[1,3]-oxygen to carbon rearrangement for the construction of carbon-carbon bonds between adjacent rings and 1,3-dioxepines in synthesis
| dc.contributor.author | Frein, Jeffrey Daniel, author | |
| dc.contributor.author | Rovis, Tomislav, advisor | |
| dc.date.accessioned | 2024-03-13T19:53:46Z | |
| dc.date.available | 2024-03-13T19:53:46Z | |
| dc.date.issued | 2007 | |
| dc.description.abstract | Several methods for the stereoselective formation of carbon-carbon bonds between contiguous rings where a stereogenic center is already present have been examined. The approaches investigated were: a [1,3]-oxygen to carbon rearrangement of cyclic vinyl acetals; an intermolecular enolsilane addition into an in situ generated oxocarbenium ion; an intramolecular conjugate addition of tethered alkoxy enones; and epimerization of several α-pyranyl cycloalkanones. These routes have been found to be complementary in several cases and have enabled formation of both the traps: anti and cis:anti stereoisomers in good to excellent yields and varying diastereoselectivities. The C2-C2' relative stereochemistry of the carbon-carbon bond between the adjacent rings was proven via a chemical correlation. The versatility of 1,3-dioxepines as precursors to the formation of 1,4-diols and 1,2,4-triols has been examined. The rapid synthesis of unsymmetrical 1,3-dioxepines and the installation of a 4-acetoxy substituent as a synthetic handle for further functionalization has been realized. The Lewis acid mediated addition into in situ generated oxocarbenium ions has been developed for variety of different nucleophiles. Furthermore, a highly trans -diastereoselective Heck reaction has been performed on unsymmetrical 1,3-dioxepines and their synthetic utility as precursors to the formation of 2,3,4-alkyl substituted tetrahydrofurans and 2-methoxy-4,5-alkyl substituted tetrahydrofurans have been exploited. | |
| dc.format.medium | born digital | |
| dc.format.medium | doctoral dissertations | |
| dc.identifier | ETDF_Frein_2007_3266393.pdf | |
| dc.identifier.uri | https://hdl.handle.net/10217/237739 | |
| 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.rights.license | Per the terms of a contractual agreement, all use of this item is limited to the non-commercial use of Colorado State University and its authorized users. | |
| dc.subject | adjacent rings | |
| dc.subject | carbon-carbon bonds | |
| dc.subject | oxygen to carbon rearrangement | |
| dc.subject | organic chemistry | |
| dc.title | [1,3]-oxygen to carbon rearrangement for the construction of carbon-carbon bonds between adjacent rings and 1,3-dioxepines in synthesis | |
| dc.title.alternative | 1,3-oxygen to carbon rearrangement for the construction of carbon-carbon bonds between adjacent rings and 1,3-dioxepines in synthesis. | |
| 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.) |
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