Angewandte Chemie, Accepted Article.
An enantioselective bifunctional squaramide‐catalyzed detrifluoroacetylative alkylation reaction under electrochemical conditions has been developed. The unified strategy based on this key tandem methodology has been divergently explored for the asymmetric synthesis of fluorine‐containing target molecules with good stereocontrol (up to 95% ee ). Furthermore, this catalytic asymmetric detrifluoroacetylative alkylation reaction demonstrated the benefits of combining electrosynthesis and organocatalysis for the preparation of biologically relevant products containing C‐F tertiary stereogenic center.