Abstract Catalytic asymmetric Friedel–Crafts alkylation is a powerful protocol for constructing a chiral C (sp 2)[BOND] C (sp 3) bond. Most previous examples rely on LUMO activation of the electrophiles using chiral catalysts with subsequent attack by electron-rich arenes. Presented herein is an alternative strategy in which the HOMO of the aromatic π system of 2- furfuryl ketones is raised through the formation of a formal trienamine species using a ...