Mandelamide-Zinc Catalyzed Alkyne Addition to Heteroaromatic Aldehydes

1 Mandelamide-Zinc Catalyzed Alkyne Addition to Heteroaromatic Aldehydes Gonzalo Blay, Isabel Fernández, Alícia Marco-Aleixandre, and José R. Pedro Departament de Química Orgànica, Facultat de Química, Universitat de València, Dr. Moliner, 50, E-46100-Burjassot (València), Spain SUPPORTING INFORMATION Table of Contents: General Experimental Methods Characterization data for compounds 3aa-3ce and for mandelamide V S1 S2-S8 1 H NMR and 13 C NMR for compounds 3aa-3ce and for mandelamide V S9-S40 General Experimental Methods: Glassware was oven-dried overnight at 120 C. Reactions were monitored by TLC analysis. Flash column chromatography was performed on silica gel 60, (0.040-0.063 mm). 1 H NMR were run at 299.95 MHz for 1 H and at 50.3 MHz for 13 C NMR in CDCl 3 and referenced to the solvent as internal standard. Specific optical rotations were measured in CHCl 3 using sodium light (D line 589 nm). IR spectra were recorded as thin films in NaCl disks. HPLC analyses were performed in a chromatograph equipped with a refraction index detector using chiral stationary phase columns. All alkynes 1 and aldehydes 2 were commercially available and used as purchuased without further purification. Toluene was distilled from CaH 2 and stored on 4 Å molecular sieves. Mandelamides were prepared according to procedures described in the literature. 1

2 (R)-(+)-1,3-Diphenyl-2-propyn-1-ol (3aa). 2,3,4 Ph 3aa Obtained in 95% yield; enantiomeric excess was determined by HPLC (Chiralcel OD-H), hexane:i- Pr 90:10, 1 ml/min, major enantiomer t r = 13.1 min, minor enantiomer t r = 21.7 min, to be 25 89%; [α] D +6.7 (c 0.54, CHCl 3, ee 89%); MS(EI) 208 (M +, 100), 191 (30), 179 (61); HRMS 208.0866, C 15 H 12 O required 208.0888; 1 H NMR (CDCl 3 ) δ 7.61 (d, J = 6.3 Hz, 2H), 7.48-7.30 (m, 8H), 5.68 (s, 1H), 2.27 (br s, 1H); 13 C NMR (CDCl 3 ) δ 140.6 (C), 131.7 (CH), 128.64 (CH), 128.58 (CH), 128.4 (CH), 128.3 (CH), 126.7 (CH), 122.3 (C), 88.6 (C), 86.6 (C), 65.1 (CH). (S)-(+)-1-(Furan-2-yl)-3-phenyl-2-propyn-1-ol (3ab). 4 Ph O 3ab Obtained in 88% yield; enantiomeric excess was determined by HPLC (Chiralcel OD-H), hexane:i- Pr 90:10, 1 ml/min, major enantiomer t r = 10.3 min, minor enantiomer t r = 21.1 min, to be 25 83%; [α] D +34 (c 0.58, CHCl 3, ee 83%); MS(EI) 198 (M +, 19), 181 (26), 141 (100); HRMS 198.0673, C 13 H 10 O 2 required 198.0681; 1 H NMR (CDCl 3 ) δ 7.50-7.40 (m, 3H), 7.35-7.25 (m, 3H), 6.51 (d, J = 3.0 Hz, 1H), 6.36 (dd, J = 5.4, 3.0 Hz, 1H), 5.68 (s, 1H), 2.50 (br s, 1H); 13 C NMR (CDCl 3 ) δ 152. 9 (C), 143.1 (CH), 131.8 (CH), 128.8 (CH), 128.3 (CH), 122.0 (C), 110.4 (CH), 107.9 (CH), 86.1 (C), 85.8 (C), 58.6 (CH). (S)-(+)-1-(Furan-3-yl)-3-phenyl-2-propyn-1-ol (3ac). 2 Ph 3ac O Obtained in 94% yield; enantiomeric excess was determined by HPLC (Chiralcel OD-H), hexane:i- Pr 90:10, 1 ml/min, major enantiomer t r = 9.6 min, minor enantiomer t r = 24.7 min, to be 89%; [α] D 25 +3.0 (c 0.53, CHCl 3, ee 89%); MS(EI) 198 (M +, 57), 181 (24), 169 (42), 141 (100);

