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1 Supporting Information Wiley-VC Weinheim, Germany

2 ighly Efficient Synthesis of Tricyclic Amines by Cyclization Cycloaddition Cascade. Total Synthesis of Aspidospermine, Aspidospermidine and Quebrachamine Iain Coldham,* Adam J.M. Burrell, Laura E. White, arry Adams and iall ram Experimental procedures and data: C C 2a Cl Preparation of nitrile 2a (n=0): To diisopropylamine (17 ml, 120 mmol) in TF (120 ml) at 78 C was added n-butyllithium (46 ml, 115 mmol, 2.5 M in hexanes). After 10 min, butyronitrile (20 ml, 229 mmol) was added dropwise. After 10 min, 4-bromobutene (6 ml, 57 mmol) was added. After 30 min, the mixture was allowed to warm to room temperature. After 30 min, saturated aqueous ammonium chloride solution (30 ml) was added and the mixture was extracted with Et 2 (3 50 ml). The organic layers were dried (MgS 4 ), evaporated and the residue was purified by column chromatography, eluting with petrol EtAc (98:2), to give 2-ethyl-hex-5-enenitrile (7.06 g, 80%) as an oil; R f 0.30 [petrol EtAc (98:2)]; ν max /cm , 2970, 2235, 1640; 1 MR (250 Mz, CDCl 3 ) δ = 5.75 (ddt, J 17.0, 10.5, 6.5, 1), (m, 2), (m, 1), (m, 2), (m, 4), 1.06 (t, J 7.5, 3); 13 C MR (63 Mz, CDCl 3 ) δ = 136.5, 122.0, 116.2, 32.5, 31.2, 31.0, 25.4, 11.5; RMS (EI) Found: M +, C 8 13 requires M +, ; LRMS m/z (EI) 124 (5%, M + ), 123 (3), 69 (83), 55 (100). In the same way as above, this nitrile (5.2 g, 42 mmol) and LDA [prepared from diisopropylamine (12.4 ml, 88 mmol) in TF (85 ml) and n-butyllithium (33.6 ml, 84 mmol, 2.5 M in hexanes)] and 1-bromo-3-chloropropane (8.4 ml, 84 mmol) gave, after purification by column chromatography, eluting with petrol EtAc (97:3), the nitrile 2a (8.01 g, 95%) as an oil; R f 0.31 [petrol EtAc (97:3)]; ν max /cm , 2970, 2230, 1640; 1 MR (250 Mz, CDCl 3 ) δ = 5.79 (ddt, J 17.0, 10.5, 6.5, 1), (m, 2), 3.56 (t, J 6.0, 2), (m, 2), (m, 8), 1.01 (t, J 7.5, 3); 13 C MR (63 Mz, CDCl 3 ) δ = 136.9, 123.3, 115.6, 44.6, 40.5, 34.8, 33.0, 28.9, 28.5, 27.5, 8.6; RMS (EI) Found: M +, C Cl requires M +, ; LRMS m/z (EI) 202 (3%, M + ( 37 Cl)), 200 (9%, M + ( 35 Cl)), 147 (36), 145 (87), 55 (100). C C 2b Cl Preparation of nitrile 2b (n=1): In the same way as the nitrile 2a, diisopropylamine (7.4 ml, 53 mmol) in TF (50 ml), n-butyllithium (20 ml, 50 mmol, 2.5 M in hexanes), butyronitrile (8.7 ml, 100 mmol) and 5-bromopentene (3.1 ml, 25 mmol) gave, after purification by column chromatography, eluting with petrol EtAc (97:3), 2-ethyl-hept-6-enenitrile (3.40 g, 99%) as an oil; R f 0.30 [petrol EtAc (98:2)]; ν max /cm , 2935, 