Expanding access to allylic amines through C–H amination
Abstract/Contents
- Abstract
- The presence of nitrogen functional groups is ubiquitous in chemotherapies across a number of categories including antibiotics, anti-tumor agents, and anti-HIV drugs. C–H amination is a promising method for introducing amines and amine derivatives into small molecules. This process requires a metal catalyst to facilitate the conversion of traditionally unreactive C–H bonds into valuable C–N bonds. While competing methods for C–H amination utilize a range of metal catalysts, this research expands upon a class of dirhodium metal catalysts previously discovered in the Du Bois Lab. As we have shown, newly designed tris- and tetrahydroxypyridine dirhodium catalyst system greatly enhances the scope and application of C–H amination technology. Specifically, this work investigates how structural ligand differences affect reactivity behavior and reaction performance in an effort to optimize C–H amination reaction conditions for selective formation of allylic amines. Allylic C–H amination reactions are broadly divided between intramolecular and intermolecular C–H amination reactions. In intramolecular allylic systems, results indicate that these catalysts operate best in a partially oxidized state, reaching full conversion with selectivities far exceeding 20:1 ratios. Results collected from intermolecular reactions suggest that tris hydroxypyridine rhodium catalysts functionalize more efficiently than their tetrakis counterparts, reaching full conversion with a selectivity of 10:1 in favor of C–H amination. This research should impact the field of medicinal chemistry and allow for more direct access to many types of therapeutics to treat human disease.
Description
| Type of resource | text |
|---|---|
| Date created | June 2021 |
| Date modified | December 5, 2022 |
| Publication date | April 30, 2022 |
Creators/Contributors
| Author | Brunello, Julianna |
|---|---|
| Degree granting institution | Stanford University, Department of Biology, 2021 |
| Thesis advisor | Du Bois, Justin |
| Thesis advisor | Frydman, Judith |
| Thesis advisor | Wender, Paul |
Subjects
| Subject | C–H amination |
|---|---|
| Subject | rhodium catalyst |
| Subject | allylic amines |
| Subject | therapeutics |
| Genre | Text |
| Genre | Thesis |
Bibliographic information
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- License
- This work is licensed under a Creative Commons Attribution Share Alike 3.0 Unported license (CC BY-SA).
Preferred citation
- Preferred citation
- Brunello, Julianna; Du Bois, Justin; Frydman, Judith; Wender, Paul. (2021). Expanding access to allylic amines through C–H amination. Stanford Digital Repository. Available at: https://purl.stanford.edu/wg011hz2894
Collection
Undergraduate Theses, Department of Biology, 2020-2021
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- julesb@stanford.edu
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