3 HRMS 198.0659, C 13 H 10 O 2 required 198.0681; 1 H NMR (CDCl 3 ) δ 7.58 (s, 1H), 7.47-7.40 (m, 3H), 7.35-7.25 (m, 3H), 6.56 (s, 1H), 5.61 (s, 1H), 2.11 (br s, 1H); 13 C NMR (CDCl 3 ) δ 143.7 (CH), 140.2 (CH), 131.7 (CH), 128.7 (CH), 126.4 (C), 122.2 (C), 109.2 (CH), 88.1 (C), 85.1 (C), 57.7 (CH). (S)-(+)-3-Phenyl-1-(thiophen-2-yl)-2-propyn-1-ol (3ad). This compound has been described in racemic form. 5 Ph 3ad S Obtained in 91% yield; enantiomeric excess was determined by HPLC (Chiralcel OD-H), hexane:i- Pr 90:10, 1 ml/min, major enantiomer t r = 11.2 min, minor enantiomer t r = 23.2 min, to be 90%; [α] 25 D +20 (c 0.53, CHCl 3, ee 90%); MS(EI) 214 (M +, 23), 197 (15), 185 (30), 102 (100); HRMS 214.0456, C 13 H 10 OS required 214.0452; 1 H NMR (CDCl 3 ) δ 7.51-7.40 (m, 2H), 7.37-7.20 (m, 3H), 7.23 (dt, J = Hz), 7.00 (dd, J = 5.0, 3.5 Hz, 1H), 5.88 (br d, J = 6.0 Hz, 1H), 2.53 (br d, J = 6.0 Hz, 1H); 13 C NMR (CDCl 3 ) δ 144.6 (C), 131.8 (CH), 128.8 (CH), 128.3 (CH), 126.8 (CH), 126.1 (CH), 125.6 (CH), 122.1 (C), 87.9 (C), 86.0 (C), 60.7 (CH). (S)-(+)-3-Phenyl-1-(thiophen-3-yl)-2-propyn-1-ol (3ae). 2 Ph 3ae S Obtained in 86% yield; enantiomeric excess was determined by HPLC (Chiralcel OD-H), hexane:i- Pr 90:10, 1 ml/min, major enantiomer t r = 11.5 min, minor enantiomer t r = 30.8 min, to be 88%; [α] 25 D +20 (c 0.53, CHCl 3, ee 88%); MS(EI) 214 (M +, 23), 197 (15), 185 (30), 102 (100); HRMS 214.0456, C 13 H 10 OS required 214.0452; 1 H NMR (CDCl 3 ) δ 7.51-7.40 (m, 2H), 7.39-7.20 (m, 5H), 5.71 (s, 1H), 2.18 (br s, 1H); 13 C NMR (CDCl 3 ) δ 142.0 (C), 131.7 (CH), 128.6 (CH), 128.3 (CH), 126.6 (CH), 126.4 (CH), 122.7 (CH), 122.3 (C), 88.5 (C), 85.8 (C), 61.0 (CH).

