Supporting Information

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1 Supporting Information P-Chirogenic Xantphos Ligands and Related Ether iphosphines Synthesis and Application in the Rhodium Catalyzed Asymmetric Hydrogenation Jens Holz,* a Katharina Rumpel, a Anke Spannenberg, a Rocco Paciello, b Haijun Jiao, a Armin Börner* a,c a Leibniz-Institut für Katalyse e.v., A.-Einstein-Str. 29a, Rostock (Germany), b BASF SE; GCB/H - M313, Ludwigshafen (Germany), c Institut für Chemie, Universität Rostock A.-Einstein-Str. 3a, Rostock (Germany). jens.holz@catalysis.de; armin.boerner@catalysis.de Content 1. General information 2. Preliminary trials to use Jugé s methodology for the construction of the title compounds 3. Synthesis of (1R,2S)-2-{[(S)-(aryl)(phenyl)phosphinyl]methylamino}-1-phenylpropan-1-ol P- borane complexes 3a-t 4. Synthesis of (S)-(aryl)(methoxy)(phenyl)phosphine P-borane complexes 4a-t 5. Synthesis (1S,1'S)-(9,9-dimethyl-9H-xanthene-4,5-diyl)bis(aryl)(phenyl)phosphines 5a-t 6. Synthesis of 4,6-bis((S)-(aryl)(phenyl)phosphinyl)dibenzo[b,d]furans 6a,g,h 7. Synthesis of (1S,1'S)-(oxybis(2,1-phenylene))bis(aryl(phenyl)phosphines) 7a-t 8. Miscellaneous 9. Calculation of least-squares planes by SHELXL-2014 for 5j, 6g, and 7j General information All solvents were dried and freshly distilled under argon before use. All reactions were performed under an argon atmosphere by using standard Schlenk techniques. Thin-layer chromatography was performed on precoated TLC plates (silica gel). Flash chromatography was carried out with silica gel 60 (particle size mm) with a CombiFlash R F system (Teledyne ISCO). NMR spectra were recorded generally at Bruker AV 400 spectrometer at the following frequencies: MHz (1H), MHz ( 13 C), MHz ( 31 P) or at Bruker AV 300 ( MHz (1H), MHz ( 13 C), MHz ( 31 P)). Chemical shifts of 1 H and 13 C NMR spectra are reported in ppm downfield from used solvent CCl 3 as internal standard (7.25 ppm / ppm). Chemical shifts of 31 P NMR spectra are referred to H 3 PO 4 as external standard. Signals are quoted as s (singlet), d (doublet), t (triplet), q (quartet), m (multiplet) and br (broad). Mass spectra were recorded on a Thermo Electron MAT 95-XP or an Agilent 1200/6210 Time-of-flight LC-MS. For chiral HPLC-analysis a device Agilent 1100 Series was used. The X-ray diffraction data were collected on a Bruker Kappa APEX II uo diffractometer with Cu-Kα radiation. The structures were solved by direct methods (SHELXS

2 97) 1 and refined by full-matrix least-squares techniques on F 2 (SHELXL-2014) 2. XP (Bruker AXS) was used for graphical representations. The (2R,4S,5R)-2,3,4,5-Tetrahydro-3,4-dimethyl-2,5-diphenyl-1,3,2-oxazaphosphole P-borane complex 2 was prepared by the procedure of Hansen et al Preliminary trials to use Jugé s methodology for the construction of the title compounds Preliminary trials for diphosphorylation of 9,9-dimethylxanthene according to Jugé methodology 4 were carried out in the following manner: 1.) Attempts for dilithiation: 2eq. of n-buli in the presence of 2 eq. of TMEA, -40 C to r.t., 20 hours, diethyl ether; 2.) After addition of the mixture to a solution of 4a (-20 C to r.t., 1.5 hours, thf) and work up the yielded raw product showed in the NMR spectra besides 38 mol-% of 4a ( P = ppm) and 5 mol-% of BH 3 -unprotected 4a ( P = ppm) only 55 mol-% of the monophosphorylated xanthene ( P = ppm). The borane group was probably removed by the effect of TMEA (figure S1). When this reaction was carried out in the absence of TMEA a mixture yielded consisting of 35 mol-% of 4a, 9 mol-% of monophosphorylated xanthene and 56 mol-% of (2-anisyl)(n-butyl)(phenyl)phosphine borane complex ( P = ppm). Obviously the complete lithiation of xanthene was hindered by the absence of TMEA and the remained n-buli reacted with 4a. In another trial it could be shown that the borane protected derivative 4a reacts readily with n- butyllithium. To simulate the introduction of an aromatic group the reaction was repeated with phenyllithium as nucleophile. A similar reaction of 4a with 4-lithio-1,2-dimethoxybenzene was also published by Hansen et al. 3 Apparently, the close proximity of the both reactive centers as found in xanthene in 4,5-position inhibits the simultaneous incorporation of two bulky phosphine-borane units. This assumption is supported by our observation that treatment of Xantphos with two equivalents of BH 3 *MS in toluene afforded 87 mol-% of the mono-protected compound ( P = +22.6/-21.8 ppm), but only 13 mol-% of the expected bis-borane adduct ( = ppm) (figure S2)

3 Figure S1. 31 P NMR spectrum after reaction of 9,9-dimethyl-9H-xanthene with 4a without in situ removing of borane group; raw mixture after working up; NMR signals of (S)-(2-anisyl)(n-butyl)(phenyl)phosphine P-borane complex and (2- anisyl)(diphenyl)phosphine P-borane complex These two derivatives were synthesized by addition of 1 equivalent of n-butyllithium solution or phenyllithium solution to methylphosphinite 4a (tetrahydrofuran, -40 C to r.t, 20 h). Working up was carried out in similar manner as described before. (S)-Butyl(2-methoxyphenyl)(phenyl)phosphine P-borane complex 1 H-NMR: 7.92 (1H, ddd, J 13.5, 7.6, 1.7 Hz, arom. H), (2H, m, arom. H), 7.48 (1H, m, arom. H), (3H, m, arom. H), 7.04 (1H, m, arom. H), 6.88 (1H, ddd, J 8.4, 3.3, 0.7 Hz, arom. H), 3.67 (3H, s, OCH 3 ), 2.57 (1H, m, H a -CH 2 ), 2.23 (1H, m, H b -CH 2 ), (4H, m, 2xCH 2 ), 0.88 (3H, t, J 7.1 Hz, CH 3 ), (3H, br q, BH 3 ); - 3 -

4 13 C-NMR: (d, J 2.0 Hz, C-OMe), (d, J 13.7 Hz, CH), (d, J 2.0 Hz, CH), (d, J 9.1 Hz, 2xCH), (d, J 57.4 Hz, C-P), (d, J 2.1 Hz, CH), (d, J 10.1 Hz, 2xCH), (d, J 12.2 Hz, CH), (d, J 52.0 Hz, C-P), (d, J 3.5 Hz, CH), 55.2 (OCH 3 ), 25.2 (CH 2 ), 24.1 (d, J 15.4 Hz, CH 2 ), 23.6 (d, J 39.2 Hz, CH 2 ), 13.4 (CH 3 ); 31 P-NMR: +16.2; (2-methoxyphenyl)diphenylphosphine P-borane complex 1 H-NMR: (5H, m, arom. H), (7H, m, arom. H), 6.95 (1H, m, arom. H), 6.83 (2H, dd, J 8.4, 3.8, Hz, arom. H), 3.42 (3H, s, OCH 3 ), (3H, br q, BH 3 ); 13 C-NMR: (C-OMe), (d, J 12.1 Hz, CH), (d, J 2.3 Hz, CH), (d, J 10.2 Hz, 4xCH), (d, J 2.6 Hz, CH), (d, J 60.4 Hz, C-P), (d, J 10.2 Hz, 4xCH), (d, J 11.6 Hz, CH), (d, J 56.7 Hz, C-P), (d, J 4.7 Hz, CH), 55.1 (OCH 3 ); 31 P-NMR: +18.9; Figure S2. 31 P NMR spectrum after reaction of Xantphos with 2 eq. of BH 3 *MS 31 P NMR: ppm (2x P*BH 3 of Xantphos*2 BH 3 ) [13 mol-%] and ppm (1x P*BH 3, Xantphos*1 BH 3 ), ppm (1x P, Xantphos*1 BH 3 ) [87 mol-%]; - 4 -

