Catalysis of Free C–C Bond Rotation: C–F---H–X H-Bonds Find a Catalytic Role

There are few dynamic processes in organic chemistry that are more central to the molecular structure than C-C bond rotation. It is notable, however, that there exist few (if any) cases in which its hindered variants can actually be catalyzed. In this communication, we report a unique model system for the clear documentation of the catalysis of 360° C-C bond rotation that employs a transient but key N-H---F-C hydrogen bond as a linchpin and secondary "dual" charge-induced n → π* interactions and ion pairing effects that bolster catalysis.