Synthesis and Reactions of Novel Oxindoles

An important issue with the assignment of E/Z alkene geometry of 3-acylidene-oxindoles was addressed. A novel UV/Visible spectroscopic assay was developed in order to achieve this, taking advantage of contrasting electronic properties for different E/Z isomer sets. Moreover, a novel acylidene oxindole was prepared and used to provide further supporting evidence for this spectroscopic assay. Finally, the stability of related E/Z isomers was investigated, and indicated facile isomerisation to a thermodynamic minimum.
A copper promoted cyclisation of o-nitrophenyl iodoacetylenes to 2-iodoisatogens was discovered. These compounds were applicable as precursors to novel isatins and consequently 3-acylidene oxindoles.
The metal free aryl and alkyl cross coupling reactions of 2-iodoisatogens was developed, providing a divergent synthetic strategy to the medicinally relevant isatogen molecular group. Furthermore, an unprecedented isatogen mode of reactivity was discovered affording pseudoindoxyls, a privileged class of molecule. The mechanism for this transformation was proposed, based on control reactions and strong literature precedent.