5 3. Synthesis of (1R,2S)-2-{[(S)-(aryl)(phenyl)phosphinyl]methylamino}-1-phenylpropan-1-ol P- borane complexes 3a-t General Procedure for the Preparation If not other remarked the synthesis followed the established procedure of Jugé et al mmol of sec- Butyllithium (14.3 ml, 1.4 M solution) were placed in a Schlenk-tube at 0 C. 20 mmol of the corresponding arylbromide was slowly added. After one hour tetrahydrofuran was slowly added to the resulted suspension until the precipitate has been dissolved. This reagent was slowly added to a solution of phosphole 2 (10 mmol, 2.85 g) in THF (10 ml) at -78 C. After stirring for 1 hour at 0 C the mixture was quenched by addition of water (5 ml). After removing the volatile solvents under vacuum the residue was extracted with dichloromethane (3x25 ml). The combined organic phases were dried (Na 2 SO 4 ) and after evaporation of CM the residue was purified either by chromatography or crystallization. (1R,2S)-2-{[(S)-(2-Methoxyphenyl)(phenyl)phosphinyl](methyl)amino}-1-phenylpropan-1-ol P- borane-complex (3a) Yield 91%; white solid, m.p. = 120 C (from i-proh/hexane); ( ] 25 [ 21 = (c 1.0, CH 2 Cl 2 ), = (c 0.36, CH 2 Cl 2 ) 6 25, other enantiomer ] = (c 1.0, CH 2 Cl 2 ) 5 ); 1 H-NMR: 7.56 (1H, ddd, J 12.6, 7.6, 1.7 Hz, arom. H), (3H, m, arom. H), (8H, m, arom. H), 7.01 (1H, m, arom. H), 6.90 (1H, ddd, J 8.3, 4.2, 0.8 Hz, arom. H), 4.89 (1H, d, J 5.3 Hz, CH-O), 4.32 (1H, m, CH-N), 3.57 (3H, s, OCH 3 ), 2.54 (3H, d, J 8.1 Hz, CH 3 -N), 1.89 (1H, br s, OH), 1.21 (3H, d, J 6.8 Hz, CH 3 ), (3H, br q, BH 3 ); 13 C-NMR: (d, J 2.5 Hz, C-O), (C-C), (d, J 10.7 Hz, CH), (d, J 10.7 Hz, CH), (d, J 70.9 Hz, C-P), (d, J 10.2 Hz, 2xCH), (d, J 2.2 Hz, CH), (2xCH), (d, J 11.0 Hz, 2xCH), (CH), (2xCH), (d, J 10.3 Hz, CH), (d, J 57.4 Hz, C-P), (d, J 4.6 Hz, CH), 78.5 (d, J 5.6 Hz, CH-O), 58.1 (d, J 10.6 Hz, CH-N), 55.1 (OCH 3 ), 31.0 (d, J 3.9 Hz, CH 3 N), 12.9 (d, J 2.2 Hz, CH 3 ); 31 P-NMR: +69.1; MS (EI, 70 ev) m/z: 392 (2%, [M-H] +, 362 (2%, [M-OH-BH 3 ] +, 286 (71%, [M-C 7 H 7 O] + ), 272 (100%, [M-C 7 H 7 O-BH 3 ] + ), 215 (98%, [PPh(o-An)] + ; HRMS (ESI) [M-BH 3 +H] + : m/z calcd. for C 23 H 27 NO 2 P , found , [M-BH 3 +Na] + : m/z calcd. for C 23 H 26 NNaOP , found ; [ - 5 -

6 (1R,2S)-2-{[(S)-(3-Methoxyphenyl)(phenyl)phosphinyl](methyl)amino}-1-phenylpropan-1-ol P- borane complex (3b) Yield 92%; thick syrup (column chromatography cyclohexane/acoet 9/1 to 4/1); 23 [ ] 25 = (c 1.0, CHCl 3 ), (other enantiomer ] = (c 1.2, CHCl 3 ) 7 ) [ 1 H-NMR: 7.44 (2H, m, arom. H), (7H, m, arom. H), (4H, m, arom. H), 7.00 (1H, m, arom. H), 4.82 (1H, d, J 6.2 Hz, CH-O), 4.30 (1H, m, CH-N), 3.78 (1H, m, OCH 3 ), 2.48 (3H, d, J 7.6 Hz, CH 3 -N), 1.82 (1H, br s, OH), 1.25 (3H, d, J 6.8 Hz, CH 3 ), (3H, br q, BH 3 ); 13 C-NMR: (d, J 12.5 Hz, C-O), (C-C), (d, J 59.5 Hz, C-P), (d, J 10.4 Hz, 2xCH), (d, J 2.6 Hz, CH), (d, J 68.4 Hz, C-P), (d, J 11.6 Hz, CH), (2xCH), (d, J 10.4 Hz, 2xCH), (CH), (2xCH), (d, J 9.8 Hz, CH), (d, J 12.5 Hz, CH), (d, J 2.1 Hz, CH), 78.7 (d, J 5.9 Hz, CH-O), 58.1 (d, J 10.6 Hz, CH-N), 55.3 (OCH 3 ), 30.5 (d, J 4.8 Hz, CH 3 N), 13.4 (d, J 2.0 Hz, CH 3 ); 31 P-NMR: +71.6; MS (EI, 70 ev) m/z: 392 (1, [M-H] + ), 378 (2, [M-H-BH 3 ] + ), 286 (92 M-PhCHOH] + ), 272 (100, [M- BH 3 -PhCHOH] + ), 215 (99, [(3-MeO-Ph)PhP] + ); HRMS (ESI) [M+Na] + : m/z calcd. for C 23 H 29 BNNaO 2 P , found ; [M-BH 3 +H] + : m/z calcd. for C 23 H 27 NO 2 P , found ; [M-BH 3 +Na] + : m/z calcd. for C 23 H 26 NNaO 2 P , found ; (1R,2S)-2-{[(S)-(4-Methoxyphenyl)(phenyl)phosphinyl](methyl)amino}-1-phenylpropan-1-ol P- borane complex (3c) Yield 90%; white solid, m.p. = C (column chromatography cyclohexane/acoet 9/1); 24 [ ] 25 = (c 1.0, CHCl 3 ), (other enantiomer ] = (c 1.6, CHCl 3 ) 7 ) [ 1 H-NMR: (10H, m, arom. H), (2H, m, arom. H), 6.96 (2H, m, arom. H), 4.81 (1H, d, J 6.2 Hz, CH-O), 4.31 (1H, m, CH-N), 3.85 (3H, s, OCH 3 ), 2.47 (3H, d, J 7.9 Hz, CH 3 -N), 2.09 (1H, br s, OH), 1.25 (3H, d, J 6.7 Hz, CH 3 ), (3H, br q, BH 3 ); 13 C-NMR: (d, J 1.9 Hz, C-O), (C-C), (d, J 11.6 Hz, 2xCH), (d, J 10.3 Hz, 2xCH), (d, J 69.5 Hz, C-P), (d, J 1.9 Hz, CH), (2xCH), (d, J 10.3 Hz, 2xCH), (CH), (2xCH), (d, J 64.4 Hz, C-P), (d, J 11.6 Hz, 2xCH), 78.5 (d, J 6.4 Hz, CH-O), 57.9 (d, J 10.3 Hz, CH-N), 55.2 (OCH 3 ), 30.1 (d, J 4.5 Hz, CH 3 N), 13.5 (d, J 1.9 Hz, CH 3 ); 31 P-NMR: +69.5; - 6 -

7 MS (EI, 70 ev) m/z: 392 (2%, [M-H] + ), 286 (77, [M-PhCHOH] + ), 282 (100, [M-BH 3 -PhCHOH] + ), 215 (95, [(4-MeO-Ph)PhP] + ); HRMS (ESI) [M+Na] + : m/z calcd. for C 23 H 29 BNNaO 2 P , found ; [M-BH 3 +Na] + : m/z calcd. for C 23 H 26 NNaO 2 P found ; [M-BH 3 +H] + : m/z calcd. for C 23 H 27 NO 2 P found ; (1R,2S)-2-{[(S)-(2-Methylphenyl)(phenyl)phosphinyl](methyl)amino}-1-phenylpropan-1-ol P- borane complex (3d) Yield 89%; white solid, m.p. = C (column chromatography cyclohexane/acoet 19/1 to 9/1); 25 [ ] 25 = (c 1.0, CHCl 3 ); (other enantiomer ] = (c 2.0, CH 2 Cl 2 ) 5 ) [ 1 H-NMR: (2H, m, arom. H), (12H, m, arom. H), 4.93 (1H, d, J 4.0 Hz, CH-O), 4.35 (1H, m, CH-N), 2.63 (3H, d, J 4.4 Hz, CH 3 -N), 2.31 (3H, s, CH 3 ), 1.76 (1H, br s, OH), 1.24 (3H, d, J 6.8 Hz, CH 3 ), (3H, br q, BH 3 ); 13 C-NMR: (C-C), (d, J 12.5 Hz, C-C), (d, J 8.5 Hz, CH), (d, J 9.6 Hz, CH), (d, J 60.5 Hz, C-P), (d, J 10.4 Hz, 2xCH), (d, J 2.3 Hz, CH), (d, J 2.2 Hz, CH), (d, J 63.9 Hz, C-P), (d, J 10.1 Hz, 2xCH), (2xCH), (CH), (2xCH), (d, J 9.4 Hz, CH), 79.0 (d, J 2.2 Hz, CH-O), 58.0 (d, J 10.3 Hz, CH-N), 31.3 (d, J 3.6 Hz, CH 3 N), 22.0 (d, J 3.9 Hz, CH 3 ), 11.4 (d, J 4.7 Hz, CH 3 ); 31 P-NMR: +70.6; MS (EI, 70 ev) m/z: 376 (3%, [M-H] +, 256 (100%, [M-C 7 H 7 O-BH 3 ] + ), 199 (98%, [PPh(o-Tol)] + ; HRMS (ESI) [M+Na] + : m/z calcd. for C 23 H 29 BNNaOP , found ; [M-BH 3 +H] + : m/z calcd. for C 23 H 27 NOP , found , [M-BH 3 +Na] + : m/z calcd. for C 23 H 26 NNaOP , found ; (1R,2S)-2-{[(S)-(3-Methylphenyl)(phenyl)phosphinyl](methyl)amino}-1-phenylpropan-1-ol P- borane-complex (3e) Yield 87%; white solid; m.p. = C (column chromatography cyclohexane/acoet 19/1); 23 =+45.6 (c 1.0, CHCl 3 ); 1 H-NMR: (12H, m, arom. H), (2H, m, arom. H), 4.81 (1H, d, J 6.3 Hz, CH-O), 4.29 (1H, m, CH-N), 2.48 (3H, d, J 7.8 Hz, CH 3 -N), 2.35 (3H, s, PhCH 3 ), 1.85 (1H, br s, OH), 1.25 (3H, d, J 6.7 Hz, CH 3 ), (3H, br q, BH 3 ); - 7 -

