Development of Bicyclo[3.3.0]octadiene- or Dicyclopentadiene-Based Chiral Diene Ligands for Transition-Metal-Catalyzed Reactions

This account summarizes our efforts on the design, synthesis, and application of two classes of chiral diene ligands bearing bicyclo[3.3.0]octadiene or dicyclopentadiene skeletons. These chiral diene ligands can be readily prepared from inexpensive commercial materials with enzymatic resolution as the key synthetic step. The ligands have been successfully applied in some rhodium-catalyzed reactions, including 1,4-addition to α,β-unsaturated carbonyl compounds, arylation of imines, and conjugate addition to nitroalkenes. In addition, they have been used in the first successful palladium-diene-catalyzed asymmetric reaction.