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Title: Pericyclic and related rearrangements for the synthesis of nitrogen heterocyclic ring systems
Author: Zhurakovskyi, Oleksandr
Awarding Body: University of Oxford
Current Institution: University of Oxford
Date of Award: 2013
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The thesis describes synthesis and reactions of allene azides tethered to various functional groups and the application of the discovered cascade transformations towards the synthesis of radianspene J model system. Chapter 1 covers reactions of simple allene azides containing alkyl and cycloalkyl substituents. Thermal rearrangements of these substrates delivered isocyanides and azadienes via the proposed azatrimethylenemethane (ATMM) intermediates. On the other hand, vinylidenecyclopropanes (VDCPs) gave dramatically different products, as described in Chapter 2. A phenyl-substituted VDCP was transformed into an unstable polycyclic compound by a divinylcyclopropane rearrangement. Chapter 3 discusses allene azides tethered to furan, N-substituted pyrroles, and E- and Z-dienes. Depending on the structure of the starting material, products of formal (3+4)- or (2+3)-cycloaddition were formed. Finally, an application of the discovered cyclisation cascade towards total synthesis is described in Chapter 4. A model system of radianspene J was assembled using a key transannular cycloaddition of a macrocyclic allene.
Supervisor: Robertson, Jeremy Sponsor: Clarendon Fund
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: Heterocyclic chemistry ; Natural products ; Organic synthesis ; Organic chemistry ; allenes ; azides ; rearrangement ; pericyclic reactions ; cycloadditions ; ene reaction ; azatrimethylenemethane ; Radianspene J ; total synthesis