Synthesis and biophysical characterization of chlorosulfolipids and the synthesis of azamerone
Abstract/Contents
- Abstract
- Natural product synthesis and methodology development have long enjoyed a symbiotic relationship with the structural complexity observed in natural products inspiring chemists to invent new reactions, as well as providing a proving ground for the utility of existing methods in complex settings. Chapter 1 of this dissertation provides a recent perspective on catalytic methodology developed to enable the synthesis of complex natural products. A focus on the last 20 years of organic chemistry demonstrates the state-of-the-art in methods development and its direct application to accessing complex natural products efficiently. Chapter 2 details our efforts to synthesize three sulfolipid natural products isolated from algae Ochromonas danica. Key features of our synthesis of danicalipin A include the application of our catalytic, enantioselective dichlorination of allylic alcohols and a diastereoselective boron allylation of the dichloroaldehyde fragment. Subsequent syntheses of two biosynthetic precursors of danicalipin A are presented. We also describe the results of an interdisciplinary collaboration enabled by the synthetic sulfolipids to investigate the biophysical properties of these exotic molecules. Chapter 3 describes our efforts towards the total synthesis of napyradiomycin natural product azamerone. Our synthesis required the development of a catalytic, enantioselective chlorocyclization reaction to access a key chlorinated benzopyran intermediate. Subsequent B-alkyl Suzuki cross-coupling between two enantioenriched fragments, followed by the late-stage installation of the pyridazine heterocycle via a tetrazine [4+2] cycloaddition yielded the natural product. This work constitutes the first enantioselective total synthesis of azamerone.
Description
| Type of resource | text |
|---|---|
| Form | electronic resource; remote; computer; online resource |
| Extent | 1 online resource. |
| Place | California |
| Place | [Stanford, California] |
| Publisher | [Stanford University] |
| Copyright date | 2020; ©2020 |
| Publication date | 2020; 2020 |
| Issuance | monographic |
| Language | English |
Creators/Contributors
| Author | McKenna, Grace Mattie |
|---|---|
| Degree supervisor | Burns, Noah |
| Thesis advisor | Burns, Noah |
| Thesis advisor | Boxer, Steven G. (Steven George), 1947- |
| Thesis advisor | Du Bois, Justin |
| Degree committee member | Boxer, Steven G. (Steven George), 1947- |
| Degree committee member | Du Bois, Justin |
| Associated with | Stanford University, Department of Chemistry |
Subjects
| Genre | Theses |
|---|---|
| Genre | Text |
Bibliographic information
| Statement of responsibility | Grace McKenna. |
|---|---|
| Note | Submitted to the Department of Chemistry. |
| Thesis | Thesis Ph.D. Stanford University 2020. |
| Location | electronic resource |
Access conditions
- Copyright
- © 2020 by Grace Mattie McKenna
- License
- This work is licensed under a Creative Commons Attribution Non Commercial 3.0 Unported license (CC BY-NC).
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