Funktionelle Phosphane: Part XI. Optisch reine β-Aminophosphane und β-Aminophosphinite für die komplexkatalysierte Reduktion organischer Carbonylverbindungen. Molekülstrukturen von [(1R,2R)-Ph2PCH(Ph)CH(Me)NH2Me]Cl, (1R,2S)-Ph2PCH(Ph)CH(Me)NHSO2Me und [{(

The preparation of optically active β-aminophosphane ligands, (−)-(1R,2S)-Ph2PCH(Ph)CH(Me)NH2 (5), (+)-(1S,2S)-Ph2PCH(Ph)CH(Me)NH2 (6), (−)-(1R,2R)-Ph2PCH(Ph)CH(Me)NHMe (7), and (1R,2S)-Ph2PCH(Ph)CH(Me)NHSO2Me (8), as well as of related β-aminophosphinites, (+)-(1R,2S)-Ph2POCH(Ph)CH(Me)NH2 (9), (−)-(1R,2R)-Ph2POCH(Ph)CH(Me)NHMe (10), (+)-(1S,2S)-Ph2POCH(Ph)CH(Me)NHMe (11), and (−)-(1R,2S)-Ph2POCH(Ph)CH(Me)NHMe (12), from commercially available ephedrine, norephedrine, and pseudoephedrine enantiomers is reported. Ligands 6 and 7 react with [M(η4-1,5-C8H12)2]BF4 (M=Rh, Ir) to afford the P,N chelate complexes [{(1S,2S)-Ph2PCH(Ph)CH(Me)NH2-κN,κP}Ir(η4-1,5-C8H12)]BF4 (13), [{(1R,2R)-Ph2PCH(Ph)CH(Me)NHMe-κN,κP}Rh(η4-1,5-C8H12)]BF4 (14), and [{(1R,2R)-Ph2PCH(Ph)CH(Me)NHMe-κN,κP}Ir(η4-1,5-C8H12)]BF4 (15), of which 14 and 15 exist as mixtures of three sterically locked ring conformers. The molecular structures of the prevailing λ(RC,RC,SN) form of rhodium complex 14, of β-aminophosphane 8 and of the hydrochloride of ligand 7 were determined by single-crystal X-ray diffraction. In the presence of added triethylamine, iridium complex 15 catalyzes the enantioselective hydrogenation of acetophenone, giving (−)-(S)-1-phenylethanol in modest enantiomeric excess (40%).