The heteroatom effect in intramolecular cyclizations of organoaluminum and -lithium compounds Public Deposited

http://ir.library.oregonstate.edu/concern/graduate_thesis_or_dissertations/pv63g2717

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  • Intramolecular cyclization of organometallic compounds represents a promising tool for synthesis in general. The use of strategically- placed heteroatoms in the cyclizing molecule can influence the stereochemistry and/or efficiency of an organometallic cyclization while providing for functionality in the cyclic product. The work described herein first concerns cyclizations of organolithiums. Prepared from the appropriate halide, heteroatom-containing alkenyllithiums cyclized to produce five and six-membered rings in some cases when analogous systems without heteroatoms failed to cyclize. Allylic and homoallylic heteroatom systems cyclized with stereochemistry opposite to that obtained in the cyclization of alkyl-substituted counterparts. The inclusion of n-butyllithium in the reaction medium was found to accentuate the heteroatom's influence. Organoaluminum cyclizations were also investigated. Prepared by the hydroalumination of a multiple bond, alkenylaluminum compounds with and without heteroatoms were cyclized. A homoallylic ether-containing alkenylaluminum cyclized with stereochemistry opposite to that of its methyl substituted replica. In cyclizations of 1, 1-dialuminocompounds, prepared from enyne precursors, alkene cyclization products, due to dehydroalumination, were obtained when ether was excluded from the reaction mixture. In the presence of ether these systems did not dehydroaluminate and saturated cyclic products were obtained.
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