Enantiospecific Synthesis of <i>ortho</i>‐Substituted 1,1‐Diarylalkanes by a 1,2‐Metalate Rearrangement/<i>anti</i>‐S_<i>N</i>2′ Elimination/Rearomatizing Allylic Suzuki–Miyaura Reaction Sequence

Abstract

The one-pot sequential coupling of benzylamines, boronic esters, and aryl iodides has been investigated. In the presence of an N-activator, the boronate complex formed from an ortho-lithiated benzylamine and a boronic ester undergoes stereospecific 1,2-metalate rearrangement/anti-S_N 2' elimination to form a dearomatized tertiary boronic ester. Treatment with an aryl iodide under palladium catalysis leads to rearomatizing γ-selective allylic Suzuki-Miyaura cross-coupling to generate 1,1-diarylalkanes. When enantioenriched α-substituted benzylamines are employed, the corresponding 1,1-diarylalkanes are formed with high stereospecificity.