An easy protocol has been developed for the formation of stereogenic carbon–fluorine centers by the organocatalytic asymmetric α‐fluorination of aldehydes 1. The 2‐fluoroaldehydes 4 are formed with 2 as the fluorinating agent and only 1 mol % of a sterically demanding silylated prolinol 3 as catalyst. The 2‐fluoroaldehydes are subsequently reduced to the corresponding alcohols 5 without loss of enantiomeric excess.

Cinchona alkaloids are employed in an organocatalyzed asymmetric Friedel–Crafts amination reaction of 2‐naphthols. These amination reactions proceed in high yields with up to 98 % ee and have led to a new class of non‐biaryl atropisomer. The rotation barriers of the chiral aminated 2‐naphthols have been investigated by experimental and computational methods.

The mechanism for the 2,5-diphenylpyrrolidine-catalyzed enantioselective alpha-chlorination of aldehydes with electrophilic halogenation reagents has been investigated by using experimental and computational methods. These studies have led us to propose a mechanism for the reaction that proceeds through an initial N-chlorination of the chiral catalyst-substrate complex, followed by a 1,3-sigmatropic shift of the chlorine atom to the enamine carbon atom. The suggested reaction course is different from previously proposed mechanisms for organocatalytic enamine reactions, in which the carbon-electrophile bond is formed directly. Furthermore, the rate-determining step in the overall reaction was determined and the presence of nonlinear effects was probed.