Rhodium-catalyzed oxidation reactions for the synthesis of diamines and polyamines
Abstract/Contents
- Abstract
- The utility of 1,2- and 1,3-diamines is far-reaching as the diamino structural motif is found in pharmaceuticals, ligands used for asymmetric catalysis, and natural products. While chemists have developed a number of effective methods for installing oxygen-containing functional groups, the synthesis of equivalent nitrogenous structures remains an enormous challenge. For example, the catalytic dihydroxylation of olefins is a transformation covered in every undergraduate organic chemistry textbook, and the development of its asymmetric variant has garnered a Nobel Prize. Yet, despite extensive effort, the analogous diamination reaction has eluded synthetic chemists for more than 40 years. Densely-functionalized nitrogen-containing molecules, such as the naturally-occurring antibiotic pactamycin, have motivated us to develop methods for the preparation of polyamine structures. The cornerstone of our approach has relied on the selective oxidation of C--H bonds and olefins by dirhodium catalysts. Our research has involved: 1) the design of novel sulfonamide reagents, 2) explorations into the oxidizing ability of unusual metal-nitrene species, 3) reactivity and mechanistic studies involving a previously unknown class of heterocycles, 4) the development of preparative processes for the rapid assembly of diamine and polyamine derivatives, and 5) efforts towards the total synthesis of pactamycin. Nitrogen-rich molecules like pactamycin continue to challenge our inventiveness as chemists, and as a result, have led to a number of advances related to the synthesis of diamines and polyamines. All told, we feel that these discoveries demonstrate the power of Rh-catalyzed oxidation reactions for synthesizing amine-containing compounds and should prove of general use for chemical synthesis.
Description
| Type of resource | text |
|---|---|
| Form | electronic; electronic resource; remote |
| Extent | 1 online resource. |
| Publication date | 2011 |
| Issuance | monographic |
| Language | English |
Creators/Contributors
| Associated with | Olson, David Edward |
|---|---|
| Associated with | Stanford University, Department of Chemistry |
| Primary advisor | Du Bois, Justin |
| Thesis advisor | Du Bois, Justin |
| Thesis advisor | Khosla, Chaitan, 1964- |
| Thesis advisor | Wender, Paul A |
| Advisor | Khosla, Chaitan, 1964- |
| Advisor | Wender, Paul A |
Subjects
| Genre | Theses |
|---|
Bibliographic information
| Statement of responsibility | David Edward Olson. |
|---|---|
| Note | Submitted to the Department of Chemistry. |
| Thesis | Ph.D. Stanford University 2011 |
| Location | electronic resource |
Access conditions
- Copyright
- © 2011 by David Edward Olson
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