Synthesis of complexes and related intermediates

5.2.3 Synthesis of complexes and

5.38-5.21 (m, 2H, CHCH₂), 4.56-4.55 (m, 2H, CH_2allyl) 3.93 (s, 3H, OCH₃), 3.69-2.92 (m, 13H, CHN & 6xCH2), 2.78 (s, 3H, NCH3). IR (film): ν(cm^-1) 2923, 2098, 1699, 1558, 1468, 1403, 1327, 1285, 1206, 1141, 1024, 950, 810, 759, 694, 635, 516. HRMS calculated for C₃₁H₃₀FN₅O₅RuS₄Na⁺ (M + Na)⁺ 824.0050, found (M + Na)⁺ 824.0044.

Measureable crystals of compound 96 were obtained after one week in (CD₃)₂CO at 4 °C.

5.2.3.3 Synthesis of organoruthenium(II) complex 87

To a solution of the solid product 96 (21 mg, 26 µmol) in methylene chloride (11 mL) was added 1,3-dimethylbarbituric acid (61 mg, 39 µmol) and Pd(PPh₃)₄ (4.5 mg, 4 µmol) under nitrogen. The result-ing mixture was stirred at ambient tem-perature for 14 h, followed by the addition of saturated NaHCO₃ (1 x 0.5 mL) solution to quench the reaction. The resulting sus-pension was dried in vacuo and the crude material was adsorbed onto silica gel and subjected to silica gel chromatography with methylene chloride : methanol : 2% triethyl-amine (10:1  5:1) as the eluting solvent to obtain the metal complex 87. The purified complex 87 was then extracted with satur-ated NH₄Cl (2 x 20 mL), saturated NaHCO₃ (4 x 15 mL) and Brine (2 x 20 mL) to remove residual NEt3. The metal complex 87 was obtained as a dark green solid (8.7 mg, 12 µmol, 47%). R_f = 0.38 (methylene chlo-ride : methanol 2% triethylamine 15:1).

1H-NMR (300 MHz, (CH₃)₂SO): δ(ppm) 11.02 (s, 1H, NH), 8.98 (m, 1H, CH_ar-4), 8.80 (dd, J = 9.3, 2.4 Hz, 1H, CHar-2), 8.30 (d, J = 2.7 Hz, 1H, CH_ar-8), 8.04 (d, J = 9.0 Hz, 1H, CH_ar-11), 7.15 (dd, J = 9.0, 2.7 Hz, 1H, CH_ar-10), 3.89 (s, 3H, OCH₃), 3.58-3.39 (m, 13H, CHN & 6xCH₂), 2.40 (s, 3H, NHCH3). ¹³C-NMR (125.8 MHz, (CH3)2SO):

δ(ppm) 170.7 (2C, C_ar-5 & C_ar-7), 170.52 (C_ar-3) 156.76 (C_ar-9), 153.7 (C_ar-12b), 147.7 (C_ar), 146.7 (C_ar), 141.1 (C_ar), 134.27 (NCS), 131.4 (C_ar), 131.1 (C_ar), 128.7 (C_ar), 124.1 (C_ar), 120.8 (C_ar), 115.7 (C_ar), 114.5 (C_ar), 110.5 (C_ar), 106.1 (C_ar-8), 69.7 (CHNHCH₃), 55.5 (OCH₃), 53.7 (SCH₂CHNHCH₃), 51.7 (SCH₂CHNHCH₃), 48.5 (CHNHCH₃), 35.9 (C_aliph), 34.2 (C_aliph), 33.3 (C_aliph), 31.8 (C_aliph).

IR (film): ν(cm^-1) 3452, 3058, 2924, 1747, 1677, 1615, 1561, 1492, 1439, 1408, 1369, 1328, 1287, 1225, 1022, 948, 883, 759, 610,

447. HRMS calculated for

C₂₇H₂₆FN₅O₃RuS₄Na (M + Na)⁺ 739.8447, found (M + Na)+739.8443.

5.2.3.4 Synthesis of organorhodium(III) complexes -(R)-106 and

-(R)-107

A suspension of 79 (17.6 mg, 44 µmol) and RhCl₃∙3H₂O (11.5 mg, 44 µmol) in an ethanol : water mixture (1:1, 20 mL) under nitrogen atmosphere in a sealed vessel was heated to 90 °C for 3 h.

During this time the suspension turned from pale brown into dark red. The reaction mix-ture was then cooled down slightly to add (R)-105 (9.9 mg, 48 µmol). After addition of (R)-105, the reaction was further proceeded

at 90 °C for 16 h. The reaction mixture was then cooled down to ambient temperature and the solvent was removed in vacuo. The crude material was purified via column chromatography using methylene chlo-ride : methanol (20:1  10:1). The separat-ed diastereomers were further purifiseparat-ed and concentrated via preparative TLC using methylene chloride : methanol (10:1). The products were obtained as red solids,

-(R)-107 (4.2 mg, 6.6 µmol, 15%) and

-(R)-106 (6.1 mg, 9.7 µmol, 22%).

-(R)-107: R_f = 0.25 (methylene chlo-ride : methanol 15:1). ¹H-NMR (500 MHz, (CD3)2SO): δ(ppm) 11.24 (s, 1H, NH), 9.68 (d, J = 5.7 Hz, 1H, CHar-6’), 9.30 (dd, J = 8.4, 1.1 Hz, 1H, CH_ar-4), 8.87 (d, J = 5.1 Hz, 1H, CH_ar-2), 8.68 (dd, J = 7.8, 0.5 Hz, 1H, CH_ar-8), 8.48 (td, J = 7.8, 1.5 Hz, 1H, CH_ar-4’), 8.08 (dd, J = 8.4, 5.2 Hz, 1H, CH_ar-3), 8.06 – 8.01 (m, 1H, CH_ar-5’), 7.99 (d, J = 7.8 Hz, 1H, CH_ar-3’), 7.28 – 7.24 (m, 1H, CH_ar-10), 7.21 (ddd, J = 8.4, 7.2, 1.4 Hz, 1H, CH_ar-9), 5.70 (d, J = 8.2 Hz, 1H, CH_ar-11), 4.60 (d, J = 15.6 Hz, 1H, NCHH), 4.34 (d, J = 15.7 Hz, 1H, NCHH), 3.81 (dd, J

= 9.6, 4.3 Hz, 1H, CH_), 2.50 (m, 1H, CH_H_), 2.28 – 2.15 (m, 2H, CH_H_&

CH_H_), 2.00 (dt, J = 11.3, 4.8 Hz, 1H, CHH), 1.58 (m, J = 11.7, 5.9 Hz, 1H, CH_H_), 1.11 – 1.01 (m, 1H, CH_H_).

13C-NMR (126 MHz, (CD₃)₂SO): δ(ppm) 182.02 (Ccarbonyl), 170.59 (Car-7), 170.23 (C_ar-5), 161.13 (C_ar-2’), 152.62 (C_ar-6’), 152.54 (C_ar-12b), 148.90 (C_ar-12a), 148.89 (C_ar-11a), 148.74 (C_ar-2), 142.09 (C_ar-4’), 141.17 (C_ar-7b), 135.24 (C_ar-4), 131.23 (Car-7a), 126.61 (C_ar-9), 126.27 (C_ar-5’), 124.75 (C_ar-8), 123.90 (C_ar-3), 123.47 (C_ar-3’), 121.34 (C_ar-10), 119.59 (C_ar-4a), 115.08 (C_ar-7c), 114.59 (C_ar-4b), 111.79 (C_ar-11), 72.91 (C_), 70.02 (NCH₂), 61.27 (C_), 30.43 (C_), 24.31 (C_). IR (film): ν (cm^-1) 3037, 2075, 1994, 1751, 1703, 1646, 1519, 1482, 1413, 1337, 1296, 1262, 1225, 1132, 1017, 930, 884, 856, 743, 704, 636, 493, 436. HRMS calculated for C₂₈H₂₁ClN₅O₄Rh (M + Na)⁺ 652.0229, found (M + Na)⁺

652.0220. -(R)-106: R_f = 0.08 (methylene chloride : methanol 15:1). ¹H-NMR (300 MHz, (CD₃)₂SO): δ(ppm) 11.24 (s, 1H, NH), 9.54 (d, J = 5.5 Hz, 1H, CH_ar-6‘), 9.17 (d, J = 7.7 Hz, 1H, CHar-4), 8.71 (d, J = 7.8 Hz, 1H, CH_ar-8), 8.38 (m, 1H, CH_ar-4‘), 7.99 – 7.89 (m, 3H, CH_ar-2, CH_ar-5‘ & CH_ar-11), 7.82 (d, J = 8.3 Hz, 1H, CH_ar-3‘), 7.74 (dd, J

= 8.4, 5.3 Hz, 1H, CH_ar-3), 7.58 – 7.51 (m, 1H, CHar-9), 7.41 – 7.33 (m, 1H, CHar-10), 4.59 (s, 2H, NCH2), 3.79 (dd, J = 9.4, 4.7 Hz, 1H, CH), 2.50 (m, 1H, CHH), 2.29 – 2.09 (m, 2H, CH_H_& CH_H_), 1.86 (dt, J = 11.3, 5.9 Hz, 1H, CH_H_), 1.44 (dt, J = 11.7, 5.8 Hz, 1H, CH_H_), 1.10 (dt, J = 12.7, 7.0 Hz, 1H, CH_H_). ¹³C-NMR (101 MHz, (CD₃)₂SO): δ(ppm) 181.89 (C_carbonyl), 159.96 (C_ar-2’), 151.72 (C_ar-6’), 151.25 (C_ar-12b), 150.17 (C_ar-2), 149.43 (C_ar-12a), 149.13 (C_ar-11a), 141.85 (C_ar-7b), 140.53 (C_ar-4‘), 134.41 (C_ar-4), 130.75 (C_ar-7a), 125.67 (C_ar-9), 125.79 (C_ar-5‘), 123.84 (C_ar-3), 123.57 (Car-8), 122.67 (Car-11), 120.87 (C_ar-10), 119.14 (C_ar-4a), 114.73 (C_ar-3‘), 114.44 (C_ar-7c), 113.63 (C_ar-4b), 73.51 (C_), 69.35 (NCH₂), 60.75 (C_), 30.74 (C_), 24.01 (C_). The ¹³C-signals of C_ar-5 and C_ar-7 are missing. IR (film): ν(cm^-1) 3045, 2724, 1819, 1750, 1704, 1644, 1519, 1481, 1413, 1336, 1297, 1225, 1134, 1014, 932, 824, 786, 743, 703, 635, 492, 436, 392. HRMS calculated for C₂₈H₂₁ClN₅O₄RhNa (M + Na)⁺ 652.0229, found (M + Na)⁺ 652.0238.

5.2.3.5 Synthesis of organorhodium(III) complexes -(S)-106 and -(S)-107

A suspension of 79 (17.6 mg, 44 µmol) and RhCl₃∙3H₂O (11.5 mg, 44 µmol) in an ethanol : water mixture (1:1, 20 mL) under nitrogen atmosphere in a sealed vessel was heated to 90 °C for 3 h.

During this time the suspension turned from pale brown into dark red. The reaction mix-ture was then cooled down slightly to add (S)-105 (9.9 mg, 48 µmol). After addition of (S)-105, the reaction was further proceeded at 90 °C for 16 h. The reaction mixture was then cooled down to ambient temperature and the solvent was removed in vacuo. The crude material was purified via column chromatography using methylene chlo-ride : methanol (20:1  10:1). The separat-ed diastereomers were further purifiseparat-ed and concentrated via preparative TLC using methylene chloride : methanol (10:1). The products were obtained as red solids,

-(S)-107 (3.9 mg, 6.6 µmol, 14%) and

-(S)-106 (6.7 mg, 10.6 µmol, 24%).

-(S)-107: Rf = 0.25 (methylene chlo-ride : methanol 15:1). ¹H-NMR (500 MHz, (CD₃)₂SO): δ(ppm) 11.25 (s, 1H, NH), 9.68 (d, J = 5.4 Hz, 1H, CH_ar-6’), 9.30 (d, J = 8.3 Hz, 1H, CH_ar-4), 8.87 (d, J = 4.8 Hz, 1H, CHar-2), 8.68 (d, J = 7.7 Hz, 1H, CHar-8), 8.51 – 8.43 (m, 1H, CH_ar-4’), 8.08 (dd, J = 8.3, 5.2 Hz, 1H, CH_ar-3), 8.06 – 8.01 (m, 1H, CH_ar-5’), 7.99 (d, J = 7.7 Hz, 1H, CH_ar-3’), 7.26 (t, J = 7.4 Hz, 1H, CH_ar-10), 7.21 (t, J = 7.4 Hz, 1H, CH_ar-9), 5.70 (d, J = 8.2 Hz, 1H, CH_ar-11), 4.60 (d, J = 15.8 Hz, 1H, NCHH), 4.34 (d, J = 15.8 Hz, 1H, NCHH), 3.81 (dd, J

= 9.3, 4.0 Hz, 1H, CH_), 2.50 (m, 1H, CH_H_), 2.21 (dd, J = 17.3, 10.9 Hz, 2H, CHH& CHH), 2.04 – 1.97 (m, 1H, CH_H_), 1.61 – 1.54 (m, 1H, CH_H_), 1.11 – 1.01 (m, 1H, CH_H_). ¹³C-NMR (126 MHz, (CD₃)₂SO): δ(ppm) 181.79 (C_carbonyl), 169.97 (C_ar-7), 169.89 (C_ar-5), 160.83 (C_ar-2’), 152.46 (C_ar-6’), 152.14 (C_ar-12b), 148.53 (Car-12a), 148.38 (Car-11a) 148.27 (Car-2), 141.77 (C_ar-4’), 140.87 (C_ar-7a), 134.93 (C_ar-4), 130.85 (C_ar-7a), 126.11 (C_ar-9), 125.92 (C_ar-5’), 124.34 (C_ar-8), 123.23 (C_ar-3), 123.01 (C_ar-3’), 121.07 (C_ar-10), 119.14 (C_ar-4a), 114.27 (C_ar-7c), 114.13 (C_ar-4b), 111.43 (C_ar-11), 72.27 (C_), 69.75 (NCH₂), 61.02 (C_), 30.13 (C_), 24.16 (C_).

