Date of Award

8-2005

Degree Type

Dissertation

Degree Name

Doctor of Philosophy

Major

Chemistry

Major Professor

David G. J. Young

Committee Members

Richard Pagni, Elizabeth Howell, J. Z. Larese

Abstract

The synthesis and application of α-allenyl ketones directed toward the synthesis of polycyclic polyprenylated acylphloroglucinols are described. A functionalized α-allenyl ketone was synthesized in twelve steps starting from 2-methyl-2-cyclohexenome in 24% overall yield. The α’ stereocenter in the α-allenyl ketone was stereoselectively quaternized using a Tsuji allylation, Mukaiyama adol condensation sequence to afford C-1 functionalized allenyl cyclohexanone building blocks. A survey of acetals and reaction conditions for the Mukaiyama reaction suggested that 3-tert-butyldiphenylsiloxypropanal dimethyl acetal could be used, and indeed this reagent in the presence of TiCl4∙Ti[OCH(CH3)2]4 gave the aldol product in 63% yield. The furthest advanced intermediate was prepared from 2-methyl-2-cyclohexenone in sixteen steps in 6% overall yield.

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Chemistry Commons

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