Synthesis of Stereochemically Flexible Cyclic Biphenylbisphosphinite Ligands: Control of the Dynamics and Selectivity

Abstract Novel l ‐tartaric acid based stereodynamic biphenylbisphosphinite ligands with anilino linkers were prepared as cyclic diamide compounds. The influence of the constitutional substitution pattern amino group at aniline moiety on diastereoselective formation ligand was investigated. While meta ‐anilino bridged showed a highly dynamic behavior and no discrimination between ( R ax ) S configuration, ortho leads to self‐alignment central biphenol axis, which controls stereoselectivity catalyst. experimental findings corroborated by theoretical calculations. In rhodium‐catalyzed enantioselective hydrogenation methyl 2‐acetamidoacrylate (MAA), an enantiomeric ratio 75 : 25 / obtained for ‐substituted ligand.