AbstractsBiology & Animal Science

Formation and reactivity of allenes and spirodiepoxides

by Yue Zhang

Institution: Rutgers University
Department: Chemistry and Chemical Biology
Degree: PhD
Year: 2010
Keywords: Allene – Oxidation; Allene – Reactivity
Record ID: 1872062
Full text PDF: http://hdl.rutgers.edu/1782.1/rucore10001600001.ETD.000056874


Disclosed are the studies on allene and functionalized medium sized ring synthesis as well as applications of spirodiepoxide based methods. A new method of making allenes via C-C bond fragmentation was developed by which, most notably, an enantioenriched functionalized cyclic allene was synthesized. Mechanistic studies provide a framework for understanding this reaction in relation to other known modes of fragmentation. The synthesis of a chiral cyclononadienone was completed. This product has been shown to be a key intermediate towards many members of the xenicane family. Three epoxomicin analogues were synthesized. The issue of selectivity in allene oxidation was addressed in the course of this study. A model study towards erythronolide A was completed in which the feasibility of selective double cuprate addition to a bis[spirodiepoxide] macrolactone controlled by the macrocyclic environment was demonstrated. Lastly, the development of new reactions using spirodiepoxides to directly access densely functionalized structures in single- or two-flask procedures is reported.