IR (film): ν (cm^-1) 3034, 2159, 2096, 1751, 1704, 1646, 1519, 1483, 1413, 1337, 1295, 1262, 1225, 1131, 1015, 930, 828, 784, 744, 705, 636, 527, 491. HRMS calculated for C₂₈H₂₁ClN₅O₄Rh (M + Na)⁺ 652.0229, found (M + Na)⁺ 652.0208. -(S)-106: Rf = 0.08 (methylene chloride : methanol 15:1). ¹ H-NMR (300 MHz, (CD₃)₂SO): δ(ppm) 11.22 (s, 1H, NH), 9.54 (d, J = 5.1 Hz, 1H, CH_ar-6‘), 9.18 (dd, J = 8.4, 1.0 Hz, 1H, CH_ar -4), 8.71 (d, J = 7.9 Hz, 1H CH_ar-8), 8.38 (td, J = 7.7, 1.5 Hz, 1H, CH_ar-4‘), 8.00 – 7.89 (m, 3H, CH_ar-2, CH_ar-5‘ & CH_ar-11), 7.82 (d, J = 8.3 Hz, 1H, CH_ar-3‘), 7.74 (dd, J = 8.4, 5.3 Hz, 1H, CH_ar-3), 7.59 – 7.50 (m, 1H, CH_ar-9), 7.41 – 7.33 (m, 1H, CH_ar-10), 4.58 (s, 2H, NCH₂), 3.79 (dd, J = 9.4, 4.8 Hz, 1H, CH_), 2.51 – 2.48 (m, 1H, CH_H_), 2.25 – 2.12 (m, 2H, CH_H_& CHH_), 1.94 – 1.77 (m, 1H, CHH), 1.50 – 1.37 (m, 1H, CHH), 1.17 – 0.98 (m, 1H, CH_H_). ¹³C-NMR (101 MHz, (CD₃)₂SO): δ(ppm) 182.29 (C_carbonyl), 160.16 (C_ar-2’), 152.22 (C_ar-6’), 151.65 (C_ar-12b), 150.37 (C_ar-2), 149.86 (C_ar-12a), 149.83 (C_ar-11a) 142.35 (C_ar-7a), 140.73 (C_ar-4‘), 134.81 (C_ar-4), 131.25 (C_ar-4b), 126.57 (C_ar-9), 126.09 (C_ar-5‘), 124.26 (C_ar-3), 123.90 (C_ar-8), 123.07 (C_ar-11), 121.10 (Car-10), 119.66 (Car-4a), 114.96 (Car-3‘), 114.89 (C_ar-7c), 114.01 (C_ar-7b), 73.52 (C_), 69.25 (NCH₂), 61.45 (C_), 30.38 (C_), 23.83 (C_). The ¹³C-signals of C_ar-5 and C_ar-7 are

missing. IR (film): ν (cm^-1) 3046, 2723, 1818, 1752, 1703, 1647, 1518, 1482, 1414, 1337, 1295, 1224, 1133, 1012, 932, 824, 786, 742, 701, 637, 492, 436. HRMS calculated for C₂₈H₂₁ClN₅O₄RhNa (M + Na)⁺ 652.0229, found (M + Na)⁺ 652.0228._

5.2.3.6 Synthesis of organorhodium(III) complexes -(S,R)-125 and

-(S,R)-126

A suspension of 79 (30 mg, 75 µmol) and RhCl₃∙3H₂O (19.6 mg, 75 µmol) in an ethanol : water mixture (1:1, 10 mL) under nitrogen atmosphere in a sealed vessel was heated to 90 °C for 3 h. During this time the suspension turned from pale brown into dark red. The reaction mixture was then cooled down slightly to add (S, R)-119 (27.9 mg, 83 µmol). After addition of (S, R)-119, the reaction was further proceeded at 90 °C for 16 h. The reaction mixture was then cooled down to ambient temperature and the sol-vent was removed in vacuo. The crude ma-terial was purified via column chroma-tography using methylene chloride : meth-anol (20:1  10:1). The separated diastere-omers were further purified and concen-trated via preparative TLC using methylene chloride : methanol (15:1). The products were obtained as red solids, -(S,R)-125 (11 mg, 17.3 µmol, 23%) and -(S,R)-126 (8.2 mg, 12.8 µmol, 17%). -(S,R)-125:

R_f = 0.14 (methylene chloride : methanol 15:1). ¹H-NMR (500 MHz, (CD₃)₂SO):

δ(ppm) 9.55 (d, J = 5.8 Hz, 1H, CH_ar-6’), 9.18 (dd, J = 8.4, 1.0 Hz, 1H, CH_ar-4), 8.71

(d, J = 8.0 Hz, 1H, CH_ar-8), 8.36 (td, J = 7.8, 1.5 Hz, 1H, CH_ar-4’), 8.10 – 7.87 (m, 3H, CHar-11, CHar-5’ & CHar-2), 7.77 (d, J = 8.3 Hz, 1H, CH_ar-3’), 7.76 – 7.73 (m, 1H, CH_ar-3), 7.54 (ddd, J = 8.3, 7.1, 1.3 Hz, 1H, CH_ar-9), 7.41 – 7.35 (m, 1H, CH_ar-10), 4.82 – 4.74 (m, 2H, NCH₂), 4.74 – 4.70 (m, 1H CH_) 4.01 (t, J = 8.8 Hz, 1H, CH_), 3.72 – 3.62 (m, 1H, CH_H_), 3.51 (s, 1H, OH) 2.52 (d, J = 1.9 Hz, 1H, CH_H_), 2.26 – 2.11 (m, 1H, CH_H_), 1.91 – 1.78 (m, 1H, CH_H_).

13C-NMR (126 MHz, (CD₃)₂SO): δ(ppm) 181.83 (C_carbonyl), 160.49 (C_ar-2’), 151.89 (C_ar-6’), 151.32 (C_ar-2), 151.31 (C_ar-12b), 150.81 (C_ar-12a), 146.75 (C_ar-11a), 142.44 (C_ar-7b) 140.95 (C_ar-4’), 135.27 (C_ar-4), 131.17 (C_ar-7a), 127.10 (C_ar-9), 126.21 (Car-5’), 124.81 (Car-3), 124.60 (Car-8), 124.09 (C_ar-11), 120.14 (C_ar-10), 119.70 (C_ar-4a), 115.09 (C_ar-3’), 114.66 (C_ar-7c), 114.22 (C_ar-4b), 73.71 (C_), 72.66 (NCH₂), 72.64 (C), 67.41 (C), 39.82 (C). The

13C-signals of Car-5 and Car-7 are missing.

IR (film): ν (cm^-1) 2925, 2855, 2724, 2252, 2126, 1750, 1705, 1649, 1498, 1446, 1412, 1342, 1294, 1231, 1148, 1001, 878, 820, 755, 707, 635, 530, 490, 432. HRMS calcu-lated for C28H21ClN5NaO5Rh (M + Na)⁺ 668.0178, found (M + Na)⁺ 668.0178.

-(S,R)-126: Rf = 0.08 (methylene chlo-ride : methanol 15:1). ¹H-NMR (300 MHz, (CD₃)₂SO): δ(ppm) 9.67 (d, J = 5.7 Hz, 1H, CH_ar-6’), 9.29 (dd, J = 8.4, 1.0 Hz, 1H, CH_ar-4), 8.84 (d, J = 5.1 Hz, 1H, CH_ar-2), 8.71 – 8.65 (m, 1H, CH_ar-8), 8.47 (td, J = 7.8, 1.4 Hz, 1H, CH_ar-4’), 8.09 (d, J = 8.4 Hz, 1H, CH_ar-3), 8.07 (d, J = 8.4 Hz, 1H, CH_ar-5’), 8.01 (dd, J = 10.3, 4.2 Hz, 1H, CH_ar-3’), 7.32 – 7.11 (m, 2H, CH_ar-10 &

CH_ar-9), 5.74 (d, J = 7.8 Hz, 1H, CH_ar-11), 5.23 (s, 1H, CH_), 4.84 (d, J = 15.8 Hz, 1H, NCHH), 4.44 (d, J = 15.8 Hz, 1H, NCHH), 4.01 (t, J = 8.5 Hz, 1H, CH_), 3.77 (s, 1H, OH), 2.51 – 2.48 (m, 1H, CH_H_), 2.30 – 2.11 (m, 2H, CHH & CHH), 2.08 – 1.87 (m, 1H, CH_H_). IR (film): ν (cm^-1) 2973, 2937, 2250, 1746, 1709, 1666, 1579, 1497, 1448, 1415, 1337, 1296, 1261, 1227, 1152,

1127, 1049, 1005, 878, 821, 763, 733, 707, 631, 532, 488. HRMS calculated for C28H21ClN5NaO5Rh (M + Na)⁺ 668.0178, found (M + Na)⁺ 668.0178.

5.2.3.7 Synthesis of organorhodium(III) complexes -(R)-127 and

-(R)-128

A suspension of 79 (30 mg, 75 µmol) and RhCl₃∙3H₂O (19.6 mg, 75 µmol) in an ethanol : water mixture (1:1, 10 mL) under nitrogen atmosphere in a sealed vessel was heated to 90 °C for 3 h. During this time the suspension turned from pale brown into dark red. The reaction mixture was then cooled down slightly to add (R)-124 (18.3 mg, 83 µmol). After addition of (R)-124, the reac-tion was further proceeded at 90 °C for 16 h.

The reaction mixture was then cooled down to ambient temperature and the solvent was removed in vacuo. The crude material was purified via column chromatography using methylene chloride : methanol (20:1  5:1).

The separated diastereomers were further purified and concentrated via preparative TLC using methylene chloride : methanol (15:1). The products were obtained as red solids, -(R)-127 (11.5 mg, 18 µmol, 24%) and -(R)-128 (7.7 mg, 12 µmol, 16%).

-(R)-127: R_f = 0.11 (methylene chlo-ride : methanol 15:1). ¹H-NMR (300 MHz, (CD₃)₂SO): δ(ppm) 11.19 (s, 1H, NH), 9.55 (d, J = 5.6 Hz, 1H, CH_ar-6‘), 9.16 (dd, J = 8.2, 1.2 Hz, 1H, CH_ar-4), 8.72 (d, J = 7.9 Hz, 1H, CH_ar-8), 8.39 (td, J = 7.8, 1.4 Hz, 1H, CH_ar-4‘), 8.06 – 7.91 (m, 3H, CH_ar-2, CH_ar-5‘

& CH_ar-11), 7.76 – 7.64 (m, 2H, CH_ar-3‘ &

CH_ar-3), 7.60 – 7.51 (m, 1H, CH_ar-9), 7.42 – 7.35 (m, 1H, CHar-10), 4.86 (d, J = 16.4 Hz, 1H, NCHH), 4.48 (d, J = 16.1 Hz, 1H, NCHH), 3.45 – 3.35 (m, 1H, CH_), 2.45 – 2.35 (m, 1H, CH_aliph), 2.33 – 2.28 (m, 1H, CH_aliph), 1.99 – 1.82 (m, 1H, CH_aliph), 1.79 – 1.59 (m, 1H, CH_aliph), 1.56 – 1.39 (m, 1H, CH_aliph), 1.32 – 1.21 (m, 2H, CH_aliph), 1.07 – 0.92 (m, 1H, CHaliph). A second set of signals for each proton was observed. IR (film): ν (cm^-1) 2956, 2920, 2853, 2268, 2209, 2169, 2133, 2058, 2008, 1754, 1708, 1648, 1444, 1339, 1229, 1012, 915, 748, 677, 637, 534, 488, 434. HRMS calculated for C₂₉H₂₃ClN₅NaO₄Rh (M + Na)⁺ 666.0386, found (M + Na)⁺ 666.0387. -(R)-128:

R_f = 0.24 (methylene chloride : methanol 15:1). ¹H-NMR (300 MHz, (CD₃)₂SO):

δ(ppm) 11.25 (s, 1H, NH), 9.71 (d, J = 4.7 Hz, 1H, CH_ar-6’), 9.32 – 9.19 (m, 1H, CH_ar-4), 8.88 (d, J = 5.2 Hz, 1H, CH_ar-2), 8.67 (t, J = 7.2 Hz, 1H, CH_ar-8), 8.54 – 8.33 (m, 1H, CHar-4’), 8.20 – 8.07 (m, 1H, CHar-3), 8.05 (dd, J = 11.4, 6.2 Hz, 1H, CH_ar-5’), 7.96 – 7.84 (m, 1H, CH_ar-3’), 7.33 – 7.07 (m, 2H, CH_ar-9 & CH_ar-10), 5.41 (d, J = 8.2 Hz, 1H, CH_ar-11), 4.92 (d, J = 15.5 Hz, 1H, NCHH), 4.20 (d, J = 15.7 Hz, 1H, NCHH), 3.43 (t, J = 5.5 Hz, 1H, CH_), 2.38 – 2.19 (m, 2H, CH_aliph), 2.00 – 1.63 (m, 4H, CHaliph), 1.58 – 1.40 (m, 2H, CHaliph). A sec-ond set of signals for each proton was ob-served. IR (film): ν(cm^-1) 1751, 1705, 1653, 1521, 1491, 1415, 1339, 1296, 1261, 1225, 1080, 1016, 821, 792, 745, 707, 636, 527.

HRMS calculated for C₂₉H₂₃ClN₅NaO₄Rh (M + Na)⁺ 666.0386, found (M + Na)⁺ 666.0386.

5.2.3.8 Synthesis of organorhodium(III) complexes -(S)-127 and -(S)-128

A suspension of 79 (30 mg, 75 µmol) and RhCl₃∙3H₂O (19.6 mg, 75 µmol) in an ethanol : water mixture (1:1, 10 mL) under nitrogen atmosphere in a sealed vessel was heated to 90 °C for 3 h. During this time the suspension turned from pale brown into dark red. The reaction mixture was then cooled down slightly to add (S)-124 (18.3 mg, 83 µmol). After addition of (S)-124, the reac-tion was further proceeded at 90 °C for 16 h.

