Enantioselective Fluorination of α‐Branched Aldehydes and Subsequent Conversion to α‐Hydroxyacetals via Stereospecific C—F Bond Cleavage.

The highly enantioselective fluorination of α-branched aldehydes was achieved using newly developed chiral primary amine catalyst 1. Furthermore, the C–F bond cleavage of the resulting α-fluoroaldehydes proceeded smoothly under alcoholic alkaline conditions to yield the corresponding α-hydroxyacetals in a stereospecific manner. Accordingly, the one-pot conversion of α-branched aldehydes into α-hydroxyacetals was achieved for the first time in high enantioselectivity.