Catalytic enantioselective dihalogenation of allylic alcohols
Abstract/Contents
- Abstract
- Enantioselective dihalogenation is an important method for the total synthesis of stereocomplex polyhalogenated natural products, but only a few methods with significant limitations currently exist for this transformation. In 2015, we developed the chemo-, regio- and enantioselective bromochlorination of allylic alcohols featuring a titanium half-salen catalyst to help address this problem. The utility of this method has been demonstrated by the enantioselective total syntheses of 11 halogenated natural products to date by our lab, each of which was directly enabled by this method. Following development, we applied the enantioselective bromochlorination to various new substrates including homoallylic alcohols, which resulted in the total synthesis of (--)-anverene, a polyhalogenated marine natural product with modest but selective antibiotic activity. Computational and experimental mechanistic work was undertaken to better understand the catalytic enantioselective bromochlorination, as well as the enantiospecific solvolysis of resulting enantioenriched bromochlorides. The enantioselective dihalogenation catalyst system has also been extended to new reactions using other electrophile-nucleophile pairs, including haloazidation, which uses TMSN3 as the nucleophilic azide source.
Description
| Type of resource | text |
|---|---|
| Form | electronic; electronic resource; remote |
| Extent | 1 online resource. |
| Publication date | 2018 |
| Issuance | monographic |
| Language | English |
Creators/Contributors
| Associated with | Seidl, Frederick James |
|---|---|
| Associated with | Stanford University, Department of Chemistry. |
| Primary advisor | Burns, Noah |
| Thesis advisor | Burns, Noah |
| Thesis advisor | Kool, Eric T |
| Thesis advisor | Trost, Barry M |
| Advisor | Kool, Eric T |
| Advisor | Trost, Barry M |
Subjects
| Genre | Theses |
|---|
Bibliographic information
| Statement of responsibility | Frederick James Seidl. |
|---|---|
| Note | Submitted to the Department of Chemistry. |
| Thesis | Thesis (Ph.D.)--Stanford University, 2018. |
| Location | electronic resource |
Access conditions
- Copyright
- © 2018 by Frederick James Seidl
- License
- This work is licensed under a Creative Commons Attribution Non Commercial 3.0 Unported license (CC BY-NC).
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