4 (R)-(+)-1,5-Diphenyl-2-pentyn-1-ol (3ba). 2,3 PhH 2 CH 2 C 3ba Obtained in 96% yield; enantiomeric excess was determined by HPLC (Chiralcel OD-H), hexane:i- Pr 90:10, 1 ml/min, major enantiomer t r = 15.7 min, minor enantiomer t r = 27.4 min, to be 25 88%; [α] D +13.0 (c 0.52, CHCl 3, ee 88%); MS(EI) 236 (M +, 98), 218 (61), 91 (100); HRMS 236.1195, C 17 H 16 O required 236.1201; 1 H NMR (CDCl 3 ) δ 7.45 (dd, J = 7.8, 2.2 Hz, 2H), 7.40-7.15 (m, 8H), 5.41 (s, 1H), 2.85 (t, J = 7.5 HZ, 2H), 2.56 (td, J = 7.5, 1.8 Hz, 2H), 2.13 (br s, 1H); 13 C NMR (CDCl 3 ) δ 141.0 (C), 140.4 (C), 128.5 (CH), 128.4 (CH), 128.2 (CH), 126.6 (CH), 126.3 (CH), 86.7 (C), 80.7 (C), 64.7 (CH), 34.8 (CH 2 ), 20.9 (CH 2 ). (S)-(+)-1-(Furan-2-yl)-5-phenyl-2-pentyn-1-ol (3bb). PhH 2 CH 2 C 3bb O Obtained in 96% yield; enantiomeric excess was determined by HPLC (Chiralcel OD-H), hexane:i- Pr 90:10, 1 ml/min, major enantiomer t r = 13.9 min, minor enantiomer t r = 21.7 min, to be 90%; [α] 25 D +14.2 (c 0.54, CHCl 3, ee 90%); IR (thin film) 3397, 3120, 3062, 3028, 2927, 2227, 1603, 1497, 1453, 1008, 744 cm -1 ; MS(EI) 226 (M +, 6), 208 (3), 91 (100); HRMS 226.0994, C 15 H 14 O 2 required 226.0994; 1 H NMR (CDCl 3 ) δ 7.32 (s, 1H), 7.25-7.10 (m, 5H), 6.25 (s, 2H), 5.34 (d, J = 6.0 Hz, 1H), 2.79 (t, J = 7.5 Hz, 2H), 2.49 (td, J = 7.5, 1.8 Hz, 2H), 2.21 (d, J = 6.0 Hz); 13 C NMR (CDCl 3 ) δ 153.4 (C), 142.8(CH), 140.3 (C), 128.43 (CH), 128.38 (CH), 126.3 (CH), 110.3 (CH), 107.5 (CH), 86.0 (C), 78.2 (C), 58.2 (CH), 34.7 (CH 2 ), 20.9 (CH 2 ).

5 (S)-(+)-1-(Furan-3-yl)-5-phenyl-2-pentyn-1-ol (33bc). PhH 2 CH 2 C 3bc O Obtained in 93% yield; enantiomeric excess was determined by HPLC (Chiralcel OD-H), hexane:i- Pr 90:10, 1 ml/min, major enantiomer t r = 11.9 min, minor enantiomer t r = 22.6 min, to be 92%; [α] 25 D +12.3 (c 0.52, CHCl 3, ee 92%); IR (thin film) 3383, 3132, 3062, 3022, 2933, 2216, 1597, 1494, 1453, 1002, 745 cm -1 ; MS(EI) 226 (M +, 50), 208 (11), 91 (100); HRMS 226.1000, C 15 H 14 O 2 required 226.0994; 1 H NMR (CDCl 3 ) δ 7.32 (d, J = 2.1 Hz, 1H), 7.30 (s, 2H), 7.26-7.10 (m, 5H), 6.37 (s, 2H), 5.27 (unresolved t, J = 1.5 Hz, 1H), 2.78 (t, J = 7.5 Hz, 2H), 2.49 (td, J = 7.5, 1.8 Hz, 2H), 1.88 (br s, 1H); 13 C NMR (CDCl 3 ) δ 143.5 (CH), 140.4 (C), 140.1(CH), 128.45 (CH), 128.40 (CH), 126.8 (C), 126.4 (CH), 109.14 (CH), 85.1 (C), 80.2 (C), 57.4 (CH), 34.8 (CH 2 ), 20.8 (CH 2 ). (S)-(+)-5-Phenyl-1-(thiophen-2-yl)-2-pentyn-1-ol (3bd) PhH 2 CH 2 C S 3bd Obtained in 89% yield; enantiomeric excess was determined by HPLC (Chiralcel OD-H), hexane:i- Pr 90:10, 1 ml/min, major enantiomer t r = 14.7 min, minor enantiomer t r = 30.6 min, to be 91%; [α] 25 D +27.5 (c 0.57, CHCl 3, ee 91%); IR (thin film) 3390, 3062, 3026, 2927, 2229, 1603, 1495, 1452, 1015, 699 cm -1 ; MS(EI) 242 (M +, 10), 110 (100); HRMS 242.0758, C 15 H 14 OS required 242.0765; 1 H NMR (CDCl 3 ) δ 7.25-7.15 (m, 6H), 6.99 (d, J = 3.3 Hz, 1H), 6.87 (dd, J = 5.4, 3.3 Hz, 1H), 5.54 (s, 1H), 2.79 (t, J = 7.5 Hz, 2H), 2.50 (td, J = 7.5, 1.8 Hz, 2H), 2.28 (d, J = 6.0 Hz); 13 C NMR (CDCl 3 ) δ 145.2 (C), 140.4 (C), 128.44 (CH), 128.39 (CH), 126.6 (CH), 126.3 (CH), 125.8 (CH), 125.4 (CH), 86.2 (C), 80.2 (C), 60.4 (CH), 34.7 (CH 2 ), 20.8 (CH 2 ).

