Developing novel multi-component coupling reactions of arynes

• Main Author: Jones, Elizabeth Pearl
• Other Authors: Barrett, Anthony
• Published: Imperial College London 2012
• Subjects: 541.39
• Online Access: http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.550986

The development of novel three-component coupling reactions of arynes is under investigation. The emphasis is on efficient, concise and elegant routes to small, highly functionalised aromatic molecules. In order to extend the three-component coupling methodology to the previously underexploited 2,3-pyridyne intermediate 2, several strategies will be described, including the development and reactivity of novel halogen-metal exchange aryne precursor 1. [Molecular structure diagrams appear here. To view, please open pdf attachment]. Approaches towards the use of arynes 4 as electrophilic α-arylating reagents for amino acids are also described. In order to circumvent undesired side-reactions it was found necessary to use lithiated Schöllkopf’s bis-lactim ether 3 as the nucleophilic glycine equivalent. This route will be introduced and its development described, concluding in the presentation of a range of chiral, arylglycine derivatives, 6, using this methodology. The extension of this technique to the synthesis of quaternary Schöllkopf adducts and the resulting hydrolysis reactions are also illustrated. [Molecular structure diagrams appear here. To view, please open pdf attachment]. In addition, the discovery of an interesting side reaction, involving the use of nitroacetates 7 and arynes 4 for the synthesis of iso-indolinones 9 will be discussed. [Molecular structure diagrams appear here. To view, please open pdf attachment].