Metathetic approach to new NORPHOS-related bisphosphanes: facile synthesis and application in asymmetric hydrogenation

A highly efficient synthesis of new chiral bisphosphanes derived from the renowned NORPHOS ligand is presented. The synthesis involves ring-opening metathesis of NORPHOS dioxide with an external olefin, followed by saturation of the new double bonds and adjustment of the oxidation level of phosphorus centers oxidation level. The synthesized bisphosphanes retain the configuration and enantiomeric purity of the starting NORPHOS. Their utility as ligands in asymmetric catalysis is exemplified using an open-NORPHOS ligand in some benchmark Rh-catalyzed hydrogenations of enamides where excellent chemical yields and enantiomeric purities of the products have been secured. The proposed protocol demonstrated the possibility of a straightforward synthesis of new chiral catalysts to be utilized in the asymmetric synthesis of pharmaceutically important compounds, such as amino acid derivatives.

Keywords

amino acids, asymmetric hydrogenation, C2-symmetry, ChemRAWN, chiral phosphanes, NORPHOS, one-pot syntheses, ROM

Citation

"Pure and Applied Chemistry", 2021, Vol. 93, nr 4, s. 409-426