2235, 1640; 1 MR (250 Mz, CDCl 3 ) δ = 5.72 (ddt, J 17.0, 10.0, 6.5, 1), (m, 2), (m, 1), (m, 2), (m, 6), 1.01 (t, J 7.5, 3); 13 C MR (63 Mz, CDCl 3 ) δ = 137.7, 122.1, 115.3, 33.2, 33.1, 31.2, 26.3, 25.5, 11.6; RMS (EI) Found: M +, C 9 15 requires M +, ; LRMS m/z (EI) 137 (6%, M + ), 109 (100). In the same way as above, this nitrile (4.29 g, 31.3 mmol) and LDA [prepared from diisopropylamine (9.2 ml, 65.7 mmol) in TF (63 ml) and n-butyllithium (27.2 ml, 62.5 mmol, 2.3 M in hexanes)] and 1-bromo-3-chloropropane (6.2 ml, 62.5 mmol) gave, after purification by column chromatography, eluting with petrol EtAc (97:3), the nitrile 2b (6.38 g, 96%) as an oil; R f 0.46 [petrol EtAc (95:5)]; ν max /cm , 2230, 1640; 1 MR (250 Mz, CDCl 3 ) δ = 5.76 (ddt, J 17.0, 10.0, 6.5, 1), (m, 2), 3.55 (t, J 6.0, 2), (m, 2), (m, 10), 0.99 (t, J 7.5, 3); 13 C MR (63 Mz, CDCl 3 ) δ = 137.7, 123.5, 115.4, 44.7, 40.6, 34.9, 33.5, 33.0, 28.8, 27.5, 23.4, 8.6; RMS (ES) Found: M +, C Cl requires M +, ; LRMS m/z (ES) 216 (10%, M + ( 37 Cl)), 214 (100%, M + ( 35 Cl)). SI 1

3 C C 2a Cl 3a Cl Preparation of aldehyde 3a (n=0): To the nitrile 2a (1.05 g, 5.3 mmol) in C 2 Cl 2 (26 ml) at 78 C was added dropwise DIBAL- (6.8 ml, 6.8 mmol, 1.0 M in hexanes). After 1.5 h, aqueous Cl (15 ml, 1 M) was added and the mixture was stirred at 78 C for 30 min, before being allowed to warm to room temperature. After 30 min, aqueous Cl (20 ml, 1 M) was added, and the mixture was extracted with Et 2 (6 30 ml). The organic layers were dried (MgS 4 ), evaporated and the residue was purified by column chromatography, eluting with petrol EtAc (98:2), to give the aldehyde 3a (0.92 g, 87%) as an oil; R f 0.49 [petrol EtAc (95:5)]; ν max /cm , 2970, 1725, 1640; 1 MR (250 Mz, CDCl 3 ) δ = 9.41 (s, 1), 5.76 (ddt, J 17.0, 10.5, 6.5, 1), (m, 2), (m, 2), (m, 2), (m, 8), 0.79 (t, J 7.5, 3); 13 C MR (63 Mz, CDCl 3 ) δ = 206.3, 137.9, 115.0, 51.7, 45.2, 31.0, 28.2, 27.8, 26.7, 24.6, 7.8; RMS (EI) Found: M +, C Cl requires M +, ; LRMS m/z (EI) 205 (2%, M + ( 37 Cl)), 203 (5%, M + ( 35 Cl)), 150 (31), 148 (70), 55 (100). C C 2b Cl 3b Cl Preparation of aldehyde 3b (n=1): In the same way as the aldehyde 3a, the nitrile 2b (2.25 g, 10.5 mmol) and DIBAL- (15.8 ml, 15.8 mmol, 1.0 M in hexanes) gave, after purification by column chromatography, eluting with petrol EtAc (98:2), the aldehyde 3b (2.03 g, 89%) as an oil; R f 0.54 [petrol EtAc (95:5)]; ν max /cm , 1725, 1640; 1 MR (250 Mz, CDCl 3 ) δ = 9.40 (s, 1), 5.75 (ddt, J 17.0, 10.0, 6.5, 1), (m, 2), (m, 2), (m, 2), (m, 10), 0.77 (t, J 7.5, 3); 13 C MR (63 Mz, CDCl 3 ) δ = 206.6, 138.1, 115.1, 