Tuning the Regioselective Functionalization of Trifluoromethylated Dienes via Lanthanum‐Mediated Single C−F Bond Activation.

The development of new fluorine‐containing building blocks and their efficient synthetic access is currently a challenging research field. Herein, the highly regio‐ and stereoselective addition of a large range of aldehydes onto trifluoromethylated benzofulvenes was achieved using a simple La/I2/DIBAL‐Cl system via a selective C−F bond activation process. This versatile methodology provided homodienyl alcohols bearing a terminal CF2‐alkene with potential further applications, as shown by the dehydration to the first benzofulvenes carrying a difluorovinyl group. In addition, for certain electron‐poor aldehydes, unprecedented ipso substitution of the CF3 group in a diene was observed, which, according to DFT studies, is related to the presence of the large, Lewis‐acidic lanthanum metal. [ABSTRACT FROM AUTHOR]