Type of Document	Dissertation
Author	Kozytska, Mariya V.
URN	etd-08242008-224231
Title	I. Siletanylmethyllithium, An Ambiphilic Siletane Ii. Synthetic Approach To Basiliolide B
Degree	Doctor of Philosophy
Department	Chemistry and Biochemistry, Department of
Advisory Committee	Advisor Name Title Gregory B. Dudley Committee Member Jack Saltiel Committee Member Marie E. Krafft Committee Member Michael Shatruk Committee Member Laura Keller Outside Committee Member
Keywords	Diels-Alder Reaction Basiliolide B Siletanylmethyllithium Silacyclobutane Halopyrone Synthesis
Date of Defense	2008-08-19
Availability	unrestricted
Abstract This dissertation is composed of two independent research projects. The first part describes the synthesis and reactivity of siletanylmethyllithium, and includes a thorough review of the chemistry of siletanes. Siletanylmethyllithium was successfully generated by transmetallation of 1-(tributyltin)methyl-1-methylsiletane, which was produced on multi-gram scale. The title compound demonstrates ambiphilic character and was employed for the olefination of benzophenone. It also holds potential as a hydroxymethyllithium equivalent. The second part focuses on the total synthesis of basiliolide B, a natural product with promising biomedical potential. A key intramolecular 5-iodopyrone Diels-Alder cycloaddition assembles the bridged decalin skeleton of basiliolide B. The reaction was firstly examined on model systems and then successfully employed to construct the framework of the natural product. The convenient functionalities were installed in the system which can be further elaborated into dihydrooxepin ring to complete the structure of basiliolide B.
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