Synthesis opens the pathway to examine a plethora of complex structures. Whether the target is a naturally occurring compound or a proposed molecule never observed before, synthetic routes can be developed to help understand a variety of properties that the molecule can contain. Synthetic efforts have helped elucidate the absolute structures isolated from nature, study the natural processes that produce complex moieties, and further research larger scale phenomena that occur in the presence of such compounds. Research into the prodiginine alkaloids has been enhanced by the synthesis of complex structures. In particular, the absolute configuration of metacycloprodigiosin was not determined until the first enantioselective synthesis of the compound was completed. Work towards providing a more efficient process to produce metacycloprodigiosin led to some intriguing insight into the oxidative coupling of aldehydes and enol silanes as well as the macrocyclization of terminal alkenes. These processes proved very substrate dependent and the efficiency of either the oxidative coupling or the macrocyclization meant an unfavorable outcome for the other. Roseophilin has been a well-studied alkaloid related to the prodiginine alkaloids. Most synthetic efforts have focused on a convergent path to the complex core, but the biosynthetic process is still unknown. The nature of the structure suggests it is produced starting from a prodiginine alkaloid, but no direct precursor is known. To help elucidate the process, the proposed structure prodigiosin R3 has been synthesized. The novel prodiginine contains a 13-membered macrocycle, similar to roseophilin, and is believed to undergo a radical cyclization biosynthetically to afford the fused cyclic structure shared by roseophilin. To determine the propensity of such a cyclization to occur with the prodiginine alkaloid, a derivative of the structure is being pursued that can produce the key radical at the desired location. Atmospherically relevant compounds were also synthesized to help further research into their properties in secondary organic aerosols. An isotopologue of α-pinene was produced, deuterium labeling the methylene bridgehead. The isotopologue has been used to examine the properties of oxidation products of α-pinene on the surface of aerosols. Eight isomers of isoprene-derived organosulfates have also been synthesized, marking the first-time pure standards of these organosulfates have been completed. Believed to be the most abundant organosulfate present in the atmosphere, pure standards will help examine the properties of the species and help determine the actual isomers formed in aerosols.

Creator

• Vega, Marvin Marcus

DOI

• https://doi.org/10.21985/n2-wa0q-x172

Subject

• Chemistry

Language

• en

Alternate Identifier

• http://dissertations.umi.com/northwestern:14544
• etdadmin_upload_641529

Date created

• 2019-01-01

Resource type

• Dissertation

Rights statement

• In Copyright