Functional phosphances Part XI. Optically pure beta-aminophosphanes and beta-aminophosphinites for complex-catalyzed reduction of organic carbonyl compounds. Molecular structure of [(1R,2R)-Ph2PCH(Ph)CH(Me)NH2ME]Cl, (1R,2S)-Ph2PCH(Ph)CH(Me)NHSO2Me and [{(1R,2R)-Ph2PCH(Ph)(CH(Me)NHMe-kappa N,kappa P}Rh(eta(4)-1,5-C8H12)]-BF4

The preparation of optically active beta -aminophosphane ligands, (-)-(1R,2 S)-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 beta -aminophosphinites, (+)-(1R,2S)-Ph2POCH(Ph)CH(Me)NH2 (9 ), (-)-(1R,2R)-Ph2POCH(Ph)CH(Me)NHMe (10), (+)-(1S,2S)-Ph2POCH(Ph)CH(Me)NHM e (11), and (-)-(1R,2S)-Ph2POCH(Ph)CH(Me)NHMe (12), from commercially avail able ephedrine, norephedrine, and pseudoephedrine enantiomers is reported. Ligands 6 and 7 react with [M(eta (4)-1,5-C8H12)(2)]BF4 (M = Rh, Ir) to aff ord the P,N chelate complexes [{(1S,2S)-Ph2PCH(Ph)CH(Me)NH2-kappaN,kappaP}I r(eta (4)-1,5-C8H12)]BF4 (13), [{(1R,2R)-Ph2PCH(Ph)CH(Me)NHMe-kappaN,kappaP }Ir(eta (4)-1,5-C8H12)]BF4 (14), and [{(1R,2R)-Ph2PCH(Ph)CH(Me)NHMe-kappaN, kappaP}Ir(eta (4)-1,5-C8H12)]BF4 (15), Of which 14 and 15 exist as mixtures of three sterically locked ring conformers. The molecular structures of th e prevailing lambda (R-C,R-C,S-N) form of rhodium complex 14, of beta -amin ophosphane 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, g iving (-)-(S)-1-phenylethanol in modest enantiomeric excess (40%). (C) 2001 Elsevier Science B.V. All rights reserved.