Enantioselective Synthesis of Tertiary Allylic Fluorides by Iridium-Catalyzed Allylic Fluoroalkylation

Few allylic electrophiles containing two different substituents at a single allyl terminus and none in which one of the two substituents is a heteroatom, have been shown previously to react with iridium catalysts to form substitution products. We report that iridium-catalysts are uniquely suited to form tertiary allylic fluorides enantioselectively by the addition of a diverse range of carbon-centered nucleophiles at the fluorine-containing terminus of 3-fluoro-substituted allylic esters. The products contain tertiary stereogenic centers bearing a single fluorine, which are isosteric with common tertiary stereocenters containing a single hydrogen. Computational studies reveal the principal steric interactions influencing the stability of endo and exo pi-allyl intermediates formed from 3,3-disubstituted allylic electrophiles.