Date of Award
2008
Degree Type
Thesis
Degree Name
Doctor of Philosophy
Program
Chemistry
Supervisor
Michael Kerr
Abstract
The previously described intermolecular nitrone - cyclopropane reaction has been adapted into an intramolecular variant. A nitrone, generated in-situ by the addition of a hydroxylamine to an aldehyde, engages in a cycloaddition with a 2-carbon-tethered cyclopropanediester. The products of the reaction are substituted [2.2.2]-aza-oxa- bicyclooctanes that are highly functionalized since a wide degree of flexibility is allowed in the tether linkage. Besides an all sp3-carbon spacer, an unsaturated tether can be used and aromatic and heteroaromatic rings can be incorporated into the tether. Importantly, a mild and high yielding procedure to obtain 1,4-aminoalcohols by reductive N-O bond rupture of these compounds has been developed and was shown to produce substituted cis- l-amino-4-cyclohexanols and cis-1-amino-4-hydroxytetrahydronaphthalenes. An expansion of this methodology was envisioned by the use of a ketonic substrate as a nitrone precursor en route to the synthesis of the erythrinan alkaloid 3- demethoxyerythratidinone and work is underway toward this goal.
Recommended Citation
Dias, Dwayne A., "The Intramolecular Reaction of Nitrones with Cyclopropanes: Toward the Total Synthesis of Selected Erythrinan and Homoerythrinan Alkaloids" (2008). Digitized Theses. 4382.
https://ir.lib.uwo.ca/digitizedtheses/4382