Enantioselective β-functionalization of enals via N-heterocyclic carbene catalysis
| dc.contributor.author | White, Nicholas Andrew, author | |
| dc.contributor.author | Rovis, Tomislav, advisor | |
| dc.contributor.author | Kennan, Alan J., committee member | |
| dc.contributor.author | Chen, Eugene Y.-X., committee member | |
| dc.contributor.author | Williams, Robert M., committee member | |
| dc.contributor.author | Kipper, Matt J., committee member | |
| dc.date.accessioned | 2016-01-11T15:13:51Z | |
| dc.date.available | 2016-01-11T15:13:51Z | |
| dc.date.issued | 2015 | |
| dc.description.abstract | A series of δ-nitroesters were synthesized through the N-heterocyclic carbene catalyzed coupling of enals and nitroalkenes. The asymmetric coupling of these substrates via the homoenolate pathway afford δ-nitroesters in good yield, diastereoselectivity, and enantioselectivity. This methodology allows for the rapid synthesis of δ-lactams. Using this approach, we synthesized the pharmaceutically relevant piperidines paroxetine and femoxetine. A novel single-electron oxidation pathway for the N-heterocyclic carbene generated Breslow intermediate has been developed. Nitroarenes have been shown to transfer an oxygen from the nitro group to the β-position of an enal in an asymmetric fashion to generate β-hydroxy esters. This reaction affords desired β-hydroxy ester products in good yield and enantioselectivity and tolerates a wide range of enal substrates. A dimerization of aromatic enals to form 3,4-disubstituted cyclopentanones has been investigated. Using a single-electron oxidant, aromatic enals couple to form cyclopenanone products in good yield, good enantioselectivity, and excellent diastereoselectivity. A cross coupling has also been developed to afford non-symmetrical cyclopentanone products. | |
| dc.format.medium | born digital | |
| dc.format.medium | doctoral dissertations | |
| dc.identifier | White_colostate_0053A_13330.pdf | |
| dc.identifier.uri | http://hdl.handle.net/10217/170358 | |
| dc.language | English | |
| dc.language.iso | eng | |
| dc.publisher | Colorado State University. Libraries | |
| dc.relation.ispartof | 2000-2019 | |
| dc.rights | Copyright and other restrictions may apply. User is responsible for compliance with all applicable laws. For information about copyright law, please see https://libguides.colostate.edu/copyright. | |
| dc.subject | asymmetric | |
| dc.subject | carbene | |
| dc.subject | catalysis | |
| dc.subject | organic | |
| dc.title | Enantioselective β-functionalization of enals via N-heterocyclic carbene catalysis | |
| dc.type | Text | |
| dcterms.rights.dpla | This Item is protected by copyright and/or related rights (https://rightsstatements.org/vocab/InC/1.0/). You are free to use this Item in any way that is permitted by the copyright and related rights legislation that applies to your use. For other uses you need to obtain permission from the rights-holder(s). | |
| thesis.degree.discipline | Chemistry | |
| thesis.degree.grantor | Colorado State University | |
| thesis.degree.level | Doctoral | |
| thesis.degree.name | Doctor of Philosophy (Ph.D.) |
Files
Original bundle
1 - 1 of 1
Loading...
- Name:
- White_colostate_0053A_13330.pdf
- Size:
- 12.69 MB
- Format:
- Adobe Portable Document Format