“Trans-Positioning” Carbons within Strained Caged Bicyclic(s): ROM/RCM (Ring-Opening/Ring-Closing) Metathesis and Dieckmann/Retro-Dieckmann Condensation Routes to a Cis-Decalin Infrastructure

<p>This dissertation describes methodology work involving a “Trans-Positioning” motif engaging strategically positioned carbons within a strained bi-carbocyclic core and on a tethered free-dangling hydrocarbon chain ultimately for skeletal rearrangement. Trans-alkenylation and trans-acylation processes are devised for investigation with bicyclo[2.2.2]octyl and bicyclo[2.2.1]heptyl strained cores. Recent advances in olefin metathesis led to an independent proposal of the now applicable, RRM (Ring-Rearranging Metathesis) for trans-alkenylation purposes. A resourceful Dieckmann/retro-Dieckmann sequence is devised for trans-acylation motives. Finally, this dissertation includes atypical diastereoselective reductions and additions which were serendipitously found with trigonal carbon atoms appended to our pertinent strained systems while in pursuit of our aforementioned methodology.</p>

Name thesis:degree_name

Doctor of Philosophy (PhD)

Level thesis:degree_level

Dissertation

Discipline thesis:degree_discipline

Chemistry

Grantor

Chemistry

Year dc:date.available

2014

Author dc:creator

• Cooper Jr, Stefan Malone

• Olfein Metathesis
• ROM/RCM
• Dieckmann Condensation
• retro-Dieckmann
• cis-Decalin
• Bicyclo[2.2.2]octanone
• Bicyclo[2.2.2]octene
• Hydridic Reduction
• Lithium Directed Aldol
• Diastereoselectivity

Statement dc:rights

• unrestricted
• Release the entire work immediately for access worldwide.

Identifier

etd-01222015-151256
https://repository.lsu.edu/gradschool_dissertations/1120

OAI identifier oai:identifier

oai:repository.lsu.edu:gradschool_dissertations-2119