8 13 C-NMR: (C-C), (d, J 10.3 Hz, C-Me), (d, J 11.1 Hz, CH), (d, J 10.4 Hz, 2xCH), (d, J 2.6 Hz, CH), (d, J 59.0 Hz, C-P), (d, J 67.9 Hz, C-P), (d, J 2.6 Hz, CH), (d, J 9.7 Hz, CH), (2xCH), (d, J 10.3 Hz, CH), (d, J 10.3 Hz, 2xCH), (CH), (2xCH), 78.6 (d, J 5.8 Hz, CH-O), 58.1 (d, J 10.2 Hz, CH-N), 30.4 (d, J 3.8 Hz, CH 3 N), 21.5 (PhCH 3 ), 13.4 (d, J 2.0 Hz, CH 3 ); 31 P-NMR: +71.0; MS (EI, 70 ev) m/z: 376 (1, [M-H] + ), 362 (1, [m-h-bh 3 ] + ), 270 (74, [M-PhCHOH] + ), 256 (100, [M- PhCHOH-BH 3 ] + ), 228 (17, [M-BH 3 -PhCHOH] + ), 199 (90, [(3-Me-Ph)PhP] + ); HRMS (ESI) [M+Na] + : m/z calcd. for C 23 H 29 BNNaOP , found ; [M-BH 3 +H] + : m/z calcd. for C 23 H 27 NOP , found ; [M-BH 3 +Na] + : m/z calcd. for C 23 H 26 NNaOP , found ; (1R,2S)-2-{[(S)-(4-Methylphenyl)(phenyl)phosphinyl](methyl)amino}-1-phenylpropan-1-ol P- borane complex (3f) Yield 42%; white solid, m.p. = C (column chromatography cyclohexane/acoet 19/1 to 9/1); 22 = (c 1.0, CHCl 3 ); 1 H-NMR: (12H, m, arom. H), (2H, m, arom. H), 4.80 (1H, d, J 6.9 Hz, CH-O), 4.29 (1H, m, CH-N), 2.46 (3H, d, J 8.0 Hz, CH 3 -N), 2.39 (3H, s, CH 3 ), 1.93 (1H, br s, OH), 1.23 (3H, d, J 6.8 Hz, CH 3 ), (3H, br q, BH 3 ); 13 C-NMR: (C-C), (d, J 2.6 Hz, C-C), (d, J 10.3 Hz, 2xCH), (d, J 10.3 Hz, 2xCH), (d, J 68.2 Hz, C-P), (d, J 2.6 Hz, CH), (d, J 10.3 Hz, 2xCH), (2xCH), (d, J 10.9 Hz, 2xCH), (CH), (d, J 61.2 Hz, C-P), (2xCH), 78.6 (d, J 5.7 Hz, CH-O), 58.0 (d, J 10.3 Hz, CH-N), 30.3 (d, J 3.9 Hz, CH 3 N), 21.4 (CH 3 ), 13.5 (d, J 1.9 Hz, CH 3 ); 31 P-NMR: +70.5; MS (EI, 70 ev) m/z: 376 (3, [M-H] + ), 286 (31, [M-H-BH 3 -Ph] + ), 270 (83, [M-BH 3 -Ph-OH] + ), 256 (100, [M-BH 3 -PhCHOH] + ), 199 (98, [(4-Me-Ph)PhP] + ); HRMS (ESI) [M+Na] + : m/z calcd. for C 23 H 29 BNNaOP , found ; [M-BH 3 +Na] + : m/z calcd. for C 23 H 26 NNaOP , found ; [M-BH 3 +H] + : m/z calcd. for C 23 H 27 NOP , found ; - 8 -

9 (1R,2S)-2-{[(S)-(2-Ethoxyphenyl)(phenyl)phosphinyl](methyl)amino}-1-phenylpropan-1-ol P- borane complex (3g) Yield 88%; white solid, m.p. = C (column chromatography cyclohexane/acoet 19/1 to 9/1); 23 = (c 1.0, CHCl 3 ); 1 H-NMR: 7.72 (1H, ddd, J 13.0 Hz, 7.7, 1.7, arom. H), (3H, m, arom. H), (8H, m, arom. H), 7.03 (1H, m, arom. H), 6.85 (1H, dd, J 8.3, 4.3 Hz, arom. H), 4.88 (1H, d, J 5.6 Hz, CH-O), 4.34 (1H, m, CH-N), 3.78 (1H, m, CH 2 -O), 2.58 (3H, d, J 8.2 Hz, CH 3 -N), 1.89 (1H, br s, OH), 1.22 (3H, d, J 6.8 Hz, CH 3 ), 0.91 (3H, t, J 7.0 Hz, CH 3 ), (3H, br q, BH 3 ); 13 C-NMR: (d, J 2.1 Hz, C-O), (C-C), (d, J 11.7 Hz, CH), (d, J 1.8 Hz, CH), (d, J 72.1 Hz, C-P), (d, J 10.9 Hz, 2xCH), (d, J 2.4 Hz, CH), (2xCH), (d, J 10.7 Hz, 2xCH), (CH), (2xCH), (d, J 11.1 Hz, CH), (d, J 56.9 Hz, C-P), (d, J 4.7 Hz, CH), 78.8 (d, J 5.9 Hz, CH-O), 63.4 (C-O), 58.1 (d, J 10.6 Hz, CH-N), 30.8 (d, J 4.0 Hz, CH 3 N), 13.7 (CH 3 ), 12.8 (d, J 2.0 Hz, CH 3 ); 31 P-NMR: +68.5; MS (EI, 70 ev) m/z: 406 (3, [M-H] + ), 286 (100, [M-BH 3 -PhCHOH] + ), 229 (85, [(2-EtO-Ph)PhP] + ); HRMS (ESI) [M+Na] + : m/z calcd. for C 24 H 31 BNNaO 2 P , found ; [M-BH 3 +H] + : m/z calcd. for C 24 H 29 NO 2 P found ; [M-BH 3 +Na] + : m/z calcd. for C 24 H 38 NNaO 2 P found ; (1R,2S)-2-{[(S)-(3-Ethoxyphenyl)(phenyl)phosphinyl](methyl)amino}-1-phenylpropan-1-ol P- borane complex (3h) Yield 90%; white solid, m.p. = 95 C (column chromatography cyclohexane/acoet 9/1); 23 = (c 1.0, CHCl 3 ); 1 H-NMR: (9H, m, arom. H), (4H, m, arom. H), 6.99 (1H, m, arom. H), 4.80 (1H, d, J 6.4 Hz, CH-O), 4.30 (1H, m, CH-N), 4.00 (2H, q, J 6.9 Hz, OCH 2 ), 2.48 (3H, d, J 7.7 Hz, CH 3 -N), 1.96 (1H, br s, OH), 1.39 (3H, t, J 6.9 Hz, CH 3 ), 1.26 (3H, d, J 6.8 Hz, CH 3 ), (3H, br q, BH 3 ); 13 C-NMR: (d, J 12.8 Hz, C-O), (C-C), (d, J 59.7 Hz, C-P), (d, J 10.3 Hz, 2xCH), (d, J 2.6 Hz, CH), (d, J 68.1 Hz, C-P), (d, J 11.6 Hz, CH), (2xCH), (d, J 10.4 Hz, 2xCH), (CH), (2xCH), (d, J 9.7 Hz, CH), (d, J 11.8 Hz, CH), (d, J 1.9 Hz, CH), 78.5 (d, J 5.9 Hz, CH-O), 63.5 (OCH 2 ), 58.0 (d, J 10.3 Hz, CH-N), 30.4 (d, J 3.9 Hz, CH 3 N), 14.6 (CH 3 ), 13.4 (d, J 1.9 Hz, CH 3 ); 31 P-NMR: +71.5; - 9 -

10 MS (EI, 70 ev) m/z: 392 (1, [M-H-BH 3 ] + ), 376 (1, [M-OH-BH 3 ] + ), 300 (32, [M-H-BH 3 -Ph-CH 3 ] + ), 286 (100, M-BH 3 -PhCHOH] + ), 229 (97, [(3-EtO-Ph)PhP] + ); HRMS (ESI) [M+Na] + : m/z calcd. for C 24 H 31 BNNaO 2 P , found ; [M-BH 3 +Na] + : m/z calcd. for C 24 H 28 NNaO 2 P found , [M-BH 3 +H] + : m/z calcd. for C 24 H 29 NO 2 P found ; (1R,2S)-2-{[(S)-(4-Ethoxyphenyl)(phenyl)phosphinyl](methyl)amino}-1-phenylpropan-1-ol P-boran complex (3i) Yield 71%; white solid, m.p = C (column chromatography cyclohexane/acoet 9/1); 22 = (c 1.0, CHCl 3 ); 1 H-NMR: (10H, m, arom. H), 7.10 (2H, m, arom. H), 6.91 (2H, m, arom. H), 4.79 (1H, d, J 6.5 Hz, CH-O), 4.28 (1H, m, CH-N), 4.05 (2H, q, J 7.0 Hz, OCH 2 ), 2.44 (3H, d, J 7.8 Hz, CH 3 - N), 1.91 (1H, br s, OH), 1.42 (3H, t, J 7.0 Hz, CH 3 ), 1.22 (3H, d, J 6.7 Hz, CH 3 ), (3H, br q, BH 3 ); 13 C-NMR: (d, J 2.7 Hz, C-O), (C-C), (d, J 11.7 Hz, 2xCH), (d, J 10.1 Hz, 2xCH), (d, J 69.7 Hz, C-P), (d, J 2.3 Hz, CH), (2xCH), (d, J 10.4 Hz, 2xCH), (CH), (2xCH), (d, J 64.5 Hz, C-P), (d, J 10.9 Hz, 2xCH), 78.6 (d, J 6.3 Hz, CH-O), 63.5 (OCH 2 ), 57.9 (d, J 10.4 Hz, CH-N), 30.1 (d, J 3.9 Hz, CH 3 N), 14.7 (CH 3 ), 13.5 (d, J 1.7 Hz, CH 3 ); 31 P-NMR: +69.6; MS (EI, 70 ev) m/z: 392 (1, [M-H-BH 3 ] + ), 300 (23, [M-H-BH 3 -Ph-CH 3 ] + ), 286 (100, M-BH 3 - PhCHOH] + ), 229 (97, [(4-EtO-Ph)PhP] +, 201 (84, [(4-HO-Ph)PhP] + ; HRMS (ESI) [M+Na] + : m/z calcd. for C 24 H 31 BNNaO 2 P , found ; [M-BH 3 +Na] + : m/z calcd. for C 24 H 28 NNaO 2 P found , [M-BH 3 +H] + : m/z calcd. for C 24 H 29 NO 2 P , found ; (1R,2S)-2-{[(S)-(2-Ethylphenyl)(phenyl)phosphinyl](methyl)amino}-1-phenylpropan-1-ol P-borane complex (3j) Yield 79%; white solid, m.p. = C (column chromatography cyclohexane/acoet 19/1 to 9/1); 23 = (c 1.0, CHCl 3 ); 1 H-NMR: 7.53 (2H, m, arom. H), (12H, m, arom. H), 4.95 (1H, d, J 3.9 Hz, CH-O), 4.35 (1H, m, CH-N), 2.67 (2H, t, J 7.5 Hz, CH 2 ), 2.61 (3H, d, J 7.4 Hz, CH 3 -N), 1.84 (1H, br s, OH), 1.24 (3H, d, J 6.8 Hz, CH 3 ), 1.14 (3H, t, J 7.5 Hz, CH 3 ), (3H, br q, BH 3 );

