Title:
Ring-opening benzannulations of cyclopropenes, alkylidene cyclopropanes, and 2,3-dihydrofuran acetals: A complementary approach to benzo-fused (hetero)aromatics
Ring-opening benzannulations of cyclopropenes, alkylidene cyclopropanes, and 2,3-dihydrofuran acetals: A complementary approach to benzo-fused (hetero)aromatics
| dc.contributor.advisor | France, Stefan | |
| dc.contributor.author | Aponte-Guzman, Joel | |
| dc.contributor.committeeMember | Collard, David M. | |
| dc.contributor.committeeMember | Fahrni, Christoph J. | |
| dc.contributor.committeeMember | Jones, Christopher W. | |
| dc.contributor.committeeMember | Oyelere, Adegboyega K. | |
| dc.contributor.department | Chemistry and Biochemistry | |
| dc.date.accessioned | 2016-05-27T13:12:14Z | |
| dc.date.available | 2016-05-27T13:12:14Z | |
| dc.date.created | 2015-12 | |
| dc.date.issued | 2016-05-27 | |
| dc.date.submitted | December 2015 | |
| dc.date.updated | 2016-05-27T13:12:14Z | |
| dc.description.abstract | Over the past decades, functional group manipulation of aromatic precursors has been a common strategy to access new aromatic compounds. However, these classical methods, such as Friedel-Crafts alkylations and electrophilic/nucleophilic aromatic substitutions, have shown lack of regioselectivity besides the use of activators in excess amounts. To this end, numerous benzannulations to form benzo-fused substrates via Diels-Alder (DA), ring-closing metathesis (RCM), cycloaddition, and transition-metal-promoted processes have been reported. Appending a benzene ring directly onto a pre-existing ring is preferable to many classical methods due to the likely reduction of reaction steps and superior regiocontrol. However, many of these benzannulation reactions require air- and/or moisture- sensitive reaction conditions, a last oxidation step, or the use of highly functionalized precursors. Here we disclose three ‘complementary’ intramolecular ring-opening benzannulations to access a large array of functionalized (hetero)aromatic scaffolds utilizing cyclopropenes-3,3-dicarbonyls, alkylidene cyclopropanes-1,1-diesters, and 2,3-dihydrofuran O,O- and N,O- acetals as building blocks. More than 70 benzo-fused aromatic compounds were synthesized using this complementary approach with yields up to 98% and low catalyst loadings. With these benzannulation reactions in hand, we aim to open the synthetic door to a handful of bioactive natural products. | |
| dc.description.degree | Ph.D. | |
| dc.format.mimetype | application/pdf | |
| dc.identifier.uri | http://hdl.handle.net/1853/54953 | |
| dc.language.iso | en_US | |
| dc.publisher | Georgia Institute of Technology | |
| dc.subject | Cyclopropenes | |
| dc.subject | Alkylidene cyclopropanes | |
| dc.subject | 2,3-dihydrofuran | |
| dc.subject | Benzo-fused aromatics | |
| dc.subject | Benzannulation | |
| dc.subject | Ring-opening | |
| dc.subject | Formal-homo-Nazarov cyclization | |
| dc.subject | Heteroaromatics | |
| dc.title | Ring-opening benzannulations of cyclopropenes, alkylidene cyclopropanes, and 2,3-dihydrofuran acetals: A complementary approach to benzo-fused (hetero)aromatics | |
| dc.type | Text | |
| dc.type.genre | Dissertation | |
| dspace.entity.type | Publication | |
| local.contributor.advisor | Jones, Christopher W. | |
| local.contributor.advisor | Oyelere, Adegboyega K. | |
| local.contributor.advisor | Fahrni, Christoph J. | |
| local.contributor.advisor | France, Stefan | |
| local.contributor.advisor | Collard, David M. | |
| local.contributor.corporatename | School of Chemistry and Biochemistry | |
| local.contributor.corporatename | College of Sciences | |
| relation.isAdvisorOfPublication | 27088bc0-032b-40d1-b0a7-7f2f25b5bdeb | |
| relation.isAdvisorOfPublication | 559ad46f-fbf0-4834-aed9-4c606a8e0790 | |
| relation.isAdvisorOfPublication | 582e68ff-4689-4d69-95bd-97bbaf927034 | |
| relation.isAdvisorOfPublication | 60127d9c-be17-4aa7-bd28-c94458c4a043 | |
| relation.isAdvisorOfPublication | 93732ff7-3229-47ad-ad56-7ccdae805102 | |
| relation.isOrgUnitOfPublication | f1725b93-3ab8-4c47-a4c3-3596c03d6f1e | |
| relation.isOrgUnitOfPublication | 85042be6-2d68-4e07-b384-e1f908fae48a | |
| thesis.degree.level | Doctoral |