The reaction mixture was then cooled down to ambient temperature and the solvent was removed in vacuo. The crude material was purified via column chromatography using methylene chloride : methanol (35:1  10:1). The separated diastereomers were further purified and concentrated via prepar-ative TLC using methylene chlo-ride : methanol (15:1). The products were obtained as red solids, -(S)-127 (10.5 mg, 15.8 µmol, 21%) and -(S)-128 (7.5 mg, 11.3 µmol, 15%). -(S)-127: Rf = 0.11 (methylene chloride : methanol 15:1). ¹ H-NMR (300 MHz, (CD₃)₂SO): δ(ppm) 9.54 (d, J = 5.7 Hz, 1H, CH_ar-6‘), 9.16 (dd, J = 8.2, 1.2 Hz, 1H, CH_ar-4), 8.72 (d, J = 7.9 Hz, 1H, CH_ar-8), 8.39 (td, J = 7.7, 1.4 Hz, 1H, CHar-4’), 7.97 (d, J = 8.2 Hz, 3H, CHar-2, CH_ar-5‘ & CH_ar-11), 7.70 (dt, J = 12.4, 4.8 Hz, 2H, CH_ar-3‘ & CH_ar-3), 7.59 – 7.52 (m, 1H, CH_ar-9), 7.42 – 7.35 (m, 1H, CH_ar-10), 4.86 (d, J = 16.6 Hz, 1H, NCHH), 4.48 (d, J

= 16.4 Hz, 1H, NCHH), 3.45 – 3.35 (m, 1H, CH_), 2.44 – 2.32 (m, 1H, CH_aliph), 2.33 – 2.28 (m, 1H, CH_aliph), 1.94– 1.80 (m, 1H,

CH_aliph), 1.79 – 1.59 (m, 1H, CH_aliph), 1.56 – 1.39 (m, 1H, CH_aliph), 1.33 – 1.20 (m, 2H, CHaliph), 1.06 – 0.90 (m, 1H, CHaliph). A sec-ond set of signals for each proton was ob-served. IR (film): ν (cm^-1) 1750, 1705, 1650, 1524, 1497, 1413, 1339, 1268, 1228, 1017, 999, 822, 794, 753, 706, 635, 585, 527, 489,

438. HRMS calculated for

C₂₉H₂₃ClN₅NaO₄Rh (M + Na)⁺ 666.0386, found (M + Na)⁺ 666.0387. -(S)-128:

Rf = 0.24 (methylene chloride : methanol 15:1). ¹H-NMR (300 MHz, (CD₃)₂SO):

δ(ppm) 11.22 (s, 1H, NH), 9.71 (d, J = 4.8 Hz, 1H, CH_ar-6’), 9.29 (ddd, J = 8.4, 4.5, 1.0 Hz, 1H, CH_ar-4), 8.88 (d, J = 5.1 Hz, 1H, CH_ar-2), 8.72 – 8.62 (m, 1H, CH_ar-8), 8.48 (td, J = 7.8, 1.4 Hz, 1H, CH_ar-4’), 8.13 (dd, J

= 8.4, 5.2 Hz, 1H, CH_ar-3), 8.02 (d, J = 7.7 Hz, 1H, CH_ar-3’), 7.91 (dd, J = 13.5, 7.0 Hz, 1H, CH_ar-5’), 7.29 – 7.21 (m, 1H, CH_ar-9), 7.19 – 7.10 (m, 1H, CH_ar-10), 5.41 (d, J = 8.2 Hz, 1H, CHar-11), 4.91 (d, J = 15.7 Hz, 1H, NCHH), 4.20 (d, J = 15.5 Hz, 1H, NCHH), 3.42 (t, J = 5.6 Hz, 1H, CH), 2.38 – 2.19 (m, 1H, CHaliph) 2.02 – 1.86 (m, 2H, CH_aliph), 1.86 – 1.63 (m, 1H, CH_aliph), 1.58 – 1.39 (m, 2H, CH_aliph), 1.38 – 1.25 (m, 1H, CH_aliph), 1.07 – 0.89 (m, 1H, CH_aliph). A sec-ond set of signals for each proton was ob-served. IR (film): ν (cm^-1) 1749, 1702, 1657, 1517, 1489, 1419, 1341, 1293, 1264, 1222, 1080, 1011, 818, 796, 745, 707, 636, 527.

5.2.3.9 Synthesis of organorhodium(III) complexes -(R)-129 and

-(R)-130

A suspension of 79 (30 mg, 75 µmol) and RhBr₃∙xH₂O (26 mg, 75 µmol) in an eth-anol : water mixture (1:1, 20 mL) under ni-trogen atmosphere in a sealed vessel was heated to 90 °C for 3 h. During this time the suspension turned from pale brown into dark red. The reaction mixture was then cooled down slightly to add (R)-105 (17 mg, 83 µmol). After addition of (R)-105, the reac-tion was further proceeded at 90 °C for 16 h.

The reaction mixture was then cooled down to ambient temperature and the solvent was removed in vacuo. The crude material was purified via column chromatography using methylene chloride : methanol (100:0  10:1). The separated diastereomers were further purified and concentrated via prepar-ative TLC using methylene chlo-ride : methanol (15:1). The products were obtained as red solids, -(R)-129 (8.1 mg, 12 µmol, 16%) and -(R)-130 (5.0 mg, 7.5 µmol, 10%). -(R)-129: Rf = 0.16 (methy-lene chloride : methanol 15:1). ¹H-NMR (300 MHz, (CD3)2SO): δ(ppm) 9.75 (d, J = 5.5 Hz, 1H, CH_ar-6‘), 9.18 (dd, J = 8.4, 2.5 Hz, 1H, CH_ar-4), 8.71 (d, J = 7.9 Hz, 1H, CH_ar-8), 8.44 – 8.32 (m, 1H, CH_ar-4’), 7.98 – 7.91 (m, 3H, CH_ar-2, CH_ar-5‘ & CH_ar-11), 7.82 (dd, J = 8.6, 4.2 Hz, 1H, CHar-3‘), 7.74 (dd, J = 8.3, 5.3 Hz, 1H, CH_ar-3), 7.59 – 7.48 (m, 1H, CH_ar-9), 7.38 (t, J = 7.5 Hz, 1H, CH_ar-10), 4.59 (s, 2H, NCH₂), 3.83 – 3.68 (m, 1H, CH_), 2.50 – 2.48 (m, 1H, CH_H_),

2.24 – 2.06 (m, 2H, CH_H_& CHH_), 1.90 – 1.78 (m, 1H, CH_H_), , 1.51 – 1.35 (m, 1H, CHH), 1.12 – 0.98 (m, 1H, CHH). IR (film):

ν (cm^-1) 2923, 2855, 2250, 2127, 1749, 1705, 1647, 1523, 1496, 1470, 1447, 1416, 1340, 1294, 1228, 1147, 1020, 1001, 820, 755, 707, 635, 573. HRMS calculated for C₂₈H₂₁BrN₅NaO₄Rh (M + Na)⁺ 695.9724, found (M + Na)⁺ 695.9726. -(R)-130:

R_f = 0.37 (methylene chloride : methanol 15:1). ¹H-NMR (300 MHz, (CD₃)₂SO):

δ(ppm) 9.68 (d, J = 5.6 Hz, 1H, CH_ar-6’), 9.29 (dd, J = 8.4, 1.1 Hz, 1H, CH_ar-4), 8.86 (d, J = 5.1 Hz, 1H, CH_ar-2), 8.68 (dd, J = 7.0, 1.0 Hz, 1H, CH_ar-8), 8.48 (td, J = 7.8, 1.5 Hz, 1H, CH_ar-4’), 8.08 (dd, J = 8.4, 5.2 Hz, 1H, CH_ar-3), 8.03 – 7.95 (m, 2H, CH_ar-5’ &

CHar-3’), 7.30 – 7.16 (m, 2H, CHar-9 &

CH_ar-10), 5.69 (d, J = 7.9 Hz, 1H, CH_ar-11), 4.60 (d, J = 16.0 Hz, 1H, NCHH), 4.33 (d, J

= 15.4 Hz, 1H, NCHH), 3.81 (dd, J = 9.5, 4.3 Hz, 1H, CH_), 2.50 – 2.48 (m, 1H, CH_H_) 2.25 -2.14 (m, 2H, CH_H_& CHH_), 2.07 – 1.90 (m, 1H, CHH), 1.67 – 1.40 (m, 1H, CH_H_), 1.11 – 1.00 (m, 1H, CH_H_). IR (film):

ν(cm^-1) 2921, 2852, 2246, 2182, 2129, 1750, 1703, 1645, 1569, 1520, 1482, 1446, 1409, 1336, 1288, 1222, 1157, 1129, 1020, 998, 931, 824, 742, 704, 635.

5.2.3.10 Synthesis of organorhodium(III) complexes -(S)-131 and -(S)-132

A suspension of 78 (34 mg, 75 µmol) and RhCl₃∙3H₂O (18.3 mg, 69 µmol) in an ethanol : water mixture (1:1, 15 mL) under nitrogen atmosphere in a sealed vessel was

heated to 90 °C for 3 h. During this time the suspension turned from pale brown into dark red. The reaction mixture was then cooled down slightly to add (S)-105 (15.5 mg, 75 µmol). After addition of (S)-105, the reac-tion was further proceeded at 90 °C for 16 h.

The reaction mixture was then cooled down to ambient temperature and the solvent was removed in vacuo. The crude material was purified via column chromatography using methylene chloride : methanol (20:1  10:1). The separated diastereomers were further purified and concentrated via preparative TLC using methylene chlo-ride : methanol (10:1). The products were obtained as dark purple solids, -(S)-131 (10.7 mg, 15.9 µmol, 23%) and -(S)-132 (5.6 mg, 8.3 µmol, 12%). -(S)-131:

R_f = 0.14 (methylene chlo-ride : methanol 15:1). ¹H-NMR (300 MHz, (CD₃)₂SO): δ(ppm) 11.26 (s, 1H, NH), 9.51 (d, J = 5.7 Hz, 1H, CH_ar-6‘), 8.85 (dd, J = 9.2, 2.3 Hz, 1H, CH_ar-4), 8.36 (td, J = 7.8, 1.5 Hz, 1H, CH_ar-4‘), 8.23 (d, J = 2.6 Hz, 1H, CH_ar-8), 8.10 (td, J = 2.5, 0.8 Hz, 1H, CH_ar-2), 7.95 – 7.87 (m, 2H, CH_ar-3’ &

CHar-5’), 7.71 (d, J = 9.0 Hz, 1H, CHar-11), 7.24 (dd, J = 9.0, 2.7 Hz, 1H, CH_ar-10), 4.75 (d, J = 16.0 Hz, 1H, NCHH), 4.55 (d, J = 16.1 Hz, 1H, NCHH), 3.92 (s, 3H, OCH₃), 3.77 (dd, J = 9.4, 5.1 Hz, 1H, CH_), 2.50 – 2.48 (m, 1H, CH_H_), 2.28 – 2.10 (m, 2H, CHH& CHH), 1.89 – 1.74 (m, 1H, CH_H_), 1.47 (tt, J = 12.1, 6.1 Hz, 1H, CH_H_), 1.17 – 0.95 (m, 1H, CH_H_). IR (film):

ν (cm^-1) 2919, 1716, 1653, 1563, 1502, 1465, 1408, 1335, 1258, 1226, 1163, 1096, 1021, 924, 860, 814, 763, 725, 633, 582, 519, 478, 443. HRMS calculated for C₂₉H₂₂ClFN₅NaO₅Rh (M + Na)⁺ 700.0241, found (M + Na)⁺ 700.0264. -(S)-132:

R_f = 0.27 (methylene chloride : methanol 15:1). ¹H-NMR (300 MHz, (CD₃)₂SO):

δ(ppm) 11.31 (s, 1H, NH), 9.66 (d, J = 5.8 Hz, 1H, CH_ar-6’), 8.98 (dd, J = 9.1, 2.4 Hz, 1H, CH_ar-4), 8.70 (dt, J = 2.3, 1.1 Hz, 1H, CHar-8), 8.48 (td, J = 7.8, 1.4 Hz, 1H, CH_ar-4’), 8.21 (d, J = 2.6 Hz, 1H, CH_ar-2),

8.05 – 7.95 (m, 2H, CH_ar-3’ & CH_ar-5’), 6.92 (dd, J = 9.0, 2.7 Hz, 1H, CH_ar-10), 5.59 (d, J

= 9.0 Hz, 1H, CHar-11), 4.61 (d, J = 15.9 Hz, 1H, NCHH), 4.32 (d, J = 15.7 Hz, 1H, NCHH), 3.83 (s, 3H, OCH₃), 3.82 – 3.74 (m, 1H, CH_), 2.50 – 2.48 (m, 1H, CH_H_), 2.30 – 2.14 (m, 2H, CHH& CHH), 2.10 – 1.94 (m, 1H, CH_H_), 1.69 – 1.58 (m, 1H, CH_H_), 1.46 (dd, J = 15.5, 9.0 Hz, 1H, CH_H_). IR (film): ν(cm^-1) 2919, 1718, 1650, 1563, 1500, 1468, 1408, 1337, 1277, 1259, 1228, 1167, 1098, 1023, 993, 923, 893, 857, 825, 793, 727, 701, 636, 523, 475, 442. HRMS calcu-lated for C₂₉H₂₂ClFN₅NaO₅Rh (M + Na)⁺ 700.0241, found (M + Na)⁺ 700.0263.

5.2.3.11 Synthesis of organorhodium(III) complexes -(R)-131 and

-(R)-132

A suspension of 78 (34 mg, 75 µmol) and RhCl₃∙3H₂O (18.3 mg, 69 µmol) in an ethanol : water mixture (1:1, 15 mL) under nitrogen atmosphere in a sealed vessel was heated to 90 °C for 3 h. During this time the suspension turned from pale brown into dark red. The reaction mixture was then cooled down slightly to add (R)-105 (15.5 mg, 75 µmol). After addition of (R)-105, the reac-tion was further proceeded at 90 °C for 16 h.