11 13 C-NMR: (d, J 12.9 Hz, C-Et), (C-C), (d, J 62.0 Hz, C-P), (d, J 8.1 Hz, CH), (d, J 9.7 Hz, 2xCH), (d, J 2.1 Hz, CH), (d, J 2.0 Hz, CH), (d, J 9.6 Hz, CH), (d, J 10.5 Hz, 2xCH), (2xCH), (d, J 63.0 Hz, C-P), (CH), (2xCH), (d, J 9.0 Hz, CH), 79.0 (d, J 2.4 Hz, CH-O), 58.0 (d, J 10.1 Hz, CH-N), 31.5 (d, J 3.6 Hz, CH 3 N), 26.6 (d, J 4.4 Hz, CH 2 ) 15.3 (CH 3 ), 11.5 (d, J 4.4 Hz, CH 3 ); 31 P-NMR: +70.9; MS (EI, 70 ev) m/z: 390 (1, [M-H] + ), 377 (1, [M-BH 3 ] + ), 270 (100, [M-BH 3 -PhCHOH] + ), 229 (85, [(2-Et-Ph)PhP] + ); HRMS (ESI) [M+Na] + : m/z calcd. for C 24 H 31 BNNaOP , found ; [M-BH 3 +H] + : m/z calcd. for C 24 H 29 NOP found ; (1R,2S)-2-{[(S)-(3-Ethylphenyl)(phenyl)phosphinyl](methyl)amino}-1-phenylpropan-1-ol P-borane complex (3k) Yield 92%; thick syrup (column chromatography cyclohexane/acoet 19/1); 23 = (c 1.0, CHCl 3 ); 1 H-NMR: (12H, m, arom. H), (2H, m, arom. H), 4.81 (1H, d, J 6.2 Hz, CH-O), 4.29 (1H, m, CH-N), 2.65 (2H, q, J 7.6 Hz, CH 2 ), 2.47 (3H, d, J 7.7 Hz, CH 3 -N), 1.91 (1H, br s, OH), 1.25 (3H, d, J 6.9 Hz, CH 3 ), 1.21 (3H, t, J 7.6 Hz, CH 3 ), (3H, br q, BH 3 ); 13 C-NMR: (d, J 9.7 Hz, C-Et), (C-C), (d, J 10.9 Hz, CH), (d, J 10.3 Hz, 2xCH), (d, J 67.6 Hz, C-P), (d, J 2.3 Hz, CH), (d, J 60.3 Hz, C-P), (d, J 2.5 Hz, CH), (d, J 9.8 Hz, CH), (2xCH), (d, J 10.3 Hz, CH), (d, J 10.2 Hz, 2xCH), (CH), (2xCH), 78.6 (d, J 5.8 Hz, CH-O), 58.1 (d, J 10.2 Hz, CH-N), 30.4 (d, J 3.9 Hz, CH 3 N), 18.8 (CH 2 ), 15.5 (CH 3 ), 13.4 (d, J 1.9 Hz, CH 3 ); 31 P-NMR: +71.2; MS (EI, 70 ev) m/z: 390 (1, [M-H] + ), 360 (2, [M-BH 3 -OH] + ),284 (49, [M-PhCHOH] + ), 270 (100, [M-BH 3 -PhCHOH] + ), 213 (95, [(3-Et-Ph)PhP] + ); HRMS (ESI) [M+Na] + : m/z calcd. for C 24 H 31 BNNaOP , found ; [M-BH 3 +H] + : m/z calcd. for C 24 H 29 NOP found ;

12 (1R,2S)-2-{[(S)-(2-Isopropoxyphenyl)(phenyl)phosphinyl](methyl)amino}-1-phenylpropan-1-ol P- borane complex (3l) Yield 80%; white solid, m.p. = C (column chromatography cyclohexane/acoet 4/1); 22 = (c 1.0, CHCl 3 ); 1 H-NMR: 7.74 (1H, ddd, J 13.3, 7.7, 1.7 Hz, arom. H), (3H, m, arom. H), (8H, m, arom. H), 6.99 (1H, m, arom. H), 6.80 (1H, dd, J 8.4, 4.2 Hz, arom. H), 4.87 (1H, d, J 5.5 Hz, CH-O), 4.41 (1H, m, CH-O), 4.32 (1H, m, CH-N), 2.60 (3H, d, J 8.4 Hz, CH 3 -N), 1.87 (1H, br s, OH), 1.22 (3H, d, J 6.8 Hz, CH 3 ), 0.92 (3H, d, J 6.1 Hz, CH 3 ), 0.89 (3H, d, J 6.1 Hz, CH 3 ), (3H, br q, BH 3 ); 13 C-NMR: (d, J 1.8 Hz, C-O), (C-C), (d, J 12.1 Hz, CH), (d, J 1.9 Hz, CH), (d, J 71.6 Hz, C-P), (d, J 10.3 Hz, 2xCH), (d, J 2.3 Hz, CH), (2xCH), (d, J 10.9 Hz, 2xCH), (CH), (2xCH), (d, J 11.1 Hz, CH), (d, J 57.8 Hz, C-P), (d, J 4.5 Hz, CH), 78.8 (d, J 5.6 Hz, CH-O), 69.1 (C-O), 58.1 (d, J 10.3 Hz, CH-N), 30.9 (d, J 3.8 Hz, CH 3 N), 21.0 (CH 3 ), 20.9 (CH 3 ), 12.9 (d, J 1.6 Hz, CH 3 ); 31 P-NMR: +68.4; MS (EI, 70 ev) m/z: 420 (4%, [M-H] + ), 300 (15, [M-BH 3 -PhCHOH] + ), 243 (22, [(2-iPrO-Ph)PhP] + ), 58 (100, [C 3 H 6 O] + ); HRMS (ESI) [M+H] + : m/z calcd. for C 25 H 34 BNO 2 P , found ; [M+Na] + : m/z calcd. for C 25 H 33 BNNaO 2 P , found ; [M-BH 3 +H] + : m/z calcd. for C 25 H 31 NO 2 P found ; [M-BH 3 +Na] + : m/z calcd. for C 25 H 30 NNaO 2 P found ; (1R,2S)-2-{[(S)-(3-Isopropoxyphenyl)(phenyl)phosphinyl](methyl)amino}-1-phenylpropan-1-ol P- borane complex (3m) Yield 88%; white solid, m.p. = C (column chromatography cyclohexane/acoet 19/1); 23 = (c 1.0, CHCl 3 ); 1 H-NMR: (9H, m, arom. H), (4H, m, arom. H), 6.98 (1H, m, arom. H), 4.81 (1H, d, J 6.1 Hz, CH-O), 4.50 (1H, sept, J 6.0 Hz, CH-O), 4.30 (1H, m, CH-N), 2.48 (3H, d, J 7.7 Hz, CH 3 -N), 1.93 (1H, br s, OH), 1.31 (3H, d, J 6.0 Hz, CH 3 ), 1.31 (3H, d, J 6.0 Hz, CH 3 ), 1.25 (3H, d, J 6.8 Hz, CH 3 ), (3H, br q, BH 3 ); 13 C-NMR: (d, J 12.5 Hz, C-O), (C-C), (d, J 59.0 Hz, C-P), (d, J 10.2 Hz, 2xCH), (d, J 2.5 Hz, CH), (d, J 68.5 Hz, C-P), (d, J 11.6 Hz, CH), (2xCH), (d, J 10.6 Hz, 2xCH), (CH), (2xCH), (d, J 9.8 Hz, CH), (d, J 12.1 Hz,

