compounds (SOCs) can undergo atmospheric
transport and deposition in cold, remote ecosystems. A better understanding of their
accumulation in the fish of these ecosystems is important to better predict...
The first part of this thesis describes a study of the
characteristics of oxidation of a 1:2 iron(III):thiolate system in
methanolic solution and in water. This system was investigated as a
potential analog for the cysteine- and cysteamine-dioxygenase catalyzed
0₂-oxidation of cysteine and cysteamine, respectively, to the
corresponding sulfinic acids....
In this dissertation, I describe spectroscopic studies of jet-cooled polycyclic aromatic hydrocarbons (PAH) and one nitrogen substituted PAH (PANH) using pulsed field zero kinetic energy (ZEKE) photoelectron spectroscopy and resonantly enhanced multiphoton ionization (REMPI) spectroscopy. Recently, there has been a demand for far-infrared (FIR) spectral information of astrophysically relevant molecules...
This dissertation describes the racemic and enantioselective synthesis cavicularin. Cavicularin is a macrocyclic bisbibenzyls family member natural product. It has been an attractive synthetic target due to its intriguing structure: the macrocyclic core imparts sufficient strain on the system to force one benzene rings to adopt a boat-shaped conformation, out...