Methyl 4-trimethylsilyl-3-dialkylaminocrotonate is synthesized by the silylation of methyl 3-dialkylaminocrotonate. It reacts with carbonyl electrophiles at its (gamma)-position. The unusual regiochemistry of this reaction is studied and rationalized. It reacts with enamines derived from acyclic ketones or cycloketones of large ring size (of 12 and 15 membered rings) to give aromatic compounds in a 3C + 3C combination and with enamines derived from cycloketones of 5-8 membered rings to give aromatic compounds in a 4C + 2C combination. The mechanism of this cycloaromatization reaction is investigated. / meta-Cyclophanes with a morpholino substituent are synthesized by the above cycloaromatization reaction. These meta-cyclophanes possess planar chirality and are successfully resolved. / A number of metacyclophanes with alkyl substituents at the intraannular position are synthesized. Depending on the ring size and the steric size of the alkyl group, some of them are also resolved. The rotation process of meta-cyclophane is studied through their temperature dependent ('1)H NMR.
| Identifer | oai:union.ndltd.org:LACETR/oai:collectionscanada.gc.ca:QMM.71883 |
| Date | January 1983 |
| Creators | Kang, Guo-jun. |
| Publisher | McGill University |
| Source Sets | Library and Archives Canada ETDs Repository / Centre d'archives des thèses électroniques de Bibliothèque et Archives Canada |
| Language | English |
| Detected Language | English |
| Type | Electronic Thesis or Dissertation |
| Format | application/pdf |
| Coverage | Doctor of Philosophy (Department of Chemistry.) |
| Rights | All items in eScholarship@McGill are protected by copyright with all rights reserved unless otherwise indicated. |
| Relation | alephsysno: 000195035, proquestno: AAINK66620, Theses scanned by UMI/ProQuest. |
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