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].