13 CH), (d, J 1.8 Hz, CH), 78.6 (d, J 5.8 Hz, CH-O), 70.0 (C-O), 58.1 (d, J 10.5 Hz, CH-N), 30.4 (d, J 4.1 Hz, CH 3 N), 21.9 (CH 3 ), 21.8 (CH 3 ), 13.4 (d, J 2.0 Hz, CH 3 ); 31 P-NMR: +71.5; MS (EI, 70 ev) m/z: 420 (8, [M-H] + ), 406 (3, [M-H-BH 3 ] + ), 300 (5, [M-BH 3 -PhCHOH] + ), 243 (23, [(2-iPrO-Ph)PhP] + ), 58 (100, [C 3 H 6 O] + ); HRMS (ESI) [M+Na] + : m/z calcd. for C 25 H 33 BNNaO 2 P , found ; [M-BH 3 +Na] + : m/z calcd. for C 25 H 30 NNaO 2 P found ; (1R,2S)-2-{[(S)-(2-Isopropylphenyl)(phenyl)phosphinyl](methyl)amino}-1-phenylpropan-1-ol P- Borane complex (3n) Yield 72%; white solid, m.p. = C (column chromatography cyclohexane/acoet 9/1); 22 = (c 1.0, CHCl 3 ); 1 H-NMR: (2H, m, arom. H), (7H, m, arom. H), (5H, m, arom. H), 5.00 (1H, m, CH-O), 4.37 (1H, m, CH-N),.3.28 (1H, m, CH), 2.64 (3H, d, J 7.2 Hz, CH 3 -N), 1.81 (1H, br s, OH), 1.24 (3H, d, J 6.9 Hz, CH 3 ), 1.17 (3H, d, J 6.7 Hz, CH 3 ), 1.06 (3H, d, J 6.7 Hz, CH 3 ), (3H, br q, BH 3 ); 13 C-NMR: (d, J 12.6 Hz, C-C), (C-C), (d, J 70.0 Hz, C-P), (d, J 8.4 Hz, CH), (d, J 10.4 Hz, 2xCH), (d, J 2.0 Hz, CH), (d, J 2.1 Hz, CH), (d, J 10.9 Hz, 2xCH), (2xCH), (d, J 9.1 Hz, CH), (d, J 63.8 Hz, C-P), (CH), (2xCH), (d, J 8.9 Hz, CH), 79.2 (d, J 2.1 Hz, CH-O), 58.0 (d, J 10.9 Hz, CH-N), 31.7 (d, J 3.8 Hz, CH), 30.8 (d, J 5.5 Hz, CH 3 N), 24.9 (CH 3 ), 23.8 (CH 3 ), 11.4 (d, J 4.7 Hz, CH 3 ); 31 P-NMR: +70.8; MS (EI, 70 ev) m/z: 404 (4, [M-H] + ), 391 (1, [M-BH 3 ] + ), 284 (100, [M-BH 3 -PhCHOH] + ), 227 (100, [(2-iPr-Ph)PhP] + ), 109 (100, [C 6 H 6 P] + ); HRMS (ESI) [M+H] + : m/z calcd. for C 25 H 34 BNOP , found ; [M+Na] + : m/z calcd. for C 25 H 33 BNNaOP , found ; [M-BH 3 +H] + : m/z calcd. for C 25 H 31 NOP found ; [M-BH 3 +Na] + : m/z calcd. for C 25 H 30 NNaOP found ; (1R,2S)-2-{[(S)-(3-Isopropylphenyl)(phenyl)phosphinyl](methyl)amino}-1-phenylpropan-1-ol P- borane complex (3o) Yield 88%; pale syrup (column chromatography cyclohexane/acoet 19/1 to 4/1); 23 = (c 1.0, CHCl 3 );

14 1 H-NMR: (3H, m, arom. H), (9H, m, arom. H), (2H, m, arom. H), 4.82 (1H, d, J 6.4 Hz, CH-O), 4.31 (1H, m, CH-N), 2.91 (1H, sept, J 6.9 Hz, CHMe 2 ), 2.46 (3H, d, J 7.8 Hz, CH 3 -N), 1.87 (1H, br s, OH), 1.25 (3H, d, J 6.6 Hz, CH 3 ), 1.23 (6H, d, J 7.0 Hz, 2xCH 3 ), (3H, br q, BH 3 ); 13 C-NMR: (d, J 9.7 Hz, C-iPr), (C-C), (d, J 10.4 Hz, 2xCH), (d, J 68.1 Hz, C-P), (d, J 58.0 Hz, C-P), (d, J 2.5 Hz, CH), (d, J 10.8 Hz, CH), (d, J 9.9 Hz, CH), (d, J 2.6 Hz, CH), (2xCH), (d, J 10.2 Hz, CH), (d, J 10.4 Hz, 2xCH), (CH), (2xCH), 78.6 (d, J 5.7 Hz, CH-O), 58.1 (d, J 10.4 Hz, CH-N), 34.0 (CHMe 2 ), 30.4 (d, J 3.9 Hz, CH 3 N), 23.9 (CH 3 ), 23.8 (CH 3 ), 13.4 (d, J 1.9 Hz, CH 3 ); 31 P-NMR: +71.4; MS (EI, 70 ev) m/z: 404 (1, [M-H] + ), 390 (1, [M-H-BH 3 ] + ), 298 (59), 284 (100, [M-BH 3 - PhCHOH] + ), 227 (23, [(3-iPr-Ph)PhP] + ); HRMS (ESI) [M+Na] + : m/z calcd. for C 25 H 33 BNNaOP , found ; [M-BH 3 +H] + : m/z calcd. for C 25 H 31 NOP found ; [M-BH 3 +Na] + : m/z calcd. for C 25 H 30 NNaOP found ; (1R,2S)-2-{[(S)-(3,5-imethoxyphenyl)(phenyl)phosphinyl](methyl)amino}-1-phenylpropan-1-ol P- Borane-Komplex (3p) Yield 87%; white solid, m.p. = C (column chromatography cyclohexane/acoet 9/1 to 4/1); 23 [ ] 25 = (c 1.0, CHCl 3 ); (other enantiomer ] = (c 1.0, CHCl 3 ) 7 ) [ 1 H-NMR: (8H, m, arom. H), 7.15 (2H, m, arom. H), 6.70 (2H, dd, J 11.5, 2.3 Hz, arom. H), 6.53 (1H, d, J 2.3 Hz, arom. H), 4.81 (1H, d, J 6.3 Hz, CH-O), 4.29 (1H, m, CH-N), 3.75 (6H, s, 2xOCH 3 ), 2.49 (3H, d, J 7.7 Hz, CH 3 -N), 1.93 (1H, br s, OH), 1.27 (3H, d, J 6.7 Hz, CH 3 ), (3H, br q, BH 3 ); 13 C-NMR: (d, J 14.5 Hz, 2xC-O), (C-C), (d, J 59.4 Hz, C-P), (d, J 10.3 Hz, 2xCH), (d, J 2.3 Hz, CH), (d, J 68.4 Hz, C-P), (2xCH), (d, J 10.4 Hz, 2xCH), (CH), (2xCH), (d, J 11.5 Hz, 2xCH) (d, J 1.3 Hz, CH), 78.5 (d, J 5.8 Hz, CH-O), 58.0 (d, J 10.5 Hz, CH-N), 55.4 (2xOCH 3 ), 30.5 (d, J 4.0 Hz, CH 3 N), 13.5 (d, J 1.9 Hz, CH 3 ); 31 P-NMR: +72.4; MS (EI, 70 ev) m/z: 422 (4%, [M-H] + ), 316 (47, [M-PhCHOH] + ), 302 (100, [M-BH 3 -PhCHOH] + ), 245 (89, [(3,5-MeO-Ph)PhP] + ); HRMS (ESI) [M+Na] + : m/z calcd. for C 24 H 31 BNNaO 3 P , found ; [M-BH 3 +Na] + : m/z calcd. for C 24 H 28 NNaO 3 P found ; [M-BH 3 +H] + : m/z calcd. for C 24 H 29 NO 3 P found ;

15 (1R,2S)-2-{Methyl[(S)-naphthalen-1-yl(phenyl)phosphinyl]amino}-1-phenylpropan-1-ol P-borane complex (3q) Yield 87%; white solid, m.p. = C (column chromatography heptane/acoet 9/1 to 4/1); 20 = (c 1.0, CHCl 3 ); ( ] = (c 0.68, CH 2 Cl 2 ) 6 ) 22 [ 1 H-NMR: 8.24 (1H, d, J 8.7 Hz, arom. H), 7.96 (1H, d, J 8.3 Hz, arom. H), 7.87 (1H, d, J 8.1 Hz, arom. H), (14H, m, arom. H), 5.01 (1H, d, J 4.0 Hz, CH-O), 4.49 (1H, m, CH-N), 2.63 (3H, d, J 7.5 Hz, CH 3 -N), 1.82 (1H, br s, OH), 1.30 (3H, d, J 6.9 Hz, CH 3 ), (3H, br q, BH 3 ); 13 C-NMR: (C-C), (d, J 7.7 Hz, C-C), (d, J 11.3 Hz, C-C), (d, J 7.4 Hz, CH), (d, J 2.6 Hz, CH), (d, J 62.3 Hz, C-P), (d, J 10.3 Hz, 2xCH), (d, J 2.2 Hz, CH), (CH), (d, J 10.5 Hz, 2xCH), (2xCH), (CH), (d, J 5.6 Hz, CH), (d, J 61.1 Hz, C-P), (CH),126.2 (CH), (2xCH), (d, J 10.3 Hz, CH), 79.1 (d, J 2.3 Hz, CH-O), 58.1 (d, J 10.3 Hz, CH-N), 31.5 (d, J 3.4 Hz, CH 3 N), 11.6 (d, J 4.2 Hz, CH 3 ); 31 P-NMR: +71.4; MS (EI, 70 ev) m/z: 306 (7, [M-PhCHOH] + ), 292 (97, [M-PhCHOH-BH 3 ] + ), 235 (100, [PPh(1- naphthyl)] + ; HRMS (ESI) [M+Na] + : m/z calcd. for C 26 H 29 BNNaOP , found ; [M+H] + : m/z calcd. for C 26 H 26 NNaOP , found , [M-BH 3 +Na] + : m/z calcd. for C 26 H 26 NNaOP , found ; [M-BH 3 +H] + : m/z calcd. for C 26 H 27 NOP , found ; (1R,2S)-2-{Methyl[(S)-naphthalen-2-yl(phenyl)phosphinyl]amino}-1-phenylpropan-1-ol P-borane complex (3r) In this case solid 2-bromonaphthalene was placed in a Schlenk-tube and sec-butyllithium solution was added at 0 C. Yield 85%; white solid, m.p. = C (from i-proh/hexane); 20 = (c 1.1, CH 2 Cl 2 ); ( ] = (c 0.524, CH 2 Cl 2 ) 6 ) 22 [ 1 H-NMR: 8.14 (1H, d, J 12.3 Hz, arom. H), (3H, m, arom. H), (13H, m, arom. H), 4.86 (1H, d, J 6.4 Hz, CH-O), 4.40 (1H, m, CH-N), 2.56 (3H, d, J 7.7 Hz, CH 3 -N), 1.98 (1H, br s, OH), 1.32 (3H, d, J 6.7 Hz, CH 3 ), (3H, br q, BH 3 ); 13 C-NMR: (C-C), (d, J 1.4 Hz, C-C), (d, J 10.6 Hz, CH), (d, J 11.1 Hz, C- C), (d, J 10.6 Hz, 2xCH), (d, J 2.2 Hz, CH), (d, J 68.3 Hz, C-P), (CH), (2xCH), (d, J 10.5 Hz, 2xCH), (d, J 55.2 Hz, C-P), (d, J 9.8 Hz, CH),

