I. Siletanylmethyllithium, an Ambiphilic Siletane II. Synthetic Approach to Basiliolide B

• Other Authors: Kozytska, Mariya V. (authoraut)
• Format: Others
• Language: English; English
• Published: Florida State University
• Subjects: Biochemistry; Biophysics; Molecular biology; Chemistry
• Online Access: http://purl.flvc.org/fsu/fd/FSU_migr_etd-2856

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. === A Dissertation submitted to the Department of Chemistry and Biochemistry in partial fulfillment of the requirements for the degree of Doctor of Philosophy. === Fall Semester, 2008. === August 19, 2008. === Diels-Alder Reaction, Basiliolide B, Siletanylmethyllithium, Silacyclobutane, Halopyrone, Synthesis === Includes bibliographical references. === Gregory B. Dudley, Professor Directing Dissertation; Laura Keller, Outside Committee Member; Marie E. Krafft, Committee Member; Jack Saltiel, Committee Member; Michael Shatruk, Committee Member.