AbstractA highly enantioselective cobalt‐catalyzed semipinacol rearrangement of symmetric α,α‐diarylallylic alcohols is disclosed. A chiral cobalt‐salen catalyst generates a highly electrophilic carbocation surrogate following hydrogen atom transfer and radical–polar crossover steps. This methodology provides access to enantioenriched α‐aryl ketones through invertive displacement of a cobalt(IV) complex during 1,2‐aryl migration. A combination of readily available reagents, silane and N‐fluoropyridinium oxidant, are used to confer this type of reactivity. An exploration into the effect of aryl substitution revealed the reaction tolerates para‐ and meta‐halogenated, mildly electron‐rich and electron‐poor aromatic rings with excellent enantioselectivities and yields. The yield of the rearrangement diminished with highly electron‐rich aryl rings whereas very electron‐deficient and ortho‐substituted arenes led to poor enantiocontrol. A Hammett analysis demonstrated the migratory preference for electron‐rich aromatic rings, which is consistent with the intermediacy of a phenonium cation.
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