51.8, 45.2, 34.1, 31.1, 28.3, 26.7, 24.6, 22.7, 7.8; RMS (ES) Found: M +, C Cl requires M +, ; LRMS m/z (ES) 219 (35%, M + ( 37 Cl)), 217 (100%, M + ( 35 Cl)). C Cl 3a 4 C 2 Et Preparation of tricyclic product 4: The aldehyde 3a (494 mg, 2.44 mmol), glycine ethyl ester hydrochloride (515 mg, 3.66 mmol) and,-diisopropylethylamine (1.3 ml, 7.3 mmol) were heated under reflux in toluene (18 ml). After 10 min (appearance of water in the reaction mixture), 4Å molecular sieves were added. After heating for 2 h, the mixture was cooled to room temperature, evaporated and the residue was purified by column chromatography, eluting with petrol EtAc (95:5), to give the product 4 (467 mg, 72%) as an oil; R f 0.20 [petrol EtAc (95:5)]; ν max /cm , 2875, 1730; 1 MR (500 Mz, CDCl 3 ) δ = (m, 2), 3.74 (t, J 7.0, 1), 3.07 (d, J 6.0, 1), (m, 1), (m, 2), 2.08 (dt, J 12.5, 8.0, 1), (m, 1), 1.83 (ddd, J 12.5, 6.5, 1.5, 1), (m, 3), (m, 8), (m, 1), 0.77 (t, J 7.5, 3); 13 C MR (125 Mz, CDCl 3 ) δ = 173.9, 71.6, 63.7, 60.3, 46.0, 44.6, 40.5, 38.8, 32.4, 31.5, 30.8, 29.9, 18.2, 14.4, 7.8; RMS (ES) Found: M + (ES), C requires M +, ; LRMS m/z (ES) 252 (100%, M + ). C C 2 Et 3b Cl 5 Preparation of tricyclic product 5: The aldehyde 3b (362 mg, 1.67 mmol), glycine ethyl ester hydrochloride (353 mg, 2.51 mmol) and,-diisopropylethylamine (0.87 ml, 5.01 mmol) were heated under reflux in toluene (15 ml). At the appearance of water in the reaction mixture, 4Å molecular sieves were added. After heating for a further 2 h, the mixture was cooled to room temperature, evaporated and the residue was purified by column SI 2

4 chromatography, eluting with C 2 Cl 2 Me 3 (98:2:0.1), to give the product 5 (327 mg, 74%) as an oil; R f 0.33 [C 2 Cl 2 Me 3 (98:2:0.1)]; ν max /cm , 1735; 1 MR (500 Mz, CDCl 3 ) δ = (m, 2), 3.24 (dd, J 9.0, 6.5, 1), (m, 1), (m, 2), 2.23 (d, J 12.0, 1), (m, 1), (m, 3), (m, 2), (m, 3), (m, 2), 1.21 (t, J 7.0, 3), (m, 2), 0.89 (m, 1), 0.80 (t, J 7.5, 3); 13 C MR (125 Mz, CDCl 3 ) δ = 174.9, 70.5, 65.8, 60.4, 49.8, 35.4, 35.2, 34.9, 34.0, 31.9, 30.1, 24.7, 22.5, 21.8, 14.2, 7.2; RMS (ES) Found: M + (ES), C requires M +, ; LRMS m/z (ES) 266 (100%, M + ). 3a C Cl 6 Preparation of tricyclic product 6: The aldehyde 3a (269 mg, 1.33 mmol), hydroxylamine hydrochloride (140 mg, 1.99 mmol) and,-diisopropylethylamine (0.35 ml, 1.99 mmol) were heated under reflux in toluene (10 ml). After 1 h, the solvent was evaporated and the residue was purified by column chromatography, eluting with petrol EtAc (1:1), to give product 6 (162 mg, 67%) as an oil; R f 0.25 [petrol EtAc (1:1)]; ν max /cm , 2860, 1455; 1 MR (500 Mz, CDCl 3 ) δ = (m, 1), 3.65 (d, J 8.5, 1), (m, 1), 3.19 (d, J, 7.5, 1), 3.04 (q, J 7.5, 1), (m, 1), (m, 4), (m, 1), (m, 4), (m, 1), 0.77 (t, J 7.5, 3); 13 C MR (125 Mz, CDCl 3 ) δ = 75.8, 70.6, 50.7, 48.4, 41.7, 32.6, 32.1, 31.4, 30.1, 14.9, 7.5; RMS (ES) Found: M +, C requires M +, ; LRMS m/z (ES) 182 (100%, M + ). 