6 (S)-(+)-5-Phenyl-1-(thiophen-3-yl)-2-pentyn-1-ol (3be) PhH 2 CH 2 C S 3be Obtained in 94% yield; enantiomeric excess was determined by HPLC (Chiralcel OD-H), hexane:i- Pr 90:10, 1 ml/min, major enantiomer t r = 14.7 min, minor enantiomer t r = 29.9 min, to be 89%; [α] 25 D +15.4 (c 0.51, CHCl 3, ee 89%); IR (thin film) 3385, 3100, 3062, 3024, 2930, 2225, 1600, 1494, 1452, 1013, 701 cm -1 ; MS(EI) 242 (M +, 100), 224 (10), 91 (61); HRMS 242.0771, C 15 H 14 OS required 242.0765; 1 H NMR (CDCl 3 ) δ 7.35-7.10 (m, 7H), 7.05 (d, J = 5.1 Hz 1H), 5.37 (s, 1H), 2.79 (t, J = 7.5 Hz, 2H), 2.50 (td, J = 7.5, 1.8 Hz, 2H), 1.96 (br s, 1H); 13 C NMR (CDCl 3 ) δ 142.5 (C), 140.4 (C), 128.5 (CH), 128.4 (CH), 126.35 (CH), 126.30 (CH), 122.5 (CH), 85.8 (C), 80.6 (C), 60.6 (CH), 34.8 (CH 2 ), 20.8 (CH 2 ). (+)-4,4-Dimethyl-1-phenyl-2-pentyn-1-ol (3ca). This compound has been described in racemic form. 5 t-bu 3ca Obtained in 93% yield; enantiomeric excess was determined by HPLC (Chiralcel OD-H), hexane:i- Pr 90:10, 1 ml/min, major enantiomer t r = 5.8 min, minor enantiomer t r = 4.7 min, to be 67%; [α] 25 D +18.8 (c 0.51, CHCl 3, ee 67%); MS(EI) 188 (M +, 100), 173 (16), 158 (21); HRMS 188.1191, C 13 H 16 O required 188.1201; 1 H NMR (CDCl 3 ) δ 7.53 (d, J = 6.3, Hz, 2H), 7.40-7.25 (m, 3H, 5.42 (s, 1H), 2.08 (br s, 1H), 1.24 (s, 9H); 13 C NMR (CDCl 3 ) δ 141.3 (C), 128.4 (CH), 128.1 (CH), 126.7 (CH), 95.8 (C), 78.3 (C), 64.7 (CH), 30.9 (CH 3 ), 27.5 (C). (+)-1-(Furan-2-yl)-4,4-dimethyl-2-pentyn-1-ol (3cb) t-bu 3cb O