The reaction mixture was then cooled down to ambient temperature and the solvent was removed in vacuo. The crude material was purified via column chromatography using methylene chloride : methanol (15:1  10:1). The separated diastereomers were further purified and concentrated via

prepar-ative TLC using methylene chlo-ride : methanol (15:1). The products were obtained as dark purple solids, -(R)-131 (10.3 mg, 15.2 µmol, 22%) and -(R)-132 (6.0 mg, 8.9 µmol, 13%). -(R)-131:

R_f = 0.14 (methylene chloride : methanol 15:1). ¹H-NMR (300 MHz, (CD₃)₂SO):

δ(ppm) 11.17 (s, 1H, NH), 9.50 (d, J = 5.7 Hz, 1H, CH_ar-6’), 8.85 (dd, J = 9.2, 2.2 Hz, 1H, CH_ar-4), 8.35 (td, J = 7.7, 1.4 Hz, 1H, CH_ar-4’), 8.22 (d, J = 2.6 Hz, 1H, CH_ar-8), 8.09 (td, J = 2.5, 0.8 Hz, 1H, CH_ar-2), 7.99 – 7.84 (m, 2H, CH_ar-3’ & CH_ar-5’), 7.70 (d, J = 8.9 Hz, 1H, CH_ar-11), 7.23 (dd, J = 9.0, 2.7 Hz, 1H, CHar-10), 4.74 (d, J = 15.9 Hz, 1H, NCHH), 4.54 (d, J = 16.5 Hz, 1H, NCHH), 3.91 (s, 3H, OCH₃), 3.77 (dd, J = 9.2, 4.9 Hz, 1H, CH_), 2.50 – 2.48 (m, 1H, CH_H_) 2.28 – 2.10 (m, 2H, CHH& CHH), 1.89 – 1.74 (m, 1H, CH_H_), 1.47 (tt, J = 12.1, 6.1 Hz, 1H, CH_H_), 1.17 – 0.95 (m, 1H, CH_H_).

13C-NMR (75 MHz, (CD₃)₂SO): δ(ppm) 182.54 (C_carbonyl), 170.54 (C_ar-7), 170.17 (C_ar-5), 160.25 (C_ar-2’), 156.93 (d, J = 249.7 Hz, Car-3), 154.05 (Car-9), 152.33 (Car-6’), 151.77 (C_ar-12b), 144.60 (C_ar), 141.20 (d, J

= 33.9 Hz, C_ar-2), 140.85 (C_ar), 140.10 (C_ar), 132.23 (C_ar), 126.21 (C_ar), 124.05 (C_ar), 123.43 (C_ar), 120.77 (d, J = 8.8 Hz, C_ar-4a), 119.15 (d, J = 20.0 Hz, Car-4), 116.68 (Car), 115.65 (Car), 114.70 (Car), 112.77 (Car), 106.28 (Car), 73.53 (C), 69.48 (NCH2), 61.53 (C_), 55.60 (OCH₃), 30.45 (C_), 23.87 (C_). IR (film): ν (cm^-1) 1751, 1711, 1652, 1562, 1502, 1467, 1409, 1332, 1284, 1204, 1162, 1023, 997, 919, 856, 816, 760, 695, 632, 581, 520, 476, 445, 404. HRMS calcu-lated for C29H23ClFN5O5Rh (M + H)⁺ 678.0421, found (M + H)⁺ 678.0427.

-(R)-132: Rf = 0.27 (methylene chlo-ride : methanol 15:1). ¹H-NMR (500 MHz, (CD₃)₂SO): δ(ppm) 9.65 (d, J = 5.7 Hz, 1H, CH_ar-6’), 8.98 (dd, J = 9.1, 2.4 Hz, 1H, CH_ar-4), 8.70 (dd, J = 2.2, 1.8 Hz, 1H, CH_ar-8), 8.47 (td, J = 7.8, 1.5 Hz, 1H, CH_ar-4’), 8.19 (d, J = 2.6 Hz, 1H, CH_ar-2), 8.02 (t, J = 6.8 Hz, 1H, CH_ar-5’), 7.98 (d, J = 7.9 Hz, 1H, CH_ar-3’), 6.91 (dd, J = 9.0, 2.7

Hz, 1H, CH_ar-10), 5.59 (d, J = 9.0 Hz, 1H, CH_ar-11), 4.62 (d, J = 15.7 Hz, 1H, NCHH), 4.32 (d, J = 15.6 Hz, 1H, NCHH), 3.82 (s, 3H, OCH₃), 3.82 – 3.77 (m, 1H, CH_a), 2.54 (dt, J = 11.2, 5.7 Hz, 1H, CH_H_), 2.29 – 2.18 (m, 2H, CH_H_& CH_H_), 2.09 – 2.00 (m, 1H, CH_H_), 1.64 (dp, J = 12.5, 6.3 Hz, 1H, CH_H_), 1.27 – 1.15 (m, 1H, CH_H_).

13C-NMR (126 MHz, (CD₃)₂SO): δ(ppm) 182.05 (C_carbonyl), 170.43 (C_ar-7), 170.07 (C_ar-5), 161.22 (C_ar-2’), 156.68 (d, J = 250.7 Hz, C_ar-3), 153.98 (C_ar-6’), 152.79 (C_ar-12b), 143.60 (C_ar), 141.41 (C_ar), 139.84 (C_ar), 138.31 (d, J = 35.1 Hz, CH_ar-2), 132.40 (C_ar), 126.45 (C_ar), 123.84 (C_ar), 123.71 (C_ar), 121.24 (d, J = 8.4 Hz, C_ar-4a), 119.80 (d, J = 20.2 Hz, C_ar-4), 116.43 (C_ar), 114.87 (C_ar), 113.36 (Car), 112.57 (Car), 107.09 (Car), 72.87 (C), 69.89 (NCH2), 61.14 (OCH3), 55.65 (C_), 30.25 (C_), 24.33 (C_). IR (film):

ν(cm^-1) 1752, 1714, 1652, 1562, 1499, 1470, 1408, 1336, 1285, 1207, 1167, 1055, 1025, 995, 920, 893, 856, 824, 793, 774, 699, 632, 614, 523. HRMS calculated for C₂₉H₂₂ClFN₅NaO₅Rh (M + Na)⁺ 700.0241, found (M + Na)⁺ 700.0262.

5.2.3.12 Synthesis of organorhodium(III) complexes -(S)-133 and -(S)-134

A suspension of 81 (45 mg, 75 µmol) and RhCl₃∙3H₂O (18.3 mg, 69 µmol) in an ethanol : water mixture (1:1, 15 mL) under nitrogen atmosphere in a sealed vessel was heated to 90 °C for 3 h. During this time the suspension turned from pale brown into dark red. The reaction mixture was then cooled

down slightly to add (S)-105 (15.5 mg, 75 µmol). After addition of (S)-105, the reac-tion was further proceeded at 90 °C for 16 h.

The reaction mixture was then cooled down to ambient temperature and the solvent was removed in vacuo. The crude material was purified via column chromatography using methylene chloride : methanol (35:1  10:1). The separated diastereomers were further purified and concentrated via prepar-ative TLC using methylene chlo-ride : methanol (15:1). The products were obtained as dark purple solids, -(S)-133 (7.8 mg, 11.1 µmol, 16%) and -(S)-134 (4.4 mg, 6.2 µmol, 9%). -(S)-133: Rf = 0.11 (methylene chloride : methanol 15:1).

1H-NMR (300 MHz, (CD₃)₂SO): δ(ppm) 11.34 (s, 1H, NH), 9.53 (d, J = 5.3 Hz, 1H, CH_ar-6’), 9.43 (s, 1H, CH_ar-4), 9.33 (d, J = 0.8 Hz, 1H, CH_ar-2), 8.39 (td, J = 7.8, 1.4 Hz, 1H, CH_ar-4’), 8.17 (d, J = 2.4 Hz, 1H, CH_ar-8), 7.97 – 7.89 (m, 3H, OH, CH_ar-3’&

CH_ar-5‘), 7.69 (d, J = 8.9 Hz, 1H, CH_ar-11), 7.14 (dd, J = 8.9, 2.5 Hz, 1H, CH_ar-10), 4.76 (d, J = 16.2 Hz, 1H, NCHH), 4.57 (d, J = 16.2 Hz, 1H, NCHH), 3.79 (dd, J = 9.4, 4.9 Hz, 1H, CH_a), 2.51 – 2.48 (m, 1H, CH_H_), 2.25 – 2.11 (m, 2H, CH_H_& CH_H_), 1.84 (dt, J = 17.9, 5.9 Hz, 1H, CH_H_), 1.48 (ddd, J = 17.8, 11.7, 5.9 Hz, 1H, CHH), 1.16 – 1.00 (m, 1H, CH_H_). IR (film): ν (cm^-1) 3226, 2923, 1757, 1712, 1613, 1558, 1526, 1496, 1420, 1332, 1295, 1244, 1178, 1135, 1089, 1054, 1026, 924, 864, 767, 729, 699, 640, 531, 505, 446. HRMS calculated for C₂₉H₂₀ClF₃N₅NaO₅Rh (M + Na)⁺ 736.0052, found (M + Na)⁺ 736.0074. -(S)-134:

R_f = 0.21 (methylene chloride : methanol 15:1). ¹H-NMR (300 MHz, (CD₃)₂SO):

δ(ppm) 11.38 (s, 1H, NH), 9.65 (d, J = 5.8 Hz, 1H, CH_ar-6’), 9.46 (d, J = 0.9 Hz, 1H, CH_ar-4), 8.81 (d, J = 0.9 Hz, 1H, CH_ar-4), 8.48 (td, J = 7.8, 1.4 Hz, 1H, CH_ar-4’), 8.15 (d, J = 2.4 Hz, 1H, CH_ar-8), 8.06 – 7.87 (m, 3H, OH, CH_ar-3’ & CH_ar-5‘), 6.80 (dd, J = 8.9, 2.5 Hz, 1H, CH_ar-10), 5.57 (d, J = 8.9 Hz, 1H, CHar-11), 4.63 (d, J = 15.7 Hz, 1H, NCHH), 4.33 (d, J = 15.7 Hz, 1H, NCHH),

3.83 (dd, J = 9.3, 4.5 Hz, 1H, CH_), 2.51 – 2.48 (m, 1H, CH_H_), 2.31 – 2.14 (m, 2H, CHH& CHH), 2.00 (td, J = 11.0, 5.5 Hz, 1H, CH_H_), 1.63 (ddd, J = 18.0, 11.9, 5.9 Hz, 1H, CH_H_), 1.14 – 0.97 (m, 1H, CH_H_).

IR (film): ν(cm^-1) 3267, 2919, 1711, 1660, 1568, 1501, 1463, 1420, 1391, 1332, 1295, 1252, 1218, 1127, 1085, 1048, 1020, 933, 901, 860, 821, 781, 729, 697, 633, 530, 503, 481, 447, 409. HRMS calculated for C₂₉H₂₀ClF₃N₅NaO₅Rh (M + Na)⁺ 736.0052, found (M + Na)⁺ 736.0076.

5.2.3.13 Synthesis of organorhodium(III) complexes -(R)-133 and

-(R)-134

A suspension of 81 (45 mg, 75 µmol) and RhCl₃∙3H₂O (18.3 mg, 69 µmol) in an ethanol : water mixture (1:1, 15 mL) under nitrogen atmosphere in a sealed vessel was heated to 90 °C for 3 h. During this time the suspension turned from pale brown into dark red. The reaction mixture was then cooled down slightly to add (R)-105 (15.5 mg, 75 µmol). After addition of (R)-105, the reac-tion was further proceeded at 90 °C for 16 h.

The reaction mixture was then cooled down to ambient temperature and the solvent was removed in vacuo. The crude material was purified via column chromatography using methylene chloride : methanol (20:1  10:1). The separated diastereomers were further purified and concentrated via prepar-ative TLC using methylene chlo-ride : methanol (15:1). The products were obtained as dark purple solids, -(R)-133

(8.6 mg, 12.4 µmol, 18%) and -(R)-134 (4.9 mg, 6.9 µmol, 10%). -(R)-133:

R_f = 0.11 (methylene chloride : methanol 15:1). ¹H-NMR (600 MHz, (CD₃)₂SO):

δ(ppm) 11.33 (s, 1H, NH), 9.53 (d, J = 5.5 Hz, 1H, CH_ar-6’), 9.44 (s, 1H, CH_ar-4), 9.33 (d, J = 1.0 Hz, 1H, CH_ar-2), 8.38 (td, J = 7.8, 1.5 Hz, 1H, CH_ar-4’), 8.17 (d, J = 2.2 Hz, 1H, CH_ar-8), 7.99 – 7.92 (m, 3H, OH, CH_ar-3’ &

CH_ar-5‘), 7.91 (s, 1H, OH), 7.68 (d, J = 8.7 Hz, 1H, CH_ar-11), 7.14 (dd, J = 8.8, 2.5 Hz, 1H, CH_ar-10), 4.76 (d, J = 16.2 Hz, 1H, NCHH), 4.57 (d, J = 16.2 Hz, 1H, NCHH), 3.79 (dd, J = 9.5, 5.0 Hz, 1H, CH), 2.51 – 2.48 (m, 1H, CH_H_), 2.20 (td, J = 11.7, 5.9 Hz, 2H, CH_H_& CHH_), 1.84 (td, J = 11.8, 5.6 Hz, 1H, CH_H_), 1.55 – 1.40 (m, 1H, CH_H_), 1.16 – 1.00 (m, 1H, CH_H_).

