Formation and reactivity of allenes and spirodiepoxides
Institution: | Rutgers University |
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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.