Author ORCID Identifier
Semester
Spring
Date of Graduation
2023
Document Type
Dissertation
Degree Type
PhD
College
Eberly College of Arts and Sciences
Department
Chemistry
Committee Chair
Gregory Dudley
Committee Member
Jessica Hoover
Committee Member
John Hu
Committee Member
Carsten Milsmann
Committee Member
Brian Popp
Abstract
Reaction discoveries, method developments, and technology advancements lie at the heart of synthetic organic chemistry. These innovations are essential for creating and manipulating complex molecules, which are the building blocks of many important chemical compounds, including pharmaceuticals, materials, and agrochemicals. Here, we first describe new methods to prepare neopentylene-tethered (NPT) 1,6-diynes which are valuable substrates for reaction discovery and target-oriented synthesis, especially in benzannulation strategies toward illudalane natural products. NPT 1,6-diynes have been employed as coupling partners in cyclotrimerization reactions for the synthesis of highly substituted benzene rings which present a persistent challenge in chemical synthesis and are underrepresented scaffolds in medicinal chemistry. Using a cationic rhodium catalyst, regioselective diyne-alkyne cyclotrimerizations have been developed which can be manipulated by varying the functional handles on the coupling partners. This enables the concise syntheses of coprinol and several alcyopterosins as well as the first chemical synthesis of fomajorin D which have shown to have interesting biological properties. Apart from advancements in chemical reactions, novel discoveries regarding potential applications of selective microwave (MW) heating in organic synthesis will also be presented. We have designed and optimized a system comprising dipolar p-nitroanisole (pNA) and MW-transparent mesitylene (MES), wherein pNA solutes assemble into nano-sized polar agglomerates than can be selectively heated using MW energy. This system is used as a mixed solvent for aryl Claisen rearrangement of allyl naphthyl ether (ANE) which serves as a probe reaction for exploiting MW-specific thermal effects.
Recommended Citation
Tavakoli, Amir, "Enabling Technologies for Chemical Synthesis: I. Selective Microwave Heating; II. Synthesis and Regioselective Cyclotrimerizations of Tethered 1,6-Diynes" (2023). Graduate Theses, Dissertations, and Problem Reports. 11655.
https://researchrepository.wvu.edu/etd/11655