13C-NMR (151 MHz, (CD₃)₂SO): δ(ppm) 182.42 (C_carbonyl), 170.42 (C_ar-7), 170.00 (C_ar-5), 160.32 (C_ar-2’), 152.18 (C_ar-9), 151.86 (C_ar-6’), 151.07 (C_ar-12b), 144.20 (C_ar), 143.78 (C_ar), 140.93 (C_ar), 133.50 (C_ar), 132.55 (C_ar), 132.11 (C_ar), 126.25 (C_ar), 123.85 (Car), 121.75 (Car), 119.25 (Car), 118.11 (C_ar), 116.10 (C_ar), 115.77 (C_ar), 112.92 (C_ar), 111.33 (C_ar), 108.52 (C_ar), 73.41 (C_), 69.36 (NCH₂), 61.52 (C_), 30.31 (C), 23.78 (C). Due to the signal to noise ratio a unambiguous assignment of the CF₃ carbon signals was not possible. IR (film): ν (cm^-1) 1750, 1709, 1657, 1606, 1502, 1461, 1421, 1391, 1330, 1295, 1252, 1212, 1171, 1129, 1084, 1021, 934, 901, 858, 822, 777, 696, 631, 530, 500, 481. HRMS calculated for C29H20ClF3N5NaO5Rh (M + Na)⁺ 736.0052, found (M + Na)⁺ 736.0074.

-(R)-134: Rf = 0.21 (methylene chlo-ride : methanol 15:1). ¹H-NMR (300 MHz, (CD₃)₂SO): δ(ppm) 9.65 (d, J = 5.4 Hz, 1H, CH_ar-6‘), 9.47 – 9.45 (m, 1H, CH_ar-4), 8.81 (d, J = 0.8 Hz, 1H, CH_ar-2), 8.48 (td, J = 7.8, 1.3 Hz, 1H, CH_ar-4‘), 8.15 (d, J = 2.4 Hz, 1H, CH_ar-8), 8.06 – 7.96 (m, 3H, OH CH_ar-3’ &

CH_ar-5‘), 6.81 (dd, J = 8.9, 2.5 Hz, 1H, CH_ar-10), 5.57 (d, J = 8.9 Hz, 1H, CH_ar-9), 4.63 (d, J = 15.4 Hz, 1H, NCHH), 4.33 (d, J

= 15.4 Hz, 1H, NCHH), 3.83 (dd, J = 9.2, 4.5

Hz, 1H, CH_), 2.58 – 2.52 (m, 1H, CH_H_), 2.32 – 2.14 (m, 2H, CH_H_& CHH_), 2.00 (td, J = 11.6, 5.5 Hz, 1H, CHH), 1.64 (tt, J

= 11.6, 5.8 Hz, 1H, CH_H_), 1.14 – 0.97 (m, 1H, CH_H_). ¹³C-NMR (75 MHz, (CD₃)₂SO):

δ(ppm) 182.05 (C_carbonyl), 170.38 (C_ar-7), 169.97 (C_ar-5), 161.19 (C_ar-2‘), 152.65 (C_ar-9), 152.19 (C_ar-6‘), 151.59 (C_ar-12b), 143.51 (Car), 143.31 (Car), 141.43 (Car), 139.65 (C_ar), 137.21 (C_ar), 132.71 (C_ar), 126.48 (C_ar), 124.12 (C_ar), 123.72 (C_ar), 121.18 (C_ar), 119.65 (C_ar), 118.06 (C_ar), 116.40 (C_ar), 113.61 (C_ar), 112.76 (C_ar), 109.09 (C_ar), 72.84 (C_), 69.96 (NCH₂), 61.29 (C_), 30.25 (C_), 24.50 (C_). Due to the signal to noise ratio a unambiguous assign-ment of the CF₃ carbon signals was not possible. IR (film): ν(cm^-1) 1757, 1715, 1663, 1611, 1565, 1497, 1419, 1337, 1293, 1246, 1134, 1083, 1049, 1022, 994, 914, 858, 822, 790, 762, 697, 629, 528, 499, 443. HRMS calculated for C₂₉H₂₀ClF₃N₅NaO₅Rh (M + Na)⁺ 736.0052, found (M + Na)⁺ 736.0072.

5.2.3.14 Synthesis of organorhodium(III) complexes -(S)-135 and -(S)-136

A suspension of 82 (42.1 mg, 75 µmol) and RhCl₃∙3H₂O (18.3 mg, 69 µmol) in an ethanol : water mixture (1:1, 15 mL) under nitrogen atmosphere in a sealed vessel was heated to 90 °C for 3 h.

During this time the suspension turned from pale brown into dark red. The reaction mix-ture was then cooled down slightly to add (S)-105 (15.5 mg, 75 µmol). After addition of

(S)-105, the reaction was further proceeded at 90 °C for 16 h. The reaction mixture was then cooled down to ambient temperature and the solvent was removed in vacuo. The crude material was purified via column chromatography using methylene chlo-ride : methanol (25:1  10:1). The separat-ed diastereomers were further purifiseparat-ed and concentrated via preparative TLC using methylene chloride : methanol (15:1). The products were obtained as dark purple sol-ids, -(S)-135 (7.9 mg, 11.7 µmol, 17%) and

-(S)-136 (5.1 mg, 7.6 µmol, 11%).

-(S)-135: Rf = 0.11 (methylene chlo-ride : methanol 15:1). ¹H-NMR (300 MHz, (CD3)2SO): δ(ppm) 11.12 (s, 1H, NH), 9.51 (dd, J = 5.8, 0.7 Hz, 1H, CH_ar-6’), 8.49 (d, J

= 2.3 Hz, 1H, CH_ar-4), 8.36 (td, J = 7.8, 1.5 Hz, 1H, CH_ar-4’), 8.09 (d, J = 2.3 Hz, 1H, CH_ar-8), 7.96 – 7.85 (m, 2H, CH_ar-3’ &

CH_ar-5’), 7.56 (d, J = 8.8 Hz, 1H, CH_ar-11), 7.45 (dd, J = 2.3, 0.9 Hz, 1H, CH_ar-2), 7.01 (dd, J = 8.8, 2.5 Hz, 1H, CH_ar-10), 4.70 (d, J

= 16.3 Hz, 1H, NCHH), 4.55 (d, J = 16.3 Hz, 1H, NCHH), 3.97 (s, 3H, OCH₃), 3.77 (dd, J

= 9.5, 4.8 Hz, 1H, CH_), 2.58 – 2.52 (m, 1H, CH_H_), 2.30 – 2.21 (m, 2H, CH_H_&

CH_H_), 2.01 – 1.92 (m, 1H, CH_H_), 1.85 (dd, J = 12.5, 6.4 Hz, 1H, CHH), 1.67 – 1.59 (m, 1H, CH_H_). ¹³C-NMR (126 MHz, (CD₃)₂SO): δ(ppm) 182.35 (C_carbonyl), 170.83 (C_ar-7), 170.33 (C_ar-5), 160.30 (C_ar-2’), 154.88 (Car-3), 152.96 (Car-9), 151.56 (C_ar-6’), 151.47 (C_ar-12b), 143.67 (C_ar), 142.17 (C_ar), 140.70 (C_ar), 137.46 (C_ar), 131.67 (C_ar), 129.59 (C_ar), 126.06 (C_ar), 123.81 (C_ar), 121.68 (C_ar), 73.50 (C_), 69.78 (NCH₂), 61.45 (C_), 56.21 (OCH₃), 31.28 (C), 22.09 (C). IR (film): ν (cm^-1) 2917, 2850, 1716, 1608, 1566, 1445, 1406, 1373, 1341, 1229, 1094, 1019, 931, 871, 800, 723.

HRMS calculated for C₂₉H₂₃ClN₅NaO₆Rh (M + Na)⁺ 698.0284, found (M + Na)⁺ 698.0286. -(S)-136: R_f = 0.24 (methylene chloride : methanol 15:1). ¹H-NMR (300 MHz, (CD₃)₂SO): δ(ppm) 11.15 (s, 1H, NH), 9.65 (d, J = 5.2 Hz, 1H, CH_ar-6‘), 9.18 (s, 1H, OH), 8.60 (d, J = 2.4 Hz, 1H, CH_ar-4),

8.46 (td, J = 7.8, 1.5 Hz, 1H, CH_ar-4‘), 8.34 (dd, J = 2.4, 0.8 Hz, 1H, CH_ar-2), 8.08 (d, J = 2.4 Hz, 1H, CHar-8), 8.04 – 7.92 (m, 2H, CH_ar-3’ & CH_ar-5’), 6.67 (dd, J = 8.8, 2.5 Hz, 1H, CH_ar-10), 5.46 (d, J = 8.8 Hz, 1H, CH_ar-11), 4.70 – 4.52 (m, 2H, NCH₂), 4.12 (s, 3H, OCH₃), 3.80 (dd, J = 5.2, 4.1 Hz, 1H, CH_), 2.51 – 2.48 (m, 1H, CH_H_), 2.07 – 1.88 (m, 2H, CH_H_& CH_H_), 1.62 (dt, J = 11.5, 5.8 Hz, 1H, CH_H_), 1.56 – 1.38 (m, 1H, CH_H_), 1.17 – 0.98 (m, 1H, CH_H_). IR (film): ν(cm^-1) 2957, 2918, 2850, 1716, 1577, 1459, 1407, 1372, 1341, 1230, 1093, 1019, 931, 871, 800, 723, 468. HRMS calculated for C₂₉H₂₃ClN₅NaO₆Rh (M + Na)⁺ 698.0284, found (M + Na)⁺ 698.0286.

5.2.3.15 Synthesis of organorhodium(III) complexes -(R)-135 and

-(R)-136

A suspension of 82 (42 mg, 75 µmol) and RhCl₃∙3H₂O (18.3 mg, 69 µmol) in an ethanol : water mixture (1:1, 15 mL) under nitrogen atmosphere in a sealed vessel was heated to 90 °C for 3 h. During this time the suspension turned from pale brown into dark red. The reaction mixture was then cooled down slightly to add (R)-105 (15.5 mg, 75 µmol). After addition of (R)-105, the reac-tion was further proceeded at 90 °C for 16 h.

The reaction mixture was then cooled down to ambient temperature and the solvent was removed in vacuo. The crude material was purified via column chromatography using methylene chloride : methanol (20:1  10:1). The separated diastereomers were

further purified and concentrated via prepar-ative TLC using methylene chlo-ride : methanol (15:1). The products were obtained as dark purple solids-(R)-135 (8.8 mg, 13.1 µmol, 19%) and -(R)-136 (4.2 mg, 6.2 µmol, 9%). -(R)-135: R_f = 0.11 (methylene chloride : methanol 15:1).

1H-NMR (600 MHz, (CD₃)₂SO): δ(ppm) 11.10 (s, 1H, NH), 9.51 (d, J = 5.5 Hz, 1H, CH_ar-6’), 9.22 (s, 1H, OH), 8.48 (d, J = 2.3 Hz, 1H, CH_ar-4), 8.35 (td, J = 7.8, 1.4 Hz, 1H, CH_ar-4’), 8.09 (d, J = 2.5 Hz, 1H, CH_ar -8), 7.96 – 7.84 (m, 2H, CH_ar-3’ & CH_ar-5’), 7.55 (d, J = 8.8 Hz, 1H, CH_ar-11), 7.44 (d, J

= 2.2 Hz, 1H, CHar-2), 7.01 (dd, J = 8.8, 2.5 Hz, 1H, CHar-10), 4.69 (d, J = 16.1 Hz, 1H, NCHH), 4.54 (d, J = 16.2 Hz, 1H, NCHH), 3.97 (s, 3H, OCH₃), 3.77 (dd, J = 9.6, 4.9 Hz, 1H, CH_a), 2.48 – 2.44 (m, 1H, CH_H_), 2.25 (dt, J = 11.7, 5.7 Hz, 1H, CH_H_), 2.21 – 2.13 (m, 1H, CH_H_), 1.85 (td, J = 11.6, 5.4 Hz, 1H, CH_H_), 1.51 – 1.41 (m, 1H, CH_H_), 1.16 – 1.08 (m, 1H, CH_H_). IR (film):

ν (cm^-1) 1749, 1707, 1630, 1567, 1496, 1449, 1419, 1339, 1297, 1260, 1215, 1054, 1015, 927, 867, 819, 764, 732, 698, 635, 568, 510, 482, 448, 401. HRMS calculated for C₂₉H₂₃ClN₅NaO₆Rh (M + Na)⁺ 698.0284, found (M + Na)⁺ 698.0286. -(R)-136:

R_f = 0.24 (methylene chloride : methanol 15:1). ¹H-NMR (500 MHz, (CD₃)₂SO):

δ(ppm) 9.64 (d, J = 5.7 Hz, 1H, CH_ar-6’), 9.21 (bs, 1H, OH), 8.59 (d, J = 2.4 Hz, 1H, CH_ar-4), 8.45 (td, J = 7.8, 1.5 Hz, 1H, CH_ar-4’), 8.34 (d, J = 2.4 Hz, 1H, CH_ar-2), 8.07 (d, J = 2.5 Hz, 1H, CHar-8), 8.04 – 7.98 (m, 1H, CH_ar-5’), 7.96 (d, J = 8.0 Hz, 1H, CH_ar-3’), 6.67 (dd, J = 8.8, 2.5 Hz, 1H, CH_ar-10), 5.45 (d, J = 8.8 Hz, 1H, CH_ar-11), 4.59 (d, J = 15.5 Hz, 1H, NCHH), 4.30 (d, J

= 15.6 Hz, 1H, NCHH), 4.12 (s, 3H, OCH₃), 3.79 (dd, J = 9.4, 4.5 Hz, 1H, CH_), 2.54 – 2.51 (m, 1H, CH_H_), 2.27 – 2.16 (m, 2H, CH_H_& CH_H_), 2.05 – 1.95 (m, 1H, CH_H_), 1.67 – 1.58 (m, 1H, CH_H_), 1.13 (tt, J = 13.5, 6.6 Hz, 1H, CH_H_). IR (film):

ν(cm^-1) 1748, 1705, 1646, 1566, 1492, 1456, 1414, 1337, 1297, 1263, 1215, 1018, 925,

864, 818, 763, 701, 666, 634, 518, 484.

HRMS calculated for C₂₉H₂₃ClN₅NaO₆Rh (M + Na)⁺ 698.0284, found (M + Na)⁺ 698.0285.

5.2.3.16 Synthesis of organorhodium(III) complexes -(S)-137 and -(S)-138

A suspension of 83 (34.6 mg, 75 µmol) and RhCl₃∙3H₂O (18.3 mg, 69 µmol) in an ethanol : water mixture (1:1, 15 mL) under nitrogen atmosphere in a sealed vessel was heated to 90 °C for 3 h.

