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Date of Award
Master of Science (MS)
O'Neil, Gregory (Gregory W.)
Murphy, Amanda R.
Gilbertson, John D.
It has been found that β-hydroxyketone compounds can be reduced to the corresponding 1,3-diol through an intramolecular carbonyl hydrosilation. Furthermore, because this hydrosilation proceeds through a cyclic 6-membered ring transition state, this reduction can be performed diastereoselectively by placing a stereocenter on the 6-membered ring transition state. Prior to further investigations into this diastereoselective intramolecular carbonyl hydrosilation, a streamlined synthesis of β-hydroxyketone compounds has been developed. This new synthesis features an enone diboration/oxidation sequence found to be successful on a broad scope of enones in high yields. Further studies have shown that placing a stereocenter outside of the transition state ring invokes moderate levels of diastereoselectivity based on the Felkin-Ahn model of carbonyl addition. However, when stereocenters are placed both inside and outside of the transition state ring, as in the case of the matched and mismatched hydrosilations, diastereoselectivity is based solely off of the stereocenter inside of the transition state ring. This stereocontrol allows for the synthesis of antipropionate subunits with both anti-syn and syn-syn stereochemistry. The synthetic utility of this hydrosilation is shown by using this reaction to synthesize the stereocenters present in the highly studied natural product discodermolide.
Western Washington University
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Medina, Casey R., "Diastereoselective intramolecular carbonyl hydrosilation for complex polyketide synthesis" (2013). WWU Masters Thesis Collection. 289.