Synthetic studies toward pactamycin using oxidative alkene and C-H amination technologies
Abstract/Contents
- Abstract
- Selective, oxidative methods for C--N bond formation have been advanced to facilitate a de novo synthesis of pactamycin. A method for the synthesis of 1,2-diamines was developed through a single-step, tandem sequence involving Rh-catalyzed alkene aziridination followed by NaI-promoted rearrangement to an isomeric cyclic sulfamide. Facile ring opening of these products in hot water and pyridine affords differentially protected vicinal diamines. The utility of the method was validated through the preparation of the polyaminoacid-derived natural products, (±)-enduracididine and (±)-allo-enduracididine. A strategy has been delineated toward a synthesis of pactamycin enabled by alkene and C--H amination technologies. Two synthetic routes to the five-membered carbocyclic core of pactamycin were developed, the first utilizing an intramolecular benzoin reaction that enabled access to advanced intermediates for testing the key amination reactions. A second approach proceeded without recourse to protecting groups and makes possible access to enantioenriched material. Efforts to assemble the C1, C2, C3 triamino motif of the cyclopentane core are highlighted by a late-stage Rh-catalyzed chemoselective allylic C--H amination reaction and a Rh-catalyzed intramolecular alkene aziridination. Different approaches for assembling the C1, C2 cis-diamine, including use of the Rh-catalyzed aziridination and subsequent isomerization, are described. In the course of these studies, the core of the C2-epi-pactamycate, which bears all of the requisite nitrogen and oxygen functional groups to the epimeric natural product, was successfully synthesized.
Description
| Type of resource | text |
|---|---|
| Form | electronic; electronic resource; remote |
| Extent | 1 online resource. |
| Publication date | 2017 |
| Issuance | monographic |
| Language | English |
Creators/Contributors
| Associated with | Su, Justin Yun-pin |
|---|---|
| Associated with | Stanford University, Department of Chemistry. |
| Primary advisor | Du Bois, Justin |
| Thesis advisor | Du Bois, Justin |
| Thesis advisor | Stack, T. (T. Daniel P.), 1959- |
| Thesis advisor | Trost, Barry M |
| Advisor | Stack, T. (T. Daniel P.), 1959- |
| Advisor | Trost, Barry M |
Subjects
| Genre | Theses |
|---|
Bibliographic information
| Statement of responsibility | Justin Yun-pin Su. |
|---|---|
| Note | Submitted to the Department of Chemistry. |
| Thesis | Thesis (Ph.D.)--Stanford University, 2017. |
| Location | electronic resource |
Access conditions
- Copyright
- © 2017 by Justin Yun-pin Su
- License
- This work is licensed under a Creative Commons Attribution Non Commercial 3.0 Unported license (CC BY-NC).
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