Asymmetric electrocyclic reactions

Thesis

Pericyclic reactions are a class of transformations that comprise sigmatropic rearrangements, group transfer reactions, cycloadditions and electrocyclic reactions. Since Woodward and Hoffmann rationalized the mechanism and stereochemistry of pericyclic reactions they have become powerful synthetic tools. Whilst sigmatropic rearrangements and cycloadditions are cornerstones of contemporary synthetic methodology, many electrocyclic reactions are not fully exploited currently; there are no general methods for the asymmetric catalysis of electrocyclic reactions and as a consequence, opportunities for exerting stereocontrol in these manifolds are limited. We aim to establish general methods for the asymmetric catalysis of 6π electrocyclic reactions. Our initial studies are focused on a pentadienyl anion moiety due to the greater ease of cyclization observed with such systems in comparison to the corresponding neutral hexatriene systems.

Authors: Maciver, E

• Publication date: 2013
• DOI: 10.5287/ora-9g60wemo5
• Type of award: DPhil
• Level of award: Doctoral
• Awarding institution: University of Oxford
• Language: English
• Keywords: Electrocyclization; Asymmetric; Catalysis
• Subjects: Asymmetric catalysis