3b C Cl 7 Preparation of tricyclic product 7: The aldehyde 3b (231 mg, 1.06 mmol), hydroxylamine hydrochloride (151 mg, 2.13 mmol) and,-diisopropylethylamine (0.37 ml, 2.13 mmol) were heated under reflux in toluene (10.5 ml). After 1 h, the solvent was evaporated and the residue was purified by column chromatography, eluting with petrol EtAc (1:1), to give product 7 (133 mg, 64%) as an oil; R f 0.28 [petrol EtAc (1:1)]; ν max /cm , 2865, 1455; 1 MR (500 Mz, CDCl 3 ) δ = 4.16 (dd, J 8.0, 6.5, 1), 3.33 (dd, J 10.5, 6.5, 1), (m, 1), (m, 2), 2.46 (d, J 11.5, 1), (m, 2), 1.76 (qdd, J 14.0, 4.0, 3.0, 1), (m, 1), (m, 3), (m, 2), (m, 2), (m, 1), 0.79 (t, J 7.5, 3); 13 C MR (125 Mz, CDCl 3 ) δ = 71.9, 71.4, 51.4, 37.9, 37.5, 34.7, 32.1, 27.1, 23.6, 22.4, 21.0, 7.2; RMS (ES) Found: M +, C requires M +, ; LRMS m/z (ES) 196 (100%, M + ). 3a C Cl 8 Preparation of tricyclic product 8: The aldehyde 3a (350 mg, 1.73 mmol) and glycine (518 mg, 6.91 mmol) were heated under reflux in toluene (15 ml). After 24 h, the mixture was cooled to room temperature and was filtered and the solid was washed with C 2 Cl 2 (20 ml). The solvent was evaporated and the residue was purified by column chromatography, eluting with C 2 Cl 2 Me 3 (95:5:0.1), to give product 8 (255 mg, 82%) as an oil; R f 0.34 [C 2 Cl 2 Me 3 (95:5:0.1)]; ν max /cm , 2770, 1460; 1 MR (500 Mz, CDCl 3 ) δ = (m, 1), (m, 1), (m, 1), (m, 2), 2.19 (d, J 6.0, 1), (m, 2), (m, 3), 1.50 (m, 1), (m, 5), (m, 1), 0.78 (t, J 7.5, 3); 13 C MR (125 Mz, CDCl 3 ) δ = 74.8, 53.1, 48.9, 44.6, 40.4, 33.2, 32.9, 31.3, 30.6, 29.5, 20.1, 7.8; RMS (ES) Found: M +, C requires M +, ; LRMS m/z (ES) 180 (100%, M + ). SI 3

5 C Me 3a Cl 9 Preparation of tricyclic product 9: The aldehyde 3a (269 mg, 1.33 mmol) and alanine (478 mg, 5.31 mmol) were heated under reflux in toluene (13 ml). After 36 h, the mixture was cooled to room temperature and was filtered and the solid was washed with C 2 Cl 2 (20 ml). The solvent was evaporated and the residue was purified by column chromatography, eluting with C 2 Cl 2 Me 3 (95:5:0.1), to give product 9 (200 mg, 78%) as an oil; R f 0.31 [C 2 Cl 2 Me 3 (95:5:0.1)]; ν max /cm , 2855, 2790, 1455; 1 MR (500 Mz, CDCl 3 ) δ = 3.28 (d, J 7.0, 1), (m, 1), 3.00 (br d, J 13.5, 1), 2.72 (td, J 13.5, 2.0, 