Ruthenacycles and Iridacycles as Catalysts for Asymmetric Transfer Hydrogenation and Racemisation

Ruthenacycles, which are easily prepared in a single step by reaction between enantiopure aromatic amines and [Ru(arene)Cl2]2 in the presence of NaOH and KPF6, are very good asymmetric transfer hydrogenation catalysts. A range of aromatic ketones were reduced using isopropanol in good yields with ee’s up to 98%. Iridacycles, which are prepared in similar fashion from [IrCp*Cl2]2 are excellent catalysts for the racemisation of secondary alcohols and chlorohydrins at room temperature. This allowed the development of a new dynamic kinetic resolution of chlorohydrins to the enantiopure epoxides in up to 90% yield and 98% enantiomeric excess (ee) using a mutant of the enzyme Haloalcohol dehalogenase C and an iridacycle as racemisation catalyst.

Dispersion of the second-order nonlinear susceptibility in ZnTe, ZnSe, and ZnS

We have measured the absolute values of the second-harmonic generation (SHG) coefficient |d| for the zinc-blende II-VI semiconductors ZnTe, ZnSe, and ZnS at room temperature. The investigated spectral region of the fundamental radiation λF ranges from 520 to 1321 nm using various pulsed laser sources. In the transparent region of the II-VI semiconductors, the SHG coefficient exceeds the values of birefringent materials as ammonium dihydrogen phosphate (ADP) and potassium dihydrogen phosphate (KDP) by one or two orders of magnitudes. Above the E0 band gap a strong dispersion of |d| is observed, showing a maximum for a second-harmonic frequency close to the E1 gap. The experimental results are compared to calculated values using a simple three-band model including spin-orbit splitting. Substantial agreement is found to the experimentally observed dispersion of the second-order nonlinear susceptibility

Synthesis of Β-aminoacid derivatives via enantioselective hydrogenation of Β substituted-Β-(acylamino) acrylates

International audienc

Hydrogenation of β-N-substituted enaminoesters in the presence of ruthenium catalysts

International audienc