During this time the suspension turned from pale brown into dark red. The reaction mix-ture was then cooled down slightly to add (S)-105 (15.5 mg, 75 µmol). After addition of (S)-105, the reaction was further proceeded at 90 °C for 16 h. The reaction mixture was then cooled down to ambient temperature and the solvent was removed in vacuo. The crude material was purified via column chromatography using methylene chlo-ride : methanol (25:1  10:1). The separat-ed diastereomers were further purifiseparat-ed and concentrated via preparative TLC using methylene chloride : methanol (15:1). The products were obtained as dark purple sol-ids, -(S)-137 (11.9 mg, 17.3 µmol, 25%) and -(S)-138 (6.6 mg, 9.7 µmol, 14%).

-(S)-137: Rf = 0.16 (methylene chlo-ride : methanol 15:1). ¹H-NMR (300 MHz, (CD₃)₂SO): δ(ppm) 11.17 (s, 1H, NH), 9.51 (d, J = 5.7 Hz, 1H, CH_ar-6’), 8.50 (d, J = 2.3 Hz, 1H, CH_ar-4), 8.36 (td, J = 7.8, 1.5 Hz, 1H, CH_ar-4’), 8.20 (d, J = 2.6 Hz, 1H, CH_ar-8), 7.97 – 7.84 (m, 2H, CH_ar-3’ &

CH_ar-5’), 7.66 (d, J = 8.9 Hz, 1H, CH_ar-11), 7.48 (dd, J = 2.3, 0.8 Hz, 1H, CH_ar-2), 7.19 (dd, J = 8.9, 2.7 Hz, 1H, CHar-10), 4.72 (d, J

= 16.2 Hz, 1H, NCHH), 4.64 (d, J = 15.7 Hz, 1H, NCHH), 3.98 (s, 3H, OCH₃), 3.91 (s, 3H, OCH₃), 3.78 (dd, J = 9.5, 4.8 Hz, 1H, CH_), 2.58 – 2.52 (m, 1H, CHH), 2.29 – 2.11 (m, 2H, CH_H_& CH_H_), 1.70 – 1.57 (m, 1H, CH_H_), 1.46 (ddd, J = 20.1, 13.3, 6.6 Hz, 2H, CH_H_& CHH_). IR (film): ν (cm^-1) 3511, 3432, 3230, 2920, 2852, 1714, 1655, 1567, 1496, 1462, 1428, 1343, 1264, 1215, 1174, 1101, 1061, 1020, 925, 859, 820, 776, 728, 698, 658, 630, 575, 518, 476, 443, 400.

HRMS calculated for C₃₀H₂₅ClN₅NaO₆Rh (M + Na)⁺ 712.0441, found (M + Na)⁺ 712.0468. -(S)-138: Rf = 0.27 (methylene chloride : methanol 15:1). ¹H-NMR (300 MHz, (CD₃)₂SO): δ(ppm) 11.21 (s, 1H, NH), 9.66 (d, J = 5.7 Hz, 1H, CH_ar-6’), 8.61 (d, J = 2.4 Hz, 1H, CH_ar-4), 8.46 (td, J = 7.8, 1.5 Hz, 1H, CH_ar-4’), 8.36 (dd, J = 2.4, 0.8 Hz, 1H, CHar-2), 8.18 (d, J = 2.6 Hz, 1H, CH_ar-8), 8.04 – 7.93 (m, 2H, CH_ar-3’ &

CH_ar-5’), 6.86 (dd, J = 9.0, 2.7 Hz, 1H, CH_ar-10), 5.55 (d, J = 8.9 Hz, 1H, CH_ar-11), 4.60 (d, J = 15.9 Hz, 1H, NCHH), 4.31 (d, J

= 15.7 Hz, 1H, NCHH), 4.13 (s, 3H, OCH3), 3.82 (s, 3H, OCH₃), 3.79 (d, J = 4.8 Hz, 1H, CH), 2.58 – 2.52 (m, 1H, CHH), 2.25 – 2.14 (m, 2H, CH_H_& CH_H_), 2.01 (dt, J = 18.9, 5.6 Hz, 1H, CH_H_), 1.71 – 1.57 (m, 1H, CH_H_), 1.54 – 1.39 (m, 1H, CH_H_). IR (film): ν(cm^-1) 3350, 2971, 1599, 1451, 1388, 1297, 1270, 1235, 1179, 1155, 1099, 1011, 971, 911, 861, 831, 780, 739, 701, 655, 595.

HRMS calculated for C₃₀H₂₅ClN₅NaO₆Rh (M + Na)⁺ 712.0441, found (M + Na)⁺ 712.0466.

5.2.3.17 Synthesis of organorhodium(III) complexes -(R)-137 and

-(R)-138

A suspension of 83 (34.6 mg, 75 µmol) and RhCl₃∙3H₂O (18.3 mg, 69 µmol) in an ethanol : water mixture (1:1, 15 mL) under nitrogen atmosphere in a sealed vessel was heated to 90 °C for 3 h.

During this time the suspension turned from pale brown into dark red. The reaction mix-ture was then cooled down slightly to add (R)-105 (15.5 mg, 75 µmol). After addition of (R)-105, the reaction was further proceeded at 90 °C for 16 h. The reaction mixture was then cooled down to ambient temperature and the solvent was removed in vacuo. The crude material was purified via column chromatography using methylene chlo-ride : methanol (25:1  10:1). The separat-ed diastereomers were further purifiseparat-ed and concentrated via preparative TLC using methylene chloride : methanol (15:1). The products were obtained as dark purple sol-ids, -(R)-137 (11.4 mg, 16.6 µmol, 24%) and -(R)-138 (6.6 mg, 9.7 µmol, 14%).

-(R)-137: Rf = 0.16 (methylene chlo-ride : methanol 15:1). ¹H-NMR (300 MHz, (CD₃)₂SO): δ(ppm) 9.51 (d, J = 5.7 Hz, 1H, CH_ar-6’), 8.50 (d, J = 2.3 Hz, 1H, CH_ar-4), 8.36 (td, J = 7.8, 1.5 Hz, 1H, CH_ar-4’), 8.20 (d, J = 2.6 Hz, 1H, CH_ar-8), 7.98 – 7.87 (m, 2H, CH_ar-3’ & CH_ar-5’), 7.65 (d, J = 8.9 Hz, 1H, CHar-11), 7.48 (dd, J = 2.3, 0.8 Hz, 1H, CH_ar-2), 7.19 (dd, J = 9.0, 2.7 Hz, 1H, CH_ar-10), 4.72 (d, J = 16.1 Hz, 1H, NCHH), 4.55 (d, J = 16.4 Hz, 1H, NCHH), 3.97 (s,

3H, OCH₃), 3.90 (s, 3H, OCH₃), 3.78 (dd, J

= 9.4, 4.8 Hz, 1H, CH_), 2.47 – 2.41 (m, 1H, CH_H_), 2.31 – 2.08 (m, 2H, CH_H_&

CH_H_), 1.92 – 1.78 (m, 1H, CH_H_), 1.53 – 1.38 (m, 1H, CHH), 1.18 – 1.02 (m, 1H, CH_H_). ¹³C-NMR (75 MHz, (CD₃)₂SO):

δ(ppm) 182.43 (C_carbonyl), 170.88 (C_ar-7), 170.34 (C_ar-5), 160.32 (C_ar-2’), 155.01 (Car-3/Car-9), 153.72 (Car-9/Car-3), 153.08 (C_ar-6’), 151.63 (C_ar-12b), 144.57 (C_ar), 142.58 (C_ar), 140.76 (C_ar), 137.52 (C_ar), 132.97 (C_ar), 131.68 (C_ar), 126.12 (C_ar), 123.96 (C_ar), 123.50 (C_ar), 121.74 (C_ar), 115.95 (C_ar), 115.28 (C_ar), 113.84 (C_ar), 112.77 (C_ar), 112.10 (C_ar), 106.36 (C_ar), 73.53 (C_), 65.07 (NCH₂) 61.53 (C_), 56.27 (OCH₃), 55.58 (OCH₃), 30.40 (C_), 23.90 (C_). IR (film): ν (cm^-1) 1748, 1707, 1652, 1567, 1499, 1465, 1425, 1340, 1269, 1211, 1145, 1018, 929, 859, 815, 759, 696, 664, 631, 515, 474, 446, 400. HRMS calculated for C30H25ClN5NaO6Rh (M + Na)⁺ 712.0441, found (M + Na)⁺ 712.0461. -(R)-138:

R_f = 0.27 (methylene chloride : methanol 15:1). ¹H-NMR (500 MHz, (CD₃)₂SO):

δ(ppm) 9.65 (d, J = 5.8 Hz, 1H, CH_ar-6’), 8.61 (d, J = 2.4 Hz, 1H, CH_ar-4), 8.46 (td, J = 7.8, 1.5 Hz, 1H, CH_ar-4‘), 8.37 (dd, J = 2.4, 0.6 Hz, 1H, CH_ar-2), 8.18 (d, J = 2.6 Hz, 1H, CH_ar-8), 8.04 – 7.99 (m, 1H, CH_ar-5‘), 7.97 (d, J = 7.7 Hz, 1H, CH_ar-3‘), 6.86 (dd, J = 8.9, 2.7 Hz, 1H, CH_ar-10), 5.55 (d, J = 9.0 Hz, 1H, CH_ar-11), 4.60 (d, J = 15.7 Hz, 1H, NCHH), 4.31 (d, J = 15.7 Hz, 1H, NCHH), 4.13 (s, 3H, OCH₃), 3.81 (s, 3H, OCH₃), 3.79 (d, J = 4.7 Hz, 1H, CH_), 2.55 – 2.51 (m, 1H, CH_H_), 2.28 – 2.17 (m, 2H, CH_H_&

CH_H_), 2.00 (td, J = 12.1, 5.6 Hz, 1H, CHH), 1.68 – 1.58 (m, 1H, CHH), 1.13 (tt, J = 14.7, 7.2 Hz, 1H, CH_H_). ¹³C-NMR (126 MHz, (CD₃)₂SO): δ(ppm) 182.01 (C_carbonyl), 170.86 (C_ar-7), 170.31 (C_ar-5), 161.15 (C_ar-2‘), 154.85 (C_ar-3/C_ar-9), 153.67 (C_ar-9/C_ar-3), 153.60 (C_ar-6‘), 152.58 (C_ar-12b), 143.56 (C_ar), 141.25 (C_ar), 140.28 (C_ar), 137.24 (C_ar), 131.84 (C_ar), 126.32 (C_ar), 123.95 (C_ar), 123.58 (C_ar), 122.12 (C_ar), 115.71 (Car), 113.90 (Car), 113.36 (Car),

112.68 (C_ar), 112.17 (C_ar), 107.18 (C_ar), 72.75 (C_), 69.89 (NCH₂) 61.09 (C_), 56.68 (OCH₃), 55.64 (OCH₃), 30.18 (C_), 24.38 (C_). IR (film): ν(cm^-1) 1818, 1751, 1708, 1648, 1563, 1492, 1466, 1413, 1332, 1287, 1263, 1209, 1169, 1059, 1003, 880, 854, 821, 779, 760, 698, 670, 625, 521, 478.

HRMS calculated for C₃₀H₂₅ClN₅NaO₆Rh (M + Na)⁺ 712.0441, found (M + Na)⁺ 712.0466.

5.2.3.18 Synthesis of organorhodium(III) complex-(S)-191

80 (50.0 mg, 0.13 mmol) was sus-pended in a mixture of ethanol/water (1:1, 15 mL) and rhodium(III)-chloride trihydrate (34.7 mg, 0.13 mmol) was added. The mix-ture was reacted at 90 °C for 3 h. Then, lig-and (S)-178 (30.2 mg, 0.13 mmol) was add-ed and the reaction was continuadd-ed at 90 °C for 16 h. The solvent was evaporated under reduced pressure and the crude material was subjected to column chromatography using methylene chloride : methanol (20:1) followed by preparative TLC using meth-ylene chloride : methanol (15:1). The prod-uct -(S)-191 was obtained as red solid (6.5 mg, 9.1 µmol, 7%). R_f = 0.45 (methy-lene chloride : methanol 15:1). ¹H-NMR (300 MHz, (CD3)2SO): δ(ppm) 9.69 (d, J = 5.6 Hz, 1H, CH_ar-6’), 9.25 (dd, J = 8.4 Hz, 0.9 Hz, 1H, CH_ar-4), 8.78 (d, J = 5.2 Hz, 1H, CH_ar-2), 8.68 (d, J = 7.4 Hz, 1H, CH_ar-8), 8.45 (dd, J

= 7.8 Hz, 1.3 Hz, 1H, CH_ar-4’), 8.06 – 7.96 (m, 3H, 3xCH_ar), 7.41 – 7.15 (m, 6H,

6xCH_ar), 7.10 – 6.99 (m, 1H, CH_ar-10), 5.54 (d, J = 8.1 Hz, 1H, CH_ar-11), 4.93 (s, 2H, CH_2benzyl), 4.23-4.07 (m, 3H, NCH₂ & CH_), 2.21-2.12 (m, 1H, CH_), 0.86 (d, J = 7.0 Hz, 6H, (CH_32). IR (film): ν (cm^-1) 3384, 1691, 1638, 1424, 1388, 1353, 1022, 995, 763, 698, 631, 552, 429. HRMS calculated for C₃₅H₂₉ClN₅O₄RhNa (M + Na)⁺ 744.0855, found (M + Na)⁺ 744.0857.

