Asymmetric Synthesis of Axially Chiral Biaryls: Inversion of Planar Chirality vs Axial Isomerization and Functionalization at the Side Chain of Biaryl Chromium Complexes

Abstract
Axially chiral syn-biaryl chromium complexes having a coordinating heteroatom substituent at the benzylic position gave anti-biaryl chromium complexes 5 with inversion of the planar chirality by heating in a nonaromatic solvent, while syn-biaryl chromium complexes with an o-methyl or formyl substituent afforded axially isomerized anti-biaryl chromium complexes under heating in an aromatic solvent. syn-Biaryl and both enantiomeric anti-biaryl chromium complexes with the o-formyl group were stereoselectively prepared from an identical planar chiral arene chromium complex as chiral source. The formyl group of the axially chiral chromium complexes was functionalized by radical cyclization and β-lactam formation, and hetero-Diels−Alder reaction.

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