Chemoenzymatic Synthesis and Application of Bicyclo[2.2.2]octadiene Ligands: Increased Efficiency in Rhodium‐Catalyzed Asymmetric Conjugate Additions by Electronic Tuning

On your bi(cycle)ke! A series of 1,4-dimethyl bicyclic [2.2.2] diene ligands with tunable substitution at the bridge positions was accessed using a lipase resolution and a high yielding six step sequence (see scheme). The bridgehead methyl groups improve efficiency allowing less aryl boronic acid to be used in the title reaction.