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.