5.2.3.19 Synthesis of organorhodium(III) complex -(S)-194

77 (58.4 mg, 0.13 mmol) was sus-pended in a mixture of ethanol/water (1:1, 15 mL) and rhodium(III)-chloride trihydrate (34.7 mg, 0.13 mmol) was added. The mix-ture was reacted at 90 °C for 3 h. Then, lig-and (S)-178 (30.2 mg, 0.13 mmol) was add-ed and the reaction was continuadd-ed at 90 °C for 16 h. The solvent was evaporated under reduced pressure and the crude material was subjected to column chromatography using methylene chloride : methanol (20:1

10:1) followed by preparative TLC using methylene chloride : methanol (15:1). The product -(S)-194 was obtained as purple solid (15.9 mg, 23.4 µmol, 18%,). Rf = 0.41 (methylene chloride : methanol 15:1). ¹ H-NMR (300 MHz, (CD₃)₂SO): δ(ppm) 9.65 (d, J = 5.5 Hz, 1H, CH_ar-6’), 9.30 (s, 1H, OH), 8.95 (dd, J = 9.1 Hz, 2.3 Hz, 1H, CH_ar-4), 8.56 (s, 1H, CHar), 8.45 (ddd, J = 8.8 Hz, 7.7 Hz, 1.0 Hz, 1H, CH_ar-4’), 8.13 (d, J = 2.3 Hz, CH_ar-2), 8.03-7.96 (m, 2H, CH_ar-3‘ &

CH_ar-5’), 7.12 (s, 1H, CH_ar), 6.69 (dd, J = 6.4 Hz, J = 2.3 Hz, 1H, CH_ar-10), 5.35 (d, J = 8.8

Hz, 1H, CH_ar-11), 4.25-4.09 (m, 3H, NCH₂ &

CH_), 3.18 (s, 3H, NCH₃), 2.24-2.11 (m, 1H, CH_), 0.88 (d, J = 7.2 Hz, 3H, CH_3), 0.58 (d, J = 6.9 Hz, 3H, CH_3). IR (film): ν (cm^-1) 3393, 2960, 2874, 1746, 1695, 1653, 1566, 1464, 1416, 1374, 1331, 1300, 1158, 1029, 884, 803, 740, 610, 510, 456. HRMS calcu-lated for C₂₉H₂₄ClFN₅O₅RhNa (M + Na)⁺ 702.0397, found (M + Na)⁺ 702.0392.

5.2.3.20 Synthesis of organorhodium(III) complexes -(R)-195 and

-(S)-195

77 (60.0 mg, 139 µmol) was sus-pended in a mixture of ethanol/water (1:1, 15 mL) and rhodium(III)-chloride trihydrate (36.3 mg, 139 µmol) was added. The mix-ture was reacted at 90 °C for 3 h. Then, lig-and (R)-182 (37.1 mg, 153 µmol) was added and the reaction was continued at 90 °C for 16 h. The solvent was evaporated under reduced pressure and the crude material was subjected to column chromatography using methylene chloride : methanol (50:1

 5:1) followed by preparative TLC using methylene chloride : methanol (20:1). The racemic products -(R)-195 and -(S)-195 were obtained as purple solid (8.9 mg, 12.5 µmol, 9%). Rf = 0.85 (methylene chlo-ride : methanol 10:1). ¹H-NMR (300 MHz, (CD₃)₂SO): δ(ppm) 9.72 (d, J = 5.9 Hz, 1H, CH_ar-6’), 9.27 (s, 1H, OH), 8.98-8.49 (dd, J = 9.0, 2.4 Hz, 1H, CH_ar), 8.81 (s, 1H, CH_ar), 8.47 (m, 1H, CH_ar), 8.03 (m, 3H, 3xCH_ar), 7.78 (m, 1H, CH_ar), 7.13 (m, 5H, 5xCH_ar),

6.66 (m, 1H, CH_ar-10), 5.31 (m, 1H, CH_ar-11), 4.45 (m, 2H, NCH₂), 4.02-3.96 (m, 1H, CH_), 3.16 (s, 3H, NCH₃).

5.2.3.21 Synthesis of organorhodium(III) complexes -196

77 (20.0 mg, 44 µmol) was suspend-ed in a mixture of ethanol/water (1:1, 15 mL) and rhodium(III)-chloride trihydrate (11.5 mg, 44 µmol) was added. The mixture was reacted at 90 °C for 3 h. Then, ligand 189 (8.6 mg, 48 µmol) was added and the reaction was continued at 90 °C for 16 h.

The solvent was evaporated under reduced pressure and the crude material was sub-jected to column chromatography using methylene chloride : methanol (30:1  5:1) followed by preparative TLC using meth-ylene chloride : methanol (20:1). The race-mic products -(R)-195 and -(S)-195 was obtained as dark green solid (4.9 mg, 7.5 µmol, 17%). Rf = 0.45 (methylene chlo-ride : methanol 10:1). ¹H-NMR (300 MHz, (CD₃)₂SO): δ(ppm) 9.63 (d, J = 5.7 Hz, 1H, CH_ar-6’), 9.31 (s, 1H, OH), 8.94 (dd, J = 9.2, 2.3 Hz, 1H, CH_ar-4’), 8.73 (dd, J = 2.2, 1.6 Hz, 1H, CH_ar-2), 8.46 (td, J = 7.8, 1.4 Hz, 1H, CH_ar-4’), 8.11 (d, J = 2.4 Hz, 1H, CH_ar-8), 8.05 – 7.96 (m, 2H, CH_ar-3’ &

CH_ar-5’), 6.74 (dd, J = 8.8, 2.5 Hz, 1H, CH_ar-10), 5.58 (d, J = 8.8 Hz, 1H, CH_ar-11), 4.55 (d, J = 16.0 Hz, 1H, NCHH), 4.25 (d, J

= 15.9 Hz, 1H, NCHH), 3.97 (d, J = 17.5 Hz, 1H, CHH), 3.64 (d, J = 17.5 Hz, 1H, CH_H_), 3.16 (s, 3H, N_imidCH₃), 1.92 (s, 3H, NCH₃). HRMS calculated for

C₂₇H₂₀ClFN₅NaO₅Rh (M + Na)⁺ 674.0084, found (M + Na)⁺ 674.0077.

5.2.3.22 Synthesis of organorhodium(III) complexes -(R)-197 and

-(R)-198

A suspension of KBr (94.5 mg, 792 µmol) and RhCl₃∙3H₂O (23 mg, 88 µmol) in water (1:1, 8 mL) under nitrogen atmosphere in a sealed vessel was heated to 90 °C for 45 min. Then, 77 (40 mg, 88 µmol) dissolved in ethanol (8 mL) was added and the reaction mixture was stirred for another 3 h at 90 °C. During this time the suspension turned from pale brown into dark green. The reaction mixture was then cooled down slightly to add 189 (17.2 mg, 96 µmol).

After addition of 189, the reaction was fur-ther proceeded at 90 °C for 16 h. The reac-tion mixture was then cooled down to ambi-ent temperature and the solvambi-ent was removed in vacuo. The crude material was purified via column chromatography using methylene chloride : methanol (20:1  10:1). The separated diastereomers were further purified and concentrated via prepar-ative TLC using methylene chlo-ride : methanol (10:1). The products were obtained as dark green solids, -197 (11.6 mg, 16.7 µmol, 19%) and -198 (6.1 mg, 8.8 µmol, 10%). , -197:

R_f = 0.30 (methylene chloride : methanol 10:1). ¹H-NMR (300 MHz, (CD3)2SO):

δ(ppm) 9.70 (dd, J = 5.0, 1.6 Hz, 1H, CH_ar-6’), 9.36 (s, 1H, OH), 8.82 (dt, J = 9.2, 2.4 Hz, 1H, CH_ar-4’), 8.39 – 8.29 (m, 1H,

CH_ar-4), 8.23 – 8.16 (m, 2H, CH_ar-2 &

CH_ar-8), 7.95 – 7.87 (m, 2H, CH_ar-3’ &

CHar-5’), 7.56 (d, J = 8.9 Hz, 1H, CHar-11), 7.09 (dd, J = 8.9, 2.6 Hz, 1H, CH_ar-10), 4.75 (d, J = 16.2 Hz, 1H, NCHH), 4.52 (d, J = 16.4 Hz, 1H, NCHH), 3.68 (d, J = 4.1 Hz, 2H, CH_2), 3.16 (s, 3H, N_imidCH₃), 1.73 (s, 3H, NCH₃). IR (film): ν (cm^-1) 2922, 2852, 2243, 2181, 2126, 2001, 1749, 1696, 1650, 1564, 1502, 1443, 1411, 1368, 1330, 1296, 1221, 1153, 1021, 992, 882, 815, 758, 690, 608, 515, 451. HRMS calculated for C₂₇H₂₀BrFN₅NaO₅Rh (M + Na)⁺ 719.2753, found (M + Na)⁺ 719.9553. -198:

R_f = 0.48 (methylene chloride : methanol 10:1). ¹H-NMR (300 MHz, (CD₃)₂SO):

δ(ppm) 9.84 (d, J = 5.8 Hz, 1H, CH_ar-6’), 9.31 (s, 1H, CH_ar), 8.94 (dd, J = 9.2, 2.4 Hz, 1H, CH_ar), 8.75 – 8.70 (m, 1H, CH_ar), 8.45 (td, J = 7.8, 1.4 Hz, 1H, CH_ar-4’), 8.11 (d, J = 2.4 Hz, 1H, CH_ar), 8.04 – 7.95 (m, 2H, CH_ar-3’ & CH_ar-5’), 6.74 (dd, J = 8.8, 2.5 Hz, 1H, CH_ar-10), 5.57 (d, J = 8.8 Hz, 1H, CHar-10), 4.54 (d, J = 16.1 Hz, 1H, NCHH), 4.23 (d, J = 15.9 Hz, 1H, NCHH), 3.91 (d, J

= 17.4 Hz, 1H, CHH), 3.59 (d, J = 17.5 Hz, 1H, CH_H_), 3.16 (s, 3H, N_imidCH₃), 1.86 (s, 3H, NCH₃). IR (film): ν(cm^-1) 1748, 1655, 1559, 1526, 1492, 1438, 1406, 1371, 1322, 1288, 1198, 1145, 1020, 984, 953, 924, 884, 842, 793, 753, 688, 610, 524, 447. HRMS calculated for C₂₇H₂₁BrFN₅O₅Rh (M + H)⁺ 697.2935, found (M + H)⁺ 697.9729.

5.2.3.23 Synthesis of organorhodium(III) complexes -(R)-199 and

-(R)-200

A suspension of 77 (20 mg, 44 µmol) and RhCl₃∙3H₂O (11.5 mg, 44 µmol) in an ethanol : water mixture (1:1, 20 mL) under nitrogen atmosphere in a sealed vessel was heated to 90 °C for 3 h. During this time the suspension turned from pale brown into dark green. The reaction mixture was then cooled down slightly to add (R)-105 (9.9 mg, 48 µmol). After addition of (R)-105, the reac-tion was further proceeded at 90 °C for 16 h.

The reaction mixture was then cooled down to ambient temperature and the solvent was removed in vacuo. The crude material was purified via column chromatography using methylene chloride : methanol (25:1  10:1). The separated diastereomers were further purified and concentrated via prepar-ative TLC using methylene chlo-ride : methanol (15:1). The products were obtained as dark green solids, -(R)-199 (6.3 mg, 9.3 µmol, 21%) and -(R)-200 (3.8 mg, 5.7 µmol, 13%). -(R)-199:

R_f = 0.13 (methylene chloride : methanol 15:1). ¹H-NMR (300 MHz, (CD₃)₂SO):

δ(ppm) 9.50 (d, J = 5.6 Hz, 1H, CH_ar-6’), 9.36 (s, 1H, OH), 8.81 (dd, J = 9.2, 2.2 Hz, 1H, CH_ar-4), 8.35 (td, J = 7.8, 1.5 Hz, 1H, CH_ar-4’), 8.14 (d, J = 2.4 Hz, 1H, CH_ar-8), 8.09 – 8.03 (m, 1H, CH_ar-2), 7.97 – 7.87 (m, 2H, CHar-3’ & CHar-5’), 7.62 (d, J = 8.8 Hz, 1H, CH_ar-11), 7.09 (dd, J = 8.8, 2.5 Hz, 1H, CH_ar-10), 4.75 (d, J = 16.1 Hz, 1H, NCHH), 4.57 (d, J = 16.1 Hz, 1H, NCHH), 3.77 (dd, J

= 9.4, 5.1 Hz, 1H, CH_), 3.15 (s, 3H, NCH₃), 2.52 – 2.48 (m, 1H, CH_H_) 2.18 (dt, J = 13.4, 6.1 Hz, 2H, CHH& CHH), 1.82 (td, J = 11.7, 5.6 Hz, 1H, CH_H_), 1.55 – 1.40 (m, 1H, CH_H_), 1.17 – 1.01 (m, 1H, CH_H_).

13C-NMR (75 MHz, (CD₃)₂SO): δ(ppm) 182.28 (C_carbonyl), 169.02 (C_ar-7), 168.73 (C_ar-5), 160.17 (C_ar-2’), 156.77 (d, J = 252.4 Hz, Car-3), 152.15 (Car-12b), 151.87 (Car-6’), 151.62 (C_ar-9), 143.68 (C_ar), 140.87 (C_ar), 140.66 (C_ar), 140.41 (C_ar), 139.68 (C_ar), 131.37 (C_ar), 126.02 (C_ar), 123.90 (C_ar), 123.67 (C_ar), 120.57 (d, J = 8.1 Hz, C_ar-4a), 118.63 (d, J = 21.0 Hz, C_ar-4), 117.03 (C_ar), 115.32 (C_ar), 114.68 (C_ar), 111.04 (C_ar), 108.64 (C_ar), 73.42 (C_), 69.36 NCH₂), 61.33 (C_), 30.34 (C_), 23.67 (C_), 23.63 (NCH₃).

IR (film): ν (cm^-1) 2921, 2852, 1747, 1697, 1619, 1566, 1502, 1444, 1411, 1373, 1331, 1272, 1220, 1151, 1065, 987, 958, 882, 805, 766, 731, 690, 610, 579. HRMS calculated for C₂₉H₂₂ClFN₅NaO₅Rh (M + Na)⁺ 700.0241, found (M + Na)⁺ 700.0257.

-(R)-200: ¹H-NMR (300 MHz, R_f = 0.22 (methylene chloride : methanol 15:1).