16 (CH), (CH), (CH), (CH), (2xCH), (CH), 78.6 (d, J 5.8 Hz, CH-O), 58.1 (d, J 10.1 Hz, CH-N), 30.4 (d, J 4.4 Hz, CH 3 N), 13.5 (d, J 2.0 Hz, CH 3 ); 31 P-NMR: +71.2; MS (EI, 70 ev) m/z: 306 (28, [M-PhCHOH] + ), 292 (99, [M-PhCHOH -BH 3 ] + ), 235 (100, [PPh(2- naphthyl)] + ; HRMS (ESI) [M+Na] + : m/z calcd. for C 26 H 29 BNNaOP , found , [M-BH 3 +H] + : m/z calcd. for C 26 H 26 NNaOP , found , [M-BH 3 +Na] + : m/z calcd. for C 26 H 26 NNaOP , found ; (1R,2S)-2-{Methyl[(S)-phenanthren-9-yl(phenyl)phosphinyl]amino}-1-phenylpropan-1-ol P-borane complex (3s) For the preparation of the lithiated 9-phenantryl derivative the aromatic bromide (20 mmol) was solved in hexane (15 ml) and treated with sec-buli (1.4 M, 14.2 ml) at 0 C. After dilution with THF the resulted slightly cloudy solution was used for the next step. Yield 79%; white solid, m.p. = C (column chromatography cyclohexane/acoet 19/1 to 4:1); 24 [ ] 20 = (c 1, CHCl 3 ); (other enantiomer ] = (c 0.243, CH 2 Cl 2 ) 6 ) [ 1 H-NMR: 8.72 (1H, br d, J 8.6 Hz, arom. H), 8.67 (1H, br d, J 8.3 Hz, arom. H), 8.34 (1H, br d, J 8.3 Hz, arom. H), (16H, m, arom. H), 5.06 (1H, d, J 4.0 Hz, CH-O), 4.53 (1H, m, CH-N), 2.69 (3H, d, J 7.4 Hz, CH 3 -N), 1.82 (1H, br s, OH), 1.35 (3H, d, J 6.9 Hz, CH 3 ), (3H, br q, BH 3 ); 13 C-NMR: (C-C), (d, J 7.2 Hz, CH), (d, J 10.0 Hz, 2xC-H), (d, J 61.3 Hz, C-P), (d, J 1.8 Hz, C-C), (d, J 2.8 Hz, CH), (d, J 11.2 Hz, C-C), (d, J 7.2 Hz, C-C), (d, J 11.0 Hz, C-C), (CH), (CH), (d, J 10.1 Hz, 2xCH), (2xCH), (d, J 5.6 Hz, CH), (CH), (2xCH), (CH), (2xCH), (d, J 60.9 Hz, C-P), (CH), (CH), 79.2 (d, J 2.6 Hz, CH-O), 58.1 (d, J 10.3 Hz, CH-N), 31.5 (d, J 3.4 Hz, CH 3 N), 11.5 (d, J 4.2 Hz, CH 3 ); 31 P-NMR: +72.2; MS (EI, 70 ev) m/z: 342 (81, [M-BH 3 -PhCHOH] + ), 285 (100, PPh(9-phenanthryl) + ); HRMS (ESI) [M-BH 3 +H]: m/z calcd. for C 30 H 29 NOP , found ; [M+H] + : m/z calcd. for C 30 H 32 BNOP , found ; [M-BH 3 +Na]: m/z calcd. for C 30 H 28 NaNOP , found ;

17 (1R,2S)-2-{[(S)-(ibenzo[b,d]furan-4-yl)(phenyl)phosphinyl](methyl)amino}-1-phenylpropan-1-ol P-borane complex (3t) For the lithiation reaction dibenzofuran in THF was treated with 1.1 eq. of n-butyllithium solution at -30 C. After stirring at ambient temperature for further 20 hours the solution was used for further reaction. Yield 82%; white solid, m.p. = C (column chromatography cyclohexane/acoet 9/1); 22 = (c 1.0, CHCl 3 ); 1 H-NMR: 8.10 (1H, m, arom. H), 7.95 (1H, m, arom. H), 7.78 (1H, ddd, J 12.0, 7.6, 1.3 Hz, arom. H), 7.48 (2H, m, arom. H), (12H, m, arom. H), 4.88 (1H, d, J 5.9 Hz, CH-O), 4.44 (1H, m, CH-N), 2.62 (3H, d, J 8.1 Hz, CH 3 -N), 1.82 (1H, br s, OH), 1.28 (3H, d, J 6.6 Hz, CH 3 ), (3H, br q, BH 3 ); 13 C-NMR: (C-O), (C-O), (C-C), (d, J 11.5 Hz, CH), (d, J 10.5 Hz, 2xCH), (d, J 72.1 Hz, C-P), (d, J 2.6 Hz, CH), (2xCH), (d, J 11.2 Hz, 2xCH), (CH), (CH), (2xCH), (d, J 5.0 Hz, C-C), (d, J 1.9 Hz, CH), (C-C), (CH), (d, J 10.1 Hz, CH), (CH), (d, J 54.6 Hz, C-P), (CH), 78.8 (d, J 6.1 Hz, CH-O), 58.3 (d, J 11.1 Hz, CH-N), 31.0 (d, J 4.4 Hz, CH 3 N), 13.0 (d, J 1.9 Hz, CH 3 ); 31 P-NMR: +67.7; MS (EI, 70 ev) m/z: 452 (1%, [M-H] + ), 346 (2, [M-PhCHOH] + ), 332 (28, [M-BH 3 -PhCHOH] + ), 291 (100), 275 (34, [(4-BF)PhP] + ), 168 (55, [BF] + ); HRMS (ESI) [M+H] + : m/z calcd. for C 28 H 30 BNO 2 P , found ; [M+Na] + : m/z calcd. forc 28 H 29 BNNaO 2 P , found ; [M-BH 3 +H] + : m/z calcd. forc 28 H 27 NO 2 P found ; [M-BH 3 +Na] + : m/z calcd. for C 25 H 26 NNaO 2 P found ;

18 4. Synthesis of (R)-(aryl)(methoxy)(phenyl)phosphine P-borane complexes 4a-t General Procedure for the Preparation To a stirred solution of 10 mmol of the corresponding phosphinamide P-borane complex 3a-t in methanol (80 ml) was slowly added one equivalent of conc. H 2 SO 4 (0.98 g) at 0 C. After 1 hour the stirring was continued at ambient temperature for further 20 hours. Water (10 ml) was added and the volatile methanol was removed under vacuum. The residue was extracted with CM (2x 25 ml) and the combined organic phases were washed with water and dried (Na 2 SO 4 ). After evaporation the residue was purified by column chromatography. (R)-(-)-Methoxy(2-methoxyphenyl)(phenyl)phosphine P-borane complex (4a) Yield 87%; colourless oil (column chromatography cyclohexane/acoet 9/1); = (c 0.5, CH 2 Cl 2 ), ( [ ] = (c 1.07, CHCl 3 8 ; for (S)-(+)-enantiomer = (c 0.565, CH 2 Cl 2 ) 6 ); 1 H-NMR: 7.80 (1H, ddd, J 1.7, 7.6, 12.2 Hz, arom. H), (2H, m, arom. H), (4H, m, arom. H), 7.06 (1H, ddt, J 1.0, 2.1, 7.6 Hz, arom. H), 6.86 (1H, ddd, J 0.6, 4.3, 8.3 Hz, arom. H), 3.73 (3H, d, J 12.2 Hz, OCH 3 ), 3.62 (3H, s, OCH 3 ), (3H, br q, BH 3 ); 13 C-NMR: (d, J 3.5 Hz, C-O), (d, J 2.1 Hz, CH), (d, J 11.2 Hz, CH), (d, J 66.1 Hz, C-P), (d, J 2.1 Hz, CH), (d, J 11.2 Hz, 2xCH), (d, J 11.1 Hz, 2xCH), (d, J 11.2 Hz, CH), (d, J 62.9 Hz, C-P), (d, J 4.9 Hz, CH), 55.4 (OCH 3 ), 53.9 (d, J 2.4 Hz, OCH 3 ); 31 P-NMR: ; MS (EI, 70 ev) m/z: 246 (100, [M-BH 3 ] + ), 231 (8, [M-BH 3 -CH 3 ] + ), 215 (8, [M-BH 3 -OCH 3 ] + ); HRMS (ESI) [M+Na] + : m/z calcd. for C 14 H 18 BNaO 2 P , found ; [M-BH 3 +Na] + : m/z calcd. for C 14 H 15 NaO 2 P , found ; HPLC: optical purity >99%ee; column: Chiralcel OJ-H (150x4.6 mm), hexane/i-proh 92/8, 1.00 ml/min, t R = 11.0 min (S)-enantiomer and 16.9 min (R)-enantiomer; (R)-(-)-Methoxy(3-methoxyphenyl)(phenyl)phosphine P-borane complex (4b) Yield 76%; colourless oil (column chromatography cyclohexane/acoet 19/1); 23 [ ] = -3.2 (c 1.00, CHCl 3 ), (for (S)-(+)-enantiomer 25 = -0.4 (c 1.20, CHCl 3 ) 7 ); 1 H-NMR: 7.74 (2H, m, arom. H), (6H, m, arom. H), 7.04 (1H, m, arom. H), 3.80 (3H, s, OCH 3 ), 3.74 (3H, d, J 12.1 Hz, OCH 3 ), (3H, br q, BH 3 ); 13 C-NMR: (d, J 13.1 Hz, C-O), (d, J 63.2 Hz, C-P), (d, J 2.7 Hz, CH), (d, J 63.2 Hz, C-P), (d, J 11.3 Hz, 2xCH), (d, J 12.1 Hz, CH), (d, J 10.3 Hz, 2xCH),

