Enantioselective Hydrogenation Catalysis Aided by a σ-Bonded Calix[4]arene to a P-Chirogenic Aminophosphane Phosphinite Rhodium Complex

The first P-chirogenic aminophosphane−phosphinite (AMP*P) ligand (4a) supported on the upper rim of a calix[4]arene moiety was synthesized in two steps using the ephedrine methodology. Ligand 4a was used for the preparation of the corresponding rhodium complex [Rh(COD)(AMP*P)]BF4 (5a) (COD = 1,8-cyclooctadienyl), which was tested for asymmetric catalyzed hydrogenation of various substrates. The structures of the AMP*P ligand as diborane and rhodium complexes 3a and 5a were established by X-ray analysis. The asymmetric hydrogenation catalyzed with the Rh complex 5a exhibits excellent enantioselectivities up to 98%. Investigation of modified P-chirogenic aminophosphane−phosphinite ligands 4b,c, bearing an isoelectronic or a sterically similar substituent on the P-chirogenic aminophosphane unit, demonstrates that the calix[4]arene substituent of the aminophosphane moiety plays a major role in the better asymmetric induction. The enantioselectivity of the catalyzed hydrogenation was weakly influenced by the hydrogen pressure, which is in good agreement with a stereodetermining step involving the substrate−rhodium complexes. Computer modeling indicated the presence of two conformers for the active AMP*P rhodium species, according to whether the rhodium metal is outside or inside the calix[4]arene cavity (called outer and inner). It is obvious that the complexation of the substrate with the active rhodium species forces this complex to adopt fully the outer conformation and hence explains why the calixarene fragment plays a key role in the stereodetermining step.