Fluoro‐Organocatalysts: Conformer Equivalents as a Tool for Mechanistic Studies

Fluorine in charge! The fluorine–iminium ion gauche effect has been exploited in the design of conformational probes for organocatalysis (see scheme). Stabilizing hyperconjugative [σCH→σ*CF] and/or electrostatic [N+⋅⋅⋅Fδ−] interactions render the CF bond an excellent steering group for controlling molecular topology without introducing additional steric constraints.