1), 2.65 (q, J 8.5, 1), (m, 2), (m, 3), (m, 1), (m, 4), (m, 1), 1.08 (d, J 6.0, 3), (m, 1), 0.63 (t, J 7.5, 3); 13 C MR (125 Mz, CDCl 3 ) δ = 71.0, 56.5, 44.0, 43.6, 42.1, 39.4, 32.1, 31.9, 31.8, 29.1, 16.3, 14.9, 7.2; RMS (ES) Found: M +, C requires M +, ; LRMS m/z (ES) 194 (100%, M + ). Ph 3a C Cl 10 Preparation of tricyclic product 10: The aldehyde 3a (310 mg, 1.53 mmol) and phenylalanine (1.03 g, 6.12 mmol) were heated under reflux in toluene (15 ml). After 18 h, the mixture was cooled to room temperature and was filtered and the solid was washed with C 2 Cl 2 (20 ml). The solvent was evaporated and the residue was purified by column chromatography, eluting with C 2 Cl 2 Me 3 (96:4:0.1), to give product 10 (246 mg, 60%) as an oil; R f 0.46 [C 2 Cl 2 Me 3 (96:4:0.1)]; ν max /cm , 2930, 2855, 2785, 1455; 1 MR (500 Mz, CDCl 3 ) δ = (m, 2), (m, 3), (m, 2), 3.13 (d, J 6.5, 1), 3.01 (dd, J 13.0, 4.0, 1), 2.73 (td, J 13.0, 2.5, 1), 2.63 (q, J 8.5, 1), 2.23 (dd, J 13.0, 10.0, 1), (m, 1), (m, 3), (m, 2), 1.36 (td, J 12.5, 4.5, 1), (m, 4), (m, 1), 0.77 (t, J 7.5, 3); 13 C MR (125 Mz, CDCl 3 ) δ = 140.2, 129.1, 128.2, 125.8, 72.2, 61.7, 44.8, 44.3, 41.4, 40.3, 39.5, 32.4, 32.0, 31.8, 30.8, 16.8, 7.7; RMS (ES) Found: M +, C requires M +, ; LRMS m/z (ES) 270 (100%, M + ). The relative stereochemistry is tentatively assigned as shown, based on ESY experiments, in which the peak for the ring junction proton α- to the nitrogen atom was enhanced on irradiation of the other ring junction proton and by one of the protons of the methylene of the ethyl group and by one of the protons of the methylene of the benzyl group. S 2 Ph C C 2b Cl 11 Cl Preparation of aldehyde 11: To the nitrile 2b (849 mg, 3.97 mmol) in degassed C 2 Cl 2 (200 ml) was added phenyl vinyl sulfone (1.35 g, 7.94 mmol). This was heated to reflux before Grubbs 2 nd generation catalyst (169 mg, 0.20 mmol) in C 2 Cl 2 (10 ml) was added dropwise. After 24 h, the mixture was allowed to cool to room temperature. The solvent was evaporated and the residue was purified by column chromatography, eluting with petrol EtAc (1:5), to give vinylsulfone nitrile (1.24 g, 88%) as an oil [together with some nitrile 2b (79 mg, 5%)]. In the same way as the aldehyde 3b, this nitrile (600 mg, 1.70 mmol) and DIBAL- (2.54 ml, 2.54 mmol, 1.0 M in hexanes) gave, after purification by column chromatography, eluting with petrol EtAc (1:5), the aldehyde 11 (520 mg, 86%) as an oil; R f 0.44 [petrol EtAc (1:5)]; ν max /cm , 1720, 1305, 1145; 1 MR (400 Mz, CDCl 3 ) δ = 9.37 (s, 1), (m, 2), (m, 3), 6.93 (dt, J 15.0, 7.0, 1), 6.32 (dt, J 15.0, 1.5, 1), (m, 2), 2.22 (qd, J 7.0, 1.5, 2), (m, 10), 0.76 (t, J 7.5, 3); 13 C MR (63 Mz, CDCl 3 ) δ = 206.1, 146.0, 140.5, 133.3, 131.1, 129.3, 127.6, 51.7, 45.1, 31.7, 30.7, 28.4, 26.7, 24.6, 21.6, 7.8; RMS (ES) Found: M +, C S 35 Cl requires M +, ; LRMS m/z (ES) 359 (12%, M + ( 37 Cl)), 357 (100%, M + ( 35 Cl)). SI 4

