Asymmetric Cyanosilylation of Aldehydes by a Lewis Acid/Base Synergistic Catalyst of Chiral Metal Clusters.

Metal clusters with well-defined crystal structures are extremely useful for studying the synergistic catalytic effects and associated catalytic mechanisms. In this study, two pairs of chiral lanthanide-transition metal clusters ( R )/( S )-Co 3 Ln 2 (Ln = Tb or Dy) were synthesized using Schiff-base ligands [( R )- or ( S )-H 3 L] with multiple Lewis base sites (O sites). The as-prepared ( R )/( S )-Co 3 Ln 2 chiral metal clusters exhibited good catalytic functionality in the asymmetric synthesis of chiral cyanohydrins, with high conversions of up to 99% and medium-to-high enantiomeric excess values of up to 78%. The catalysis process followed a mechanism in which the bifunctional metal clusters of ( R )/( S )-Co 3 Ln 2 , containing Lewis acid sites and Lewis base sites, simultaneously activated the aldehydes and trimethylsilyl cyanide, respectively. Consequently, synergistic catalysis was realized. The enantioselectivity of the different aldehydes and stereochemical configuration of the resulting products are attributed to the formation of a steric chiral pocket via the external chiral ligands on the clusters. In addition, heterogeneous asymmetric cyanosilylation using ( R )/( S )-Co 3 Ln 2 chiral metal clusters achieved high chemoselectivity and regioselectivity under mild conditions.