Preparation of <i>C</i>₂-Symmetric Bicyclo[2.2.2]octa-2,5-diene Ligands and Their Use for Rhodium-Catalyzed Asymmetric 1,4-Addition of Arylboronic Acids

C2-Symmetric bicyclo[2.2.2]octa-2,5-dienes containing benzyl, phenyl, and substituted phenyl groups at 2 and 5 positions were prepared enantiomerically pure by way of bicyclo[2.2.2]octane-2,5-dione as a key intermediate. These chiral diene ligands were successfully applied to rhodium-catalyzed asymmetric 1,4-addition of arylboronic acids to α,β-unsaturated ketones. High enantioselectivity (up to 99% ee) as well as high catalytic activity was observed in the addition to both cyclic and linear substrates.