(CD₃)₂SO): δ(ppm) 9.65 (d, J = 5.6 Hz, 1H, CH_ar-6’), 9.32 (s, 1H, OH), 8.93 (dd, J = 9.1, 2.3 Hz, 1H, CH_ar-4), 8.72 – 8.60 (m, 1H, CH_ar-2), 8.47 (td, J = 7.7, 1.2 Hz, 1H, CH_ar-4’), 8.12 (d, J = 2.4 Hz, 1H, CH_ar-8), 8.06 – 7.93 (m, 2H, CH_ar-3’ & CH_ar-5’), 6.74 (dd, J = 8.8, 2.5 Hz, 1H, CH_ar-10), 5.51 (d, J

= 8.8 Hz, 1H, CHar-11), 4.63 (d, J = 15.7 Hz, 1H, NCHH), 4.32 (d, J = 15.6 Hz, 1H, NCHH), 3.80 (dd, J = 9.3, 5.0 Hz, 1H, CH_), 3.14 (s, 3H, NCH3), 2.62 – 2.52 (m, 1H, CHH), 2.34 – 2.16 (m, 2H, CHH&

CH_H_), 2.12 – 1.98 (m, 1H, CH_H_), 1.65 (dt, J = 18.6, 6.0 Hz, 1H, CH_H_), 1.24 – 1.02 (m, 1H, CH_H_). ¹³C-NMR (75 MHz, (CD₃)₂SO): δ(ppm) 181.83 (C_carbonyl), 168.94 (C_ar-7), 168.65 (C_ar-5), 161.12 (C_ar-2’), 156.54 (d, J = 252.9 Hz, C_ar-3), 152.72 (C_ar-12b), 152.58 (C_ar-6’), 151.87 (C_ar-9), 142.69 (Car), 142.67 (Car), 141.25 (Car), 139.46 (Car), 137.81 (d, J = 34.5 Hz, Car-2), 131.56 (C_ar), 126.29 (C_ar), 124.06 (C_ar), 123.56 (C_ar), 121.03 (d, J = 8.3 Hz, C_ar-4a),

119.31 (d, J = 20.2 Hz, C_ar-4), 116.92 (C_ar), 114.87 (C_ar), 112.28 (C_ar), 111.64 (C_ar-10), 109.19 (C_ar-11), 72.76 (C_), 69.84 (NCH₂), 61.00 (C_), 30.17 (C_), 24.20 (C_), 23.65 (NCH₃). IR (film): ν(cm^-1) 2921, 2850, 1744, 1694, 1615, 1563, 1502, 1441, 1411, 1370, 1329, 1270, 1217, 1151, 1062, 985, 958, 880, 801, 762, 731, 688, 607, 575. HRMS calculated for C₂₉H₂₂ClFN₅NaO₅Rh (M + Na)+ 700.0241, found (M + Na)+

700.0254.

5.2.3.24 Synthesis of organorhodium(III) complexes -(S)-199 and -(S)-200

A suspension of 77 (20 mg, 44 µmol) and RhCl₃∙3H₂O (11.5 mg, 44 µmol) in an ethanol : water mixture (1:1, 20 mL) under nitrogen atmosphere in a sealed vessel was heated to 90 °C for 3 h. During this time the suspension turned from pale brown into dark green. The reaction mixture was then cooled down slightly to add (S)-105 (9.9 mg, 48 µmol). After addition of (S)-105, the reac-tion was further proceeded at 90 °C for 16 h.

The reaction mixture was then cooled down to ambient temperature and the solvent was removed in vacuo. The crude material was purified via column chromatography using methylene chloride : methanol (25:1  10:1). The separated diastereomers were further purified and concentrated via prepar-ative TLC using methylene chlo-ride : methanol (15:1). The products were obtained as dark green solids, -(S)-199 (6.8 mg, 10.1 µmol, 23%) and -(S)-200 (4.7 mg, 7.0 µmol, 16%). -(S)-199:

R_f = 0.13 (methylene chloride : methanol 15:1). ¹H-NMR (300 MHz, (CD₃)₂SO):

δ(ppm) 9.50 (d, J = 5.6 Hz, 1H, CHar-6’), 9.41 (s, 1H, OH), 8.82 (dd, J = 9.2, 2.1 Hz, 1H, CH_ar-4), 8.36 (td, J = 7.8, 1.4 Hz, 1H, CH_ar-4’), 8.14 (d, J = 2.4 Hz, 1H, CH_ar-8), 8.10 – 8.05 (m, 1H, CH_ar-2), 7.98 – 7.88 (m, 2H, CHar-3’ & CHar-5’), 7.61 (d, J = 8.8 Hz, 1H, CH_ar-11), 7.08 (dd, J = 8.8, 2.5 Hz, 1H, CH_ar-10), 4.74 (d, J = 16.0 Hz, 1H, NCHH), 4.54 (d, J = 16.1 Hz, 1H, NCHH), 3.77 (dd, J

= 9.5, 5.2 Hz, 1H, CH_), 3.16 (s, 3H, NCH₃), 2.45 – 2.38 (m, 1H, CH_H_), 2.24 – 2.10 (m, 2H, CHH& CHH), 1.90 – 1.72 (m, 1H, CH_H_), 1.53 – 1.38 (m, 1H, CH_H_), 1.17 – 1.01 (m, 1H, CH_H_). ¹³C-NMR (75 MHz, (CD₃)₂SO): δ(ppm) 182.29 (C_carbony), 169.02 (C_ar-7), 168.73 (C_ar-5), 160.17 (C_ar-2’), 156.47 (d, J = 245.5 Hz, C_ar-3), 152.16 (Car-12b), 151.87 (Car-6’), 151.62 (Car-9), 147.32 (Car), 144.37 (Car), 143.68 (Car), 140.67 (C_ar), 139.81 (d, J = 19.1 Hz, C_ar-2), 132.52 (C_ar), 131.37 (C_ar), 126.02, 123.79 (d, J = 18.0 Hz, C_ar-4), 119.33 (C_ar), 118.49 (C_ar), 117.04 (C_ar), 115.32 (C_ar), 114.67 (C_ar), 110.98 (C_ar), 108.63 (C_ar), 73.42 (C_), 69.35 (NCH₂), 61.33 (C_), 30.35 (C_), 23.67 (C_), 23.64 (NCH₃). IR (film): ν (cm^-1) 2920, 2852, 1747, 1698, 1619, 1567, 1502, 1444, 1412, 1374, 1332, 1272, 1221, 1152, 1089, 987, 960, 937, 882, 806, 770, 732, 691, 611, 581.

HRMS calculated for C₂₉H₂₂ClFN₅NaO₅Rh (M + Na)⁺ 700.0241, found (M + Na)⁺ 700.0225. -(S)-200: R_f = 0.22 (methylene chloride : methanol 15:1). ¹H-NMR (300 MHz, CD₃CN): δ(ppm) 9.82 – 9.73 (m, 1H, CH_ar-6‘), 8.98 (dd, J = 9.2, 2.4 Hz, 1H, CH_ar-4), 8.69 (td, J = 2.4, 0.9 Hz, 1H, CH_ar-4‘), 8.33 (td, J = 7.8, 1.5 Hz, 1H, CH_ar-2), 8.21 (d, J = 2.6 Hz, 1H, CH_ar-8), 7.94 – 7.79 (m, 2H, CH_ar-3‘ & CH_ar-5‘), 6.76 (dd, J = 8.9, 2.6 Hz, 1H, CH_ar-10), 5.66 – 5.57 (m, 1H, CH_ar-11), 4.44 (d, J = 15.5 Hz, 1H, NCHH), 4.36 (d, J = 15.2 Hz, 1H, NCHH), 3.67 (dd, J = 9.4, 5.2 Hz, 1H, CH_), 3.19 (s, 3H, NCH₃), 2.52 – 2.41 (m, 1H, CH_H_), 2.40 – 2.31 (m, 2H, CH_H_&

CH_H_), 1.70 – 1.59 (m, 1H, CH_H_), 1.37 –

1.29 (m, 2H, CH_H_& CHH_). ¹³C-NMR (75 MHz, (CD₃)₂SO): δ(ppm) 181.84 (C_carbonyl), 168.94 (C_ar-7), 168.65 (C_ar-5), 161.12 (C_ar-2‘), 156.56 (d, J = 251.0 Hz, C_ar-3), 152.72 (Car-12b), 152.58 (Car-6’), 151.88 (C_ar-9), 142.70 (C_ar), 141.26 (C_ar), 139.46 (C_ar), 137.82 (d, J = 34.7 Hz, C_ar-2), 131.57 (C_ar), 126.30 (C_ar), 124.06 (C_ar), 123.57 (C_ar), 121.03 (d, J = 8.0 Hz, C_ar-4a), 119.32 (d, J = 20.3 Hz, Car-4), 116.92 (Car), 114.87 (Car), 112.29 (Car-10), 111.58 (Car), 109.19 (Car-11), 72.76 (C), 69.85 (NCH2), 61.00 (C_), 30.17 (C_), 24.21 (C_), 23.66 (NCH₃).

IR (film): ν(cm^-1) 2923, 2851, 1747, 1678, 1622, 1562, 1492, 1439, 1408, 1369, 1328, 1291, 1225, 1201, 1154, 1058, 985, 957, 932, 883, 839, 794, 763, 688, 646, 611, 581, 520, 448, 397. HRMS calculated for C₂₉H₂₂ClFN₅NaO₅Rh (M + Na)+ 700.0241, found (M + Na)+ 700.0254.

5.2.3.25 Synthesis of organorhodium(III) complexes -(S)-201 and -(S)-202

A suspension of KBr (94.5 mg, 792 µmol) and RhCl3∙3H2O (23 mg, 88 µmol) in water (1:1, 8 mL) under nitrogen atmosphere in a sealed vessel was heated to 90 °C for 45 min. Then, 77 (40 mg, 88 µmol) dissolved in ethanol (8 mL) was added and the reaction mixture was stirred for another 3 h at 90 °C. During this time the suspension turned from pale brown into dark green. The reaction mixture was then cooled down slightly to add (S)-105 (19.8 mg, 96 µmol). After addition of (S)-105, the reac-tion was further proceeded at 90 °C for 16 h.

The reaction mixture was then cooled down to ambient temperature and the solvent was removed in vacuo. The crude material was purified via column chromatography using methylene chloride : methanol (20:1  10:1). The separated diastereomers were further purified and concentrated via prepar-ative TLC using methylene chlo-ride : methanol (10:1). The products were obtained as dark green solids, -(S)-201 (12.1 mg, 16.7 µmol, 19%) and -(S)-202 (7.6 mg, 10.6 µmol, 12%). -(S)-201:

R_f = 0.11 (methylene chloride : methanol 15:1). ¹H-NMR (300 MHz, (CD₃)₂SO):

δ(ppm) 9.70 (d, J = 6.3 Hz, 1H, CHar-6’), 9.35 (s, 1H, OH), 8.82 (dd, J = 9.2, 2.2 Hz, 1H, CH_ar-4), 8.35 (td, J = 7.8, 1.4 Hz, 1H, CH_ar-4’), 8.14 (d, J = 2.3 Hz, 1H, CH_ar-8), 8.11 – 8.04 (m, 1H, CH_ar-2), 7.98 – 7.86 (m, 2H, CH_ar-3’ & CH_ar-5’), 7.60 (d, J = 8.8 Hz, 1H, CH_ar-11), 7.07 (dd, J = 8.8, 2.5 Hz, 1H, CH_ar-10), 4.73 (d, J = 15.8 Hz, 1H, NCHH), 4.55 (d, J = 16.3 Hz, 1H, NCHH), 3.72 (dd, J

= 9.4, 5.1 Hz, 1H, CH_), 3.16 (s, 3H, NCH₃), 2.45 – 2.39 (m, 1H, CHH), 2.15 (ddd, J = 17.5, 12.3, 6.3 Hz, 2H, CH_H_& CH_H_), 1.87 – 1.74 (m, 1H, CH_H_), 1.49 – 1.39 (m, 1H, CH_H_), 1.15 – 1.00 (m, 1H, CH_H_). IR (film): ν (cm^-1) 2928, 2872, 1748, 1695, 1651, 1564, 1502, 1442, 1411, 1371, 1330, 1290, 1203, 1150, 1102, 1053, 1026, 995, 962, 934, 882, 811, 766, 688, 649, 610, 522, 484, 453, 404. HRMS calculated for C₂₉H₂₂BrFN₅NaO₅Rh (M + Na)⁺ 743.9736, found (M + Na)⁺ 743.9722. -(S)-202:

Rf = 0.30 (methylene chloride : methanol 15:1). ¹H-NMR (300 MHz, (CD₃)₂SO):

δ(ppm) 9.86 (d, J = 6.5 Hz, 1H, CH_ar-6’), 9.33 (s, 1H, OH), 8.95 (dd, J = 9.2, 2.3 Hz, 1H, CH_ar-4), 8.66 (d, J = 2.5 Hz, 1H, CH_ar-2), 8.46 (td, J = 7.6, 1.4 Hz, 1H, CH_ar-4’), 8.13 (d, J = 2.5 Hz, 1H, CH_ar-8), 8.06 – 7.93 (m, 2H, CH_ar-3’ & CH_ar-5’), 6.73 (dd, J = 8.9, 2.5 Hz, 1H, CH_ar-10), 5.50 (d, J = 8.8 Hz, 1H, CH_ar-11), 4.61 (d, J = 15.4 Hz, 1H, NCHH), 4.29 (d, J = 14.8 Hz, 1H, NCHH), 3.75 (dd, J

= 9.1, 4.4 Hz, 1H, CH_), 3.17 (s, 3H, NCH₃), 2.60 – 2.56 (m, 1H, CH_H_), 2.24 – 2.12 (m,

2H, CH_H_& CHH_), 2.05 – 1.92 (m, 1H, CH_H_), 1.59 (ddd, J = 14.9, 11.0, 4.2 Hz, 1H, CHH), 1.37 – 1.27 (m, 1H, CHH).

HRMS calculated for C29H22BrFN5NaO5Rh (M + Na)⁺ 743.9736, found (M + Na)⁺ 743.9732.

5.3 Biological Experiments

Im Dokument Design and Synthesis of Enantiopure Organometallic Kinase Inhibitors as Potential Chemotherapeutics (Seite 165-187)