for newer compounds in late-stage clinical trials and further to 50% for the most successful blockbuster drugs. Because regio-and stereoselectivity of fluorine are critical for bioactivity, fluorine chemocatalysis has blossomed with asymmetric methods that can be largely divided into three strategies: electrophilic fluorination, nucleophilic fluorination, and elaboration of achiral or racemic organofluorines. However, one challenge that has only been specifically addressed more recently is the construction of the stereogenic tertiary fluoride moiety (also referred to in literature as a carbon-fluorine quaternary stereocenter ), exemplified by the fact that only three major approved drugs bear this motif (Figure ).