The retro-ene reaction of 2-vinylcyclohexanols and approaches to the synthesis of botryococcene Public Deposited

http://ir.library.oregonstate.edu/concern/graduate_thesis_or_dissertations/vt150n45k

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  • The retro-ene reaction of 2-vinylcyclohexanols occurs readily in the vapor phase at 400-450° producing unsaturated carbonyl compounds in good yields. The starting- materials were prepared in general by the carbenoid addition reaction of ethyl diazoacetate, appropriately substituted cyclohexene, and copper catalyst to produce bicyclic esters which were reduced to the alcohols and rearranged with aqueous acid. Stereochemical examination of several examples suggest the reaction is concerted and the products are kinetically determined. The reaction constitutes a useful stereoselective procedure for the synthesis of tri-substituted olefins. The synthesis of botryococcene, a geochemically important, abundant hydrocarbon of Botryococcus braunii, focused on an appropriate half-molecule which could be asymmetrically coupled. A retro-ene route was examined, but an alternative, more conventional route provided better results. This reaction scheme was founded on the convergent coupling of an organometallic reagent from the THP derivative of 6-bromo-3-methyl -2-hexen-l-ol and 4, 5- dimethyl- 5- hexenal. The aldehyde was prepared from ethyl methyl acetoacetate in seven steps with an overall yield of 24%. The second component, 6-bromo-3-methyl -2-hexen-l-ol was prepared from 2, 5-hexanedione in five steps with an overall yield of 22%. The correct conditions to generate the organometallic reagent have not yet been discovered.
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  • description.provenance : Approved for entry into archive by Patricia Black(patricia.black@oregonstate.edu) on 2013-11-06T20:00:10Z (GMT) No. of bitstreams: 1 RusayRonaldJ1977.pdf: 1335972 bytes, checksum: 70cef6527ecc29b9a13c48fbdb1d469b (MD5)
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