19 123.3 (d, J 10.9 Hz, CH), (d, J 2.1 Hz, CH), (d, J 12.8 Hz, CH), 55.3 (OCH 3 ), 54.0 (d, J 2.5 Hz, OCH 3 ); 31 P-NMR: ; MS (EI, 70 ev) m/z: 246 (100, [M-BH 3 ] + ), 231 (93, [M-BH 3 -CH 3 ] + ), 215 (30, [M-BH 3 -OCH 3 ] + ); HRMS (ESI) [M+Na] + : m/z calcd. for C 14 H 18 BNaO 2 P , found ; M-BH 3 +H] + : m/z calcd. for C 14 H 16 O 2 P , found ; [M-BH 3 +Na] + : m/z calcd. for C 14 H 15 NaO 2 P , found ; HPLC: optical purity >98%ee; column: Chiralpak AS-H (150x4.6 mm), hexane/i-proh 99.75/0.25, 1.20 ml/min, t R = 7.7 min (S)-enantiomer and 11.1 min (R)-enantiomer; (R)-(+)-Methoxy(4-methoxyphenyl)(phenyl)phosphine P-borane complex (4c) Yield 81%; colourless oil (column chromatography cyclohexane/acoet 19/1); 25 [ ] = (c 1.07, CHCl 3 ), (for (S)-(-)-enantiomer 25 = (c 1.1, CHCl 3 ) 7 ); 1 H-NMR: (4H, m, arom. H), (3H, m, arom. H), 6.96 (2H, m, arom. H), 3.82 (3H, s, OCH 3 ), 3.70 (3H, d, J 12.3 Hz, OCH 3 ), (3H, br q, BH 3 ); 13 C-NMR: (d, J 2.7 Hz, C-O), (d, J 11.9 Hz, 2xCH), (d, J 65.8 Hz, C-P), (d, J.2.7 Hz, CH), (d, J 11.0 Hz, 2xCH), (d, J 10.1 Hz, 2xCH), (d, J 67.6 Hz, C- P), (d, J 11.9 Hz, 2xCH), 55.3 (OCH 3 ), 53.8 (d, J 1.8 Hz, OCH 3 ); 31 P-NMR: ; MS (EI, 70 ev) m/z: 246 (100, [M-BH 3 ] + ), 231 (95, [M-BH 3 -CH 3 ] + ), 215 (74, [M-BH 3 -OCH 3 ] + ), 138 (56, [4-MeO-PhP] + ); HRMS (ESI) [M+Na] + : m/z calcd. for C 14 H 18 BNaO 2 P , found ; HPLC: optical purity >98%ee; Chiralpak AS-H (150x0.46 mm), hexane/i-proh 99.5/0.5, 1.00 ml/min, t R = 8.8 min (S)-enantiomer and 10.5 min (R)-enantiomer; (R)-(+)-Methoxy(2-methylphenyl)(phenyl)phosphine P-borane complex (4d) Yield 76%, colourless oil (column chromatography cyclohexane/acoet 19/1); 24 = +3.8 (c 1.0, CH 2 Cl 2 ); 1 H-NMR: 7.79 (1H, ddd, J 1.4, 7.7, 12.8 Hz, arom. H), (2H, m, arom. H), (4H, m, arom. H), 7.31 (1H, m, arom. H), 7.20 (1H, m, arom. H), 3.74 (3H, d, J 12.0 Hz, OCH 3 ), 2.24 (3H, s, CH 3 ), (3H, br q, BH 3 ); 13 C-NMR: (d, J 7.7 Hz, C-C), (d, J 14.8 Hz, CH), (d, J 2.6 Hz, CH), (d, J 64.0 Hz, C-P), (d, J 2.3 Hz, CH), (d, J 8.8 Hz, CH), (d, J 11.6 Hz, 2xCH), (d, J 58.6 Hz, C-P), (d, J 10.3 Hz, 2xCH), (d, J 11.6 Hz, CH), 53.7 (d, J 2.6 Hz, OCH 3 ), 21.2 (d, J 3.9 Hz, CH 3 );

20 31 P-NMR: ; MS (EI, 70 ev) m/z: 230 (100, [M-BH 3 ] + ), 215 (85, [M-BH 3 -CH 3 ] + ), 199 (51, [M-BH 3 -OCH 3 ] + ); HRMS (ESI) [M+Na] + : m/z calcd. for C 14 H 18 BNaOP , found ; [M-BH 3 +Na] + : m/z calcd. for C 14 H 15 NaOP , found ; [M-BH 3 +H] + : m/z calcd. for C 14 H 15 NaOP , found ; HPLC: optical purity >99%ee; column: Chiralcel OJ-H (150x4.6 mm), hexane/ i-proh 95/5, 1.00 ml/min, t R = 7.8 min (S)-enantiomer and 11.8 min (R)-enantiomer; (R)-(-)-Methoxy(3-methylphenyl)(phenyl)phosphine P-borane complex (4e) Yield 80%; colourless oil (column chromatography cyclohexane/acoet 19/1); 23 = -1.5 (c 1.00, CHCl 3 ); 1 H-NMR: (2H, m, arom. H), (5H, m, arom. H), (2H, m, arom. H), 3.74 (3H, d, J 12.1 Hz, OCH 3 ), 2.37 (3H, s, CH 3 ), (3H, br q, BH 3 ); 13 C-NMR: (d, J Hz, C-C), (d, J 2.4 Hz, CH), (d, J 2.5 Hz, CH), (d, J 64.0 Hz, C-P), (d, J 11.8 Hz, CH), (d, J 63.8 Hz, C-P), (d, J 11.0 Hz, 2xCH), (d, J 10.6 Hz, 2xCH), (d, J 10.8 Hz, CH), (d, J 10.9 Hz, CH), 54.0 (d, J 2.5 Hz, OCH 3 ), 21.4 (CH 3 ); 31 P-NMR: ; MS (EI, 70 ev) m/z: 243 (3, [M-H] + ), 230 (100, [M-BH 3 ] + ), 215 (91, [M-BH 3 -CH 3 ] + ), 199 (20, [(3- Me-Ph)PhP] + ); HRMS (ESI) [M+Na] + : m/z calcd. for C 14 H 18 BNaOP , found ; [M-BH 3 +H] + : m/z calcd. for C 14 H 16 OP , found ; [M-BH 3 +Na] + : m/z calcd. for C 14 H 15 NaOP , found ; HPLC: optical purity >98%ee; column: Chiralcel OJ-H (150x4.6 mm), hexane/ i-proh 99/1, 1.10 ml/min, t R = 15.6 min (R)-enantiomer and 18.0 min (S)-enantiomer; (R)-(+)-Methoxy(4-methylphenyl)(phenyl)phosphine P-borane complex (4f) Yield 86%; colourless oil (column chromatography cyclohexane/acoet 9/1); 24 = (c 1.0, CHCl 3 ); 1 H-NMR: (2H, m, arom. H), 7.62 (2H, m, arom. H), (3H, m, arom. H), 7.26 (2H, m, arom. H), 3.71 (3H, d, J 12.1 Hz, OCH 3 ), 2.38 (3H, s, CH 3 ), (3H, br q, BH 3 ); 13 C-NMR: (d, J 2.6 Hz, C-C), (d, J 64.4 Hz, C-P), (d, J.2.6 Hz, CH), (d, J 11.6 Hz, 2xCH), (d, J 10.9 Hz, 2xCH), (d, J 10.9 Hz, 2xCH), (d, J 10.3 Hz, 2xCH), (d, J 67.0 Hz, C-P), 53.9 (d, J 2.6 Hz, OCH 3 ), 21.5 (CH 3 ); 31 P-NMR: ;

