Studies on the photochemical [2+2] cycloadditions of unactivated olefins
Abstract/Contents
- Abstract
- [2+2] cycloadditions are arguably the most powerful reactions for constructing cyclobutanes which are prominent motifs in natural products and are becoming increasingly common pharmacophores in medicinal chemistry. Despite the growing number of [2+2] methodologies, virtually all of them rely on the cyclization of at least one activated π partner. An exception to this rule is the Kochi-Salomon reaction, which is able to cyclize aliphatic olefins in the presence of simple Cu(I) catalysts. Introduced over 50 years ago, it has seen very little in the way of methodological development and still suffers from a number of drawbacks including the need for moisture- and air-sensitive reagents, a limited substrate scope and a lack of stereocontrol. This thesis describes strategies to address these shortcomings starting with our efforts at rendering the Kochi-Salomon reaction enantioselective, first using weakly coordinating chiral counterions and then using chiral diene ligands. Although ultimately unsuccessful, these attempts provided valuable insight into Cu-catalyzed [2+2] photocycloadditions which led to the development of aqueous amine-tolerant cyclizations of unactivated olefins. Basic amines, hitherto incompatible in these types of reactions, may be protonated then cyclized in water, an unlikely solvent, using some of the most standard reagents available in any chemistry lab. This discussion is followed by a series of smaller ventures into further developments of the Kochi-Salomon reaction, including strategies to exert diastereocontrol and efforts to cyclize sulfur-containing substrates and quaternary ammonium substrates. The final chapter details the development of a scalable route to anti-[3]-ladderdiene. While not related to the Kochi-Salomon reaction, this strained molecule fits well into the realm of cyclobutanes which is central to this thesis.
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 | 2023; ©2023 |
| Publication date | 2023; 2023 |
| Issuance | monographic |
| Language | English |
Creators/Contributors
| Author | Mansson, Carl Magnus Fabian |
|---|---|
| Degree supervisor | Burns, Noah |
| Thesis advisor | Burns, Noah |
| Thesis advisor | Kanan, Matthew William, 1978- |
| Thesis advisor | Stack, T. (T. Daniel P.), 1959- |
| Degree committee member | Kanan, Matthew William, 1978- |
| Degree committee member | Stack, T. (T. Daniel P.), 1959- |
| Associated with | Stanford University, School of Humanities and Sciences |
| Associated with | Stanford University, Department of Chemistry |
Subjects
| Genre | Theses |
|---|---|
| Genre | Text |
Bibliographic information
| Statement of responsibility | Carl Magnus Fabian Mansson. |
|---|---|
| Note | Submitted to the Department of Chemistry. |
| Thesis | Thesis Ph.D. Stanford University 2023. |
| Location | https://purl.stanford.edu/mq145pf1607 |
Access conditions
- Copyright
- © 2023 by Carl Magnus Fabian Mansson
- License
- This work is licensed under a Creative Commons Attribution Non Commercial 3.0 Unported license (CC BY-NC).
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