Development of an asymmetric intermolecular stetter reaction and organocatalyst design
Date
2012
Authors
Glover, Garrett S., author
Rovis, Tomislav, advisor
Wood, John L., committee member
Kanatous, Shane, committee member
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Abstract
The intermolecular Stetter represents a powerful carbon-carbon bond forming reaction that involves addition of an acyl anion equivalent to an untethered Michael acceptor. Despite the appeal of rendering the intermolecular reaction asymmetric, this area remains particularly underdeveloped. We describe a catalytic asymmetric intermolecular Stetter reaction for the coupling of 2-pyridinecarboxaldehydes and β-substituted vinyl triflones. In pursuit of increasing the efficiency of this reaction, we developed a series of base-activated NHC pre-catalysts that are capable of catalyzing the intramolecular Stetter reaction without an external base. As an indirect result of our attempts to form activated pre-catalysts, we discovered a catalyst hydration product, that itself generates free-carbene in solution. Additionally, we gathered conclusive evidence for a previously unknown SNAR type decomposition pathway of an electron deficient triazolinylidene catalyst.
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Subject
asymmetric catalysis
Stetter reaction
organocatalysis
NHC
intermolecular