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

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

Angew. Chem. Int. Ed. 201857, 13125-13129.

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 π‐allyl intermediates formed from 3,3‐disubstituted allylic electrophiles.

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