7 Obtained in 79% yield; enantiomeric excess was determined by HPLC (Chiralcel OD-H), hexane:i- Pr 90:10, 1 ml/min, major enantiomer t r = 5.6 min, minor enantiomer t r = 5.3 min, to be 85%; [α] 25 D +16.8 (c 0.53, CHCl 3, ee 85%); IR (thin film) 3425, 2968, 2239, 1643, 1081, 1009 cm - 1 ;MS(EI) 178 (M +, 85), 163 (82), 135 (66) 121 (97), 91 (100); HRMS 178.1003, C 11 H 14 O 2 required 178.0994; 1 H NMR (CDCl 3 ) δ 7.38 (m, 1H), 6.40 (d, J = 3.0 Hz), 6.32 (dd, J = 3.0, 2.1 Hz, 1H), 5.41 (s, 1H), 2.23 (br s, 1H), 1.24 (s, 9H); 13 C NMR (CDCl 3 ) δ 153.8 (C), 142.8 (CH), 110.2 (CH), 107.5 (CH), 94.8 (C), 75.9 (C), 58.2 (CH), 30.8 (CH 3 ), 27.4 (C). (+)-1-(Furan-3-yl)-4,4-dimethyl-2-pentyn-1-ol (3cc) t-bu O 3cc Obtained in 98% yield; enantiomeric excess was determined by HPLC (Chiralcel OD-H), hexane:i- Pr 90:10, 0.5 ml/min, major enantiomer t r = 9.5 min, minor enantiomer t r = 9.1 min, to be 90%; [α] 25 D +16.2 (c 0.56, CHCl 3, ee 90%); IR (thin film) 3366, 2970, 2235, 1027, 753 cm -1 ; MS(EI) 178 (M +, 84), 163 (1), 121 (72), 91 (100); HRMS 178.1003, C 11 H 14 O 2 required 178.0984; 1 H NMR (CDCl 3 ) δ 7.47 (s, 1H), 7.36 (unresolved t, 1H), 6.47 (unresolved d, 1H), 5.34 (s, 1H), 1.94 (br s, 1H), 1.23 (s, 9H); 13 C NMR (CDCl 3 ) δ 143.5 (CH), 140.1 (CH), 127.1 (C), 109.3 (CH), 94.1 (C), 77.9 (C), 57.4 (CH), 30.8 (CH 3 ), 27.4 (C). (+)-1-(Thiophen-2-yl)-4,4-dimethyl-2-pentyn-1-ol (3cd) S t-bu 3cd Obtained in 95% yield; enantiomeric excess was determined by HPLC (Chiralcel OD-H), hexane:i- Pr 90:10, 1 ml/min, major enantiomer t r = 5.7 min, minor enantiomer t r = 5.1 min, to be 90%; [α] 25 D +38.4 (c 0.51, CHCl 3, ee 90%); IR (thin film) 3381, 3105, 2969, 2238, 976, 702 cm -1, MS(EI) 194 (M +, 100), 179 (17); HRMS 194.0759, C 11 H 14 OS required 194.0765; 1 H NMR (CDCl 3 ) δ 7.26 (dd, J = 4.8, 1.5 Hz, 1H), 7.13 (dt, J = 3.5, 1.5 Hz, 1H), 6.95 (dd, J = 4.8, 3.5 Hz, 1H), 5.60 (d, J = 5.6 Hz), 2.33 (d, J = 5.6Hz, 1H), 1.25 (s, 9H); 13 C NMR (CDCl 3 ) δ 145.7 (C), 126.7 (CH), 125.8 (CH), 125.3 (CH), 95.1 (C), 78.0 (C), 60.3 (CH), 30.7 (CH 3 ), 27.4 (C).

