Regioselective Reductive Elimination from Bismuth(V) Compounds for Aryl Transfer to Nucleophiles

Abstract

AbstractWe demonstrate that regioselective aryl transfer to the nucleophile occurs rapidly under mild conditions via reductive elimination and show that regioselectivity is primarily governed by steric factors imparted by ortho substituents on the recipient ring. Computational modeling and x‐ray crystallography confirm that the recipient aryl ring is positioned in the equatorial coordination site and oriented orthogonally to the axial X−Bi−Ph bond (X=nucleophile) in a trigonal bipyramidal structure. The orientation of the ortho‐substituted aryl ring allows the appropriate orbital to overlap between its ipso carbon and nucleophile, which enhances the rate of aryl transfer to the nucleophile and dictates the regioselective reductive elimination from Bi(V) compounds. This level of stereoelectronic control results in significantly enhanced reaction rate and selectivity and creates an opportunity to rationally design ligand systems for selective aryl transfer reactions.