“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
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.
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
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