The Aryne Ene Reaction

Abstract Intermolecular aryne ene reactions present opportunities to arylate a wide range of unsaturated substrates in a single step, whilst intramolecular reactions provide expedient access to valuable benzofused carbo- and heterocyclic frameworks. This short review will chart the development of the aryne ene reaction from initial reports that rationalise unexpected byproduct formation in competing [4+2] and [2+2] cycloadditions through to its exploitation in contemporary synthetic methodology. 1 Introduction 2 Alkene Ene Reactions 2.1 Intermolecular 2.2 Intramolecular 3 Alkyne Ene Reactions 3.1 Intermolecular 3.2 Intramolecular 4 Allene Ene Reactions 5 Aromatic Ene Reactions 6 Hetero Ene Reactions 6.1 Enols 6.2 Enamines 6.3 Imines 7 Conclusions