Remarkably High Asymmetric Amplification in the Chiral Lanthanide Complex-Catalyzed Hetero-Diels−Alder Reaction:  First Example of the Nonlinear Effect in ML<sub>3</sub> System

A remarkably high asymmetric amplification was realized in the Yb[(<i>R</i>)-BNP]<sub>3</sub>-catalyzed hetero-Diels−Alder reaction as the first example in the metal/chiral ligand 1:3 system. The mechanism may be explained by the autogenetic formation of the enantiopure complex as the most active catalyst. The enantiomer-discriminative formation of homochiral ML<sub>3</sub> complexes is quite general within the lanthanide metal ions with similar ionic radii to that of the ytterbium ion.