8 (+)-1-(Thiophen-3-yl)-4,4-dimethyl-2-pentyn-1-ol (3ce) t-bu S 3ce Obtained in 90% yield; enantiomeric excess was determined by HPLC (Chiralcel OD-H), hexane:i- Pr 90:10, 1 ml/min, major enantiomer t r = 5.5 min, minor enantiomer t r = 5.0 min, to be 77%; [α] 25 D +17.7 (c 0.57, CHCl 3, ee 77%); IR (thin film) 3351, 3106, 2969, 2238, 995, 793 cm - 1, MS(EI) 194 (M +, 100), 179 (24), 164 (13); HRMS 194.0753, C 11 H 14 OS required 194.0765; 1 H NMR (CDCl 3 ) δ 7.35 (dt, J = 3.0, 1.2 Hz, 1H), 7.28 (dd, J = 4.8, 3.0 Hz, 1H), 7.17 (dd, J = 4.8, 1.2 Hz, 1H), 5.44 (s, 1H), 1.25 (s, 9H); 13 C NMR (CDCl 3 ) δ 142.9 (C), 126.5 (CH), 126.2 (CH), 122.4 (CH), 94.9 (C), 78.3 (C), 60.6 (CH), 30.9 (CH 3 ), 27.4 (C). (S)-N-(2-methoxybenzyl)-2-hydroxy-2-phenylacetamide (V) O HO V HN MeO [α] 25 D +56.7 (c 0.53, CHCl 3 ); IR (thin film) 3338, 3064, 2938, 1659, 1531, 1494, 1244, 754 cm - 1 MS(EI) 271 (M +, 16), 253 (20), 121 (100); HRMS 271.1187, C 16 H 17 NO 3 required 271.1208; 1 H NMR (CDCl 3 ) δ 7.36-7.32 (m, 5H); 7.26 (td, J = 7.6, 1.6 Hz, 1H), 7.17 (dd, J = 7.5, 1.6 Hz, 1H), 6.88 (t, J = 7.5 Hz, 1H), 6.83 (d, J = 7.5 Hz, 1H), 6.52 (br s, 1H), 5.00 (d, J = 3.3 Hz, 1H), 4.42 (AB system, 2H), 3.73 (s, 3H); 13 C NMR (CDCl 3 ) δ 171.9 (C), 157.4 (C), 139.5 (C), 129.4 (CH), 128.9 (CH), 128.6 (2 x CH), 128.4 (CH), 126.8 (2 x CH), 125.6 (C), 120.5 (CH), 110.2 (CH), 74.0 (CH), 55.1 (CH 3 ), 39.6 (CH 2 ). 1. Blay, G.; Fernández, I.; Hernández-Olmos, V.; Marco-Aleixandre, A.; Pedro, J. R. Tetrahedron: Asymmetry 2005, 16, 1953-1958. 2. Takita, R.; Yakura, K.; Ohshima, T.; Shibashaki, M. J. Am. Chem. Soc. 2005, 127, 13760-13761. 3. Frantz, D. E.; Fässler, R.; Carreira, E. M. J. Am. Chem. Soc. 2000, 122, 1806-1807. 4. Li. Z. B.; Pu, L. Org. Lett. 2004, 6, 1065-1068. 5. Sakai, N.; Kanada, R.; Hirasawa, M.; Konakahara, T. Tetrahedron 2005, 61, 9298-9304.

9 Ph 3aa 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0

10 Ph 3aa 150 140 130 120 110 100 90 80 70 60 50 40 30

11 Ph 3ab O 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0

12 Ph 3ab O 160 150 140 130 120 110 100 90 80 70 60 50 40 30

13 Ph 3ac O 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0

14 Ph 3ac O 150 140 130 120 110 100 90 80 70 60 50

15 Ph 3ad S 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5

16 Ph 3ad S 150 140 130 120 110 100 90 80 70 60 50

17 Ph 3ae S 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5

18 Ph 3ae S 150 140 130 120 110 100 90 80 70 60 50 40

19 PhH 2 CH 2 C 3ba 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5

20 PhH 2 CH 2 C 3ba 140 130 120 110 100 90 80 70 60 50 40 30 20 10

21 PhH 2 CH 2 C 3bb O 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5

22 PhH 2 CH 2 C 3bb O 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20

23 PhH 2 CH 2 C 3bc O 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5

24 PhH 2 CH 2 C 3bc O 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10

25 PhH 2 CH 2 C 3bd S 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0

26 PhH 2 CH 2 C 3bd S 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10

27 PhH 2 CH 2 C 3be S 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0

28 PhH 2 CH 2 C 3be S 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10

29 t-bu 3ca 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0

30 t-bu 3ca 150 140 130 120 110 100 90 80 70 60 50 40 30 20

31 t-bu 3cb O 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5

32 t-bu 3cb O 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20

33 t-bu 3cc O 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0

34 t-bu 3cc O 140 130 120 110 100 90 80 70 60 50 40 30 20

35 t- Bu 3cd S 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0

36 t- Bu 3cd S 150 140 130 120 110 100 90 80 70 60 50 40 30 20

37 t-bu 3ce S 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5

38 t-bu 3ce S 140 130 120 110 100 90 80 70 60 50 40 30 20

39 O HO V HN MeO 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0

40 O HO V HN MeO 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30