A Study of BF3‐Promoted ortho Lithiation of Anilines and DFT Calculations on the Role of Fluorine–Lithium Interactions

Director's cut: The poor directing ability of the dimethylamino group in directed ortho metalation is altered by complexation to BF3, which makes it more strongly activating than methoxy and chloro groups. DFT calculations of simplified lithiated intermediates reveal a small role of the inductive effect, but a distinctive F⋅⋅⋅Li interaction that leads to a F–Li distance which is remarkably similar to the C–Li distance.