The novel N,N,O-tridentate phenanthroline ligand (BinThro) bearing an axially chiral binaphthyl backbone prepared from BINOL was found to be an effective chiral catalyst for enantioselective addition of diethylzinc to aromatic aldehydes with high enantioselectivity (up to 95% ee).

In the presence of a Cu(ii) complex of axially chiral, N,N,O-tridentate phenanthroline ligand (S)-2, asymmetric oxygen atom transfer of oxindole derivatives (3) using Davis' oxaziridine (4) occurred to give the corresponding 3-aryl-3-hydroxy-2-oxindole derivatives (1) with excellent enantioselectivity (up to 96% ee). The X-ray crystallographic analysis of the isolated Cu(ii) complex disclosed its N,N,O-tridentate coordination, which is critical to realize effective catalytic activity.

The N,N,O-tridentate chiral phenanthroline ligand was employed for Cu(II)-catalyzed enantioselective a-hydroxylation of b-ketoesters with racemic Davis' oxaziridine to provide the corresponding product. We also tried to understand the plausible mechanism for asymmetric induction of this reaction, achieved by the effective shielding of prochiral Cu(II) enolate. With this working hypothesis, enantioselective a-chlorination of b-ketoesters to give the corresponding products was achieved with high enantioselectivity.[a] Dr.

Bei der Reaktion mit Trimethylsilyldiazomethan (II) erhält man aus den Oxo‐Verbindungen (I) unter Einschiebung die Methylen‐ketone (III).