An Exploration of Novel Metal-Mediated Vinylcyclopropane Reactivity
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2020-08
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Abstract
Vinycyclopropanes (VCPs) are an important building block for synthetic and medicinal chemistry as they can undergo a variety of useful cycloaddition reactions to rapidly prepare complex molecular frameworks. Although VCPs contain ring strain, useful energy to drive chemical reactions, they typically still require activation to induce cycloadditions. The activation of vinylcyclopropanes using first row transition metal catalysis is not broadly studied and may offer opportunities for novel reactivity. First row transition metals were used to study the reactivity of three different vinylcyclopropanes toward cycloadditions. This thesis describes the results of screening these unactivated vinylcyclopropanes with Cu, Co, Ni and Fe catalysts. Subsequently, vinycyclopropane-containing natural products were screened for their reactivity toward cycloaddition reactions. Monoterpenes sabinene and 2-carene were utilized as starting materials for these annulations which were tested via rhodium catalysis. Also explored, was the induction of a 1,4-sigmatropic rearrangement reaction with first row transition metal catalysis. The Derksen group has previously reported a photomediated rearrangement in which 6:3:5 and 7:3:5 vinylcyclopropane ring systems were quickly introduced. The synthesis of these materials in good yields and selectivity provides rapid access to polycyclic vinycyclopropanes that offer opportunities for further reactivity. This thesis describes the screening of this transformation via Mn, Ti, Cu, Co, Ni and Fe catalysis rather than photochemical conditions.
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Timmons, M. T. (2020). An Exploration of Novel Metal-Mediated Vinylcyclopropane Reactivity (Master's thesis, University of Calgary, Calgary, Canada). Retrieved from https://prism.ucalgary.ca.