21 MS (EI, 70 ev) m/z: 244 (7, [M] + ), 230 (100, M-BH 3 ] + ), 215 (88, [M-BH 3 -CH 3 ] + ), 199 (12, Ph(4- Me-Ph)P + ); HRMS (ESI) [M+Na] + : m/z calcd. for C 14 H 18 BNaOP , found ; [M-BH 3 +Na] + : m/z calcd. for C 14 H 15 NaOP , found ; [M-BH 3 +H] + : m/z calcd. for C 14 H 16 OP , found ; HPLC: optical purity 97%ee; Chiralcel OJ-H (150x4.6 mm), hexane/etoh 85/15, 1.00 ml/min, t R = 9.2 min (S)-enantiomer and 15.9 min (R)-enantiomer; (R)-(-)-(2-Ethoxy-phenyl)(methoxy)(phenyl)phosphine P-borane complex (4g) Yield 76%; white solid, m.p. = C (column chromatography cyclohexane/acoet 19/1 to 9/1); 23 = (c 1.0, CHCl 3 ); 1 H-NMR: 7.80 (1H, ddd, J 1.7, 7.6, 12.1 Hz, arom. H), (2H, m, arom. H), (4H, m, arom. H), 7.04 (1H, ddt, J 1.0, 2.1, 7.6 Hz, arom. H), 6.81 (1H, ddd, J 0.6, 4.5, 8.3 Hz, arom. H), 3.87 (2H, m, OCH 2 ), 3.73 (3H, d, J 12.1 Hz, OCH 3 ), 1.10 (3H, t, J 7.1 Hz, CH 3 ), (3H, br q, BH 3 ); 13 C-NMR: (d, J 3.8 Hz, C-O), (d, J 1.9 Hz, CH), (d, J 10.4 Hz, CH), (d, J 65.1 Hz, C-P), (d, J 2.7 Hz, CH), (d, J 11.4 Hz, 2xCH), (d, J 11.0 Hz, 2xCH), (d, J 10.6 Hz, CH), (d, J 64.1 Hz, C-P), (d, J 5.2 Hz, CH), 63.9 (OCH 2 ), 53.8 (d, J 2.7 Hz, OCH 3 ), 14.0 (CH 3 ); 31 P-NMR: ; MS (EI, 70 ev) m/z: 273 (4, [M-H] + ), 260 (100, [M-BH 3 ] + ), 245 (43, [M-BH 3 -CH 3 ] + ), 229 (20, [M- BH 3 -OCH 3 ] + ); HRMS (ESI) [M+Na] + : m/z calcd. for C 15 H 20 BNaO 2 P , found ; [M-BH 3 +Na] + : m/z calcd. for C 15 H 17 NaO 2 P , found ; HPLC: optical purity >98%ee; column: Chiralcel O-H (150x4.6 mm), hexane/ i-proh 99.75/0.25, 1.25 ml/min, t R = 8.7 min (R)-enantiomer and 10.4 min (S)-enantiomer; (R)-(-)-(3-Ethoxy-phenyl)(methoxy)(phenyl)phosphine P-borane complex (4h) Yield 83%; colourless oil (column chromatography cyclohexane/acoet 9/1); 24 = -1.7 (c 1.00, CHCl 3 ); 1 H-NMR: 7.75 (2H, m, arom. H), (6H, m, arom. H), 7.02 (1H, m, arom. H), 4.03 (2H, q, J 7.0 Hz, CH 2 ), 3.74 (3H, d, J 12.1 Hz, OCH 3 ), 1.41 (3H, t, J 7.0 Hz, CH 3 ), (3H, br q, BH 3 ); 13 C-NMR: (d, J 13.3 Hz, C-O), (d, J 63.1 Hz, C-P), (d, J 2.5 Hz, CH), (d, J 64.3 Hz, C-P), (d, J 11.6 Hz, 2xCH), (d, J 12.5 Hz, CH), (d, J 10.2 Hz 2xCH),

22 123.1 (d, J 10.9 Hz, CH), (d, J 1.9 Hz, CH), (d, J 12.8 Hz, CH), 63.5(OCH 2 ), 54.0 (d, J 2.0 Hz, OCH 3 ), 14.6 (CH 3 ); 31 P-NMR: ; MS (EI, 70 ev) m/z: 273 (1, [M-H] + ), 260 (100, [M-BH 3 ] + ), 245 (94, [M-BH 3 -CH 3 ] + ), 229 (15, [M- BH 3 -OCH 3 ] + ); HRMS (ESI) [M+Na] + : m/z calcd. for C 15 H 20 BNaO 2 P , found ; [M-BH 3 +Na] + : m/z calcd. for C 15 H 17 NaO 2 P , found ; HPLC: optical purity >98%ee; column: Chiralpak AS-H (150x4.6 mm), hexane/i-proh 99.75/0.25, 1.00 ml/min, t R = 6.7 min (S)-enantiomer and 7.4 min (R)-enantiomer; (R)-(-)-(4-Ethoxy-phenyl)(methoxy)(phenyl)phosphine P-borane complex (4i) Yield 79%; colourless oil (column chromatography cyclohexane/acoet 49/1); 23 = (c 1.00, CHCl 3 ); 1 H-NMR: (4H, m, arom. H), (3H, m, arom. H), 6.95 (2H, m, arom. H), 4.04 (2H, q, J 7.0 Hz, CH 2 ), 3.70 (3H, d, J 12.1 Hz, OCH 3 ), 1.41 (3H, t, J 7.0 Hz, CH 3 ), (3H, br q, BH 3 ); 13 C-NMR: (d, J 2.4 Hz, C-O), (d, J 12.6, 2xCH), (d, J 65.6 Hz, C-P), (d, J 2.4 Hz, CH), (d, J 11.3 Hz, 2xCH), (d, J 10.7 Hz 2xCH), (d, J 67.8 Hz, C-P), (d, J 11.4 Hz, 2xCH), 63.5(OCH 2 ), 53.7 (d, J 2.6 Hz, OCH 3 ), 14.5 (CH 3 ); 31 P-NMR: ; MS (EI, 70 ev) m/z: 260 (100, [M-BH 3 ] + ), 245 (96, [M-BH 3 -CH 3 ] + ), 229 (37, [M-BH 3 -OCH 3 ] + ); HRMS (ESI) [M+Na] + : m/z calcd. for C 15 H 20 BNaO 2 P , found ; [M-BH 3 +Na] + : m/z calcd. for C 15 H 17 NaO 2 P , found ; HPLC: optical purity >99%ee; column: Reprosil 100 (150x4.6 mm), hexane/i-proh 99.75/0.25, 1.25 ml/min, t R = 8.4 min (R)-enantiomer and 8.9 min (S)-enantiomer; (R)-(-)-(2-Ethylphenyl)(methoxy)(phenyl)phosphine P-borane complex (4j) Yield 52%; colourless oil (column chromatography cyclohexane/acoet 19/1); 23 = -5.1 (c 1.00, CHCl 3 ); 1 H-NMR: 7.87 (1H, m, arom. H), (2H, m, arom. H), (4H, m, arom. H), (2H, m, arom. H), 3.75 (3H, d, J 12.2 Hz, OCH 3 ), 2.65 (2H, m, CH 2 ), 0.95 (3H, t, J 7.5 Hz, CH 3 ), (3H, br q, BH 3 ); 13 C-NMR: (d, J 8.6 Hz, C-C), (d, J 1.9 Hz, CH), (d, J 14.6 Hz, CH), (d, J 64.1 Hz, C-P), (d, J 2.6 Hz, CH), (d, J 2.6 Hz, CH), (d, J 11.4 Hz, 2xCH),

23 (d, J 8.4 Hz, CH), (d, J 60.3 Hz, C-P), (d, J 10.5 Hz, 2xCH), (d, J 11.4 Hz, CH), 53.8 (d, J 2.3 Hz, OCH 3 ), 26.8 (CH 2 ), 15.1 (CH 3 ); 31 P-NMR: ; MS (EI, 70 ev) m/z: 244 (100, [M-BH 3 ] + ), 229 (43, [M-BH 3 -CH 3 ] + ), 213 (40, [M-BH 3 -OCH 3 ] + ); HRMS (ESI) [M+Na] + : m/z calcd. for C 15 H 20 BNaOP , found ; [M-BH 3 +H] + : m/z calcd. for C 15 H 18 OP , found ; [M-BH 3 +Na] + : m/z calcd. for C 15 H 17 NaOP , found ; HPLC: optical purity >99%ee; column: Chiralcel OJ-H (150x4.6 mm), hexane/i-proh 99/1, 1.00 ml/min, t R = 8.2 min (R)-enantiomer and 10.5 min (S)-enantiomer; (R)-(-)-(3-Ethylphenyl)(methoxy)(phenyl)phosphine P-borane complex (4k) Yield 84%; colourless oil (column chromatography cyclohexane/acoet 19/1); 23 = -0.4 (c 1.00, CHCl 3 ); 1 H-NMR: 7.74 (2H, m, arom. H), 7.58 (1H, m, arom. H), (4H, m, arom. H), (2H, m, arom. H), 3.74 (3H, d, J 12.0 Hz, OCH 3 ), 2.68 (2H, q, J 7.6 Hz, CH 2 ), 1.23 (3H, t, J 7.6 Hz, CH 3 ), (3H, br q, BH 3 ); 13 C-NMR: (d, J 10.1 Hz, C-C), (d, J 2.1 Hz, CH), (d, J 63.8 Hz, C-P), (d, J 2.7 Hz, CH), (d, J 63.4 Hz, C-P), (d, J 10.9 Hz, 2xCH), (d, J 11.9 Hz, CH), (d, J 10.9 Hz, CH), (d, J 10.9 Hz, 2xCH), (d, J 10.9 Hz, CH), 54.0 (d, J 2.7 Hz, OCH 3 ), 28.7 (CH 2 ), 15.3 (CH 3 ); 31 P-NMR: ; MS (EI, 70 ev) m/z: 257 (2, [M-H] + ), 244 (100, [M-BH 3 ] + ), 229 (96, [M-BH 3 -CH 3 ] + ), 213 (26, [M- BH 3 -OCH 3 ] + ); HRMS (ESI) [M+Na] + : m/z calcd. for C 15 H 20 BNaOP , found ; [M-BH 3 +H] + : m/z calcd. for C 15 H 18 OP , found ; HPLC: optical purity >98%ee; Column: Chiralcel OJ-H (150x4.6 mm), hexane/i-proh 99/1, 1.00 ml/min, t R = 12.7 min (S)-enantiomer and 16.1 min (R)-enantiomer; (R)-(-)-(2-Isopropoxyphenyl)(methoxy)(phenyl)phosphine P-borane complex (4l) Yield 81%; colourless oil (column chromatography cyclohexane/acoet 19/1) 23 = (c 1, CHCl 3 ); 1 H-NMR: 7.82 (1H, ddd, J 12.0, 7.6, 1.8 Hz, arom. H), (2H, m, arom. H), (4H, m, arom. H), 7.01 (1H, ddd, J 7.6, 2.0, 0.9 Hz, arom. H), 6.80 (1H, dd, J 8.4, 4.5 Hz, arom. H), 4.46 (1H, sept, J 6.1 Hz, CH-O), 3.71 (3H, d, J 12.1 Hz, OCH 3 ), 1.06 (3H, d, J 6.0 Hz, CH 3 ), 0.96 (3H, d, J 6.0 Hz, CH 3 ), (3H, br q, BH 3 );