A C–F Bond Directed Diels–Alder Reaction

We demonstrate a C–F bond driven Diels–Alder reaction of a fluorinated dienophile and a borole that shows remarkable diastereoselectivity. The product’s structure was confirmed by X-ray crystallography, revealing an unusual conformation featuring a hypercoordinate boron. Calculations suggest that a B···F interaction instigates the reaction chemistry, the magnitude of which is maximized in the transition statein essence, the B···F distance “yo-yos” from long to short in the transition state and back again to long in the product.