6 C S 2 Ph S 2 Ph + S 2 Ph 11 Cl Preparation of tricyclic products 12 and 13: The aldehyde 11 (750 mg, 2.10 mmol) and glycine (637 mg, 8.41 mmol) were heated under reflux in toluene (21 ml). After 24 h, the mixture was filtered and the solid was washed with C 2 Cl 2. The solvent was evaporated and the residue was purified by column chromatography, eluting with petrol EtAc (3:1), to give the product 12 (250 mg, 36%) as a white solid, which recrystallised from C 2 Cl 2 petrol to give colourless cubes. Further elution with C 2 Cl 2 Me (96:4) gave the product 13 (265 mg, 38%) as a white solid, which recrystallised from C 2 Cl 2 to give colourless cubes. Data for the product 12: m.p C; R f 0.18 [petrol EtAc (3:1)]; ν max /cm , 1445, 1300, 1140; 1 MR (500 Mz, C 6 D 6 ) δ = (m, 2), (m, 3), (m, 1), 3.00 (t, J 9.0, 1), (m, 2), 2.60 (dd, J 9.0, 7.0, 1), 1.92 (d, J 5.0, 1), 1.72 (ddd, J 12.5, 10.5, 2.5, 1), (m, 1), (m, 1), (m, 1), (m, 6), (m, 2), 0.78 (td, J 13.5, 4.5, 1), 0.66 (t, J 7.5, 3); 13 C MR (125 Mz, C 6 D 6 ) δ = 140.1, 133.0, 129.0, 128.7, 69.3, 67.3, 54.2, 52.7, 37.9, 34.7, 34.1, 30.7, 29.9, 25.7, 21.9, 21.0, 6.9; RMS (ES) Found: M +, C S requires M +, ; LRMS m/z (ES) 334 (100%, M + ); C S (333.18): calcd. C 68.43, 8.16, 4.20, S 9.62; found C 68.38, 8.37, 4.16, S Data for the product 13: m.p C; R f 0.21 [C 2 Cl 2 Me (96:4)]; ν max /cm , 1445, 1305, 1145; 1 MR (500 Mz, CDCl 3 ) δ = (m, 2), (m, 1), (m, 2), (m, 2), (m, 1), (m, 2), (m, 1), 2.09 (d, J 11.5, 1), (m, 1), (m, 1), (m, 5), (m, 3), 1.00 (td, J 14.0, 4.5, 1), (m, 1), 0.76 (t, J 7.5, 3); 13 C MR (125 Mz, CDCl 3 ) δ = 139.5, 133.6, 129.3, 128.1, 72.4, 68.7, 54.1, 48.6, 37.0, 35.7, 34.7, 31.6, 29.5, 23.6, 22.1, 21.3, 7.1; RMS (ES) Found: M +, C S requires M +, ; LRMS m/z (ES) 334 (100%, M + ); C S (333.18): calcd. C 68.43, 8.16, 4.20, S 9.62; found C 68.40, 8.46, 4.10, S S 2 Ph Preparation of tricyclic product 14: Sodium-mercury amalgam (0.85 g, 1.80 mmol) was added to the amine 12 (200 mg, 0.60 mmol) and sodium hydrogen phosphate (350 mg, 2.40 mmol) in Me (2 ml) at 0 C. After 4 h, the mixture was filtered and washed with Me. The solvent was evaporated and the residue was purified by column chromatography, eluting with C 2 Cl 2 Me 3 (98:2:0.1), to give the product 14 (48 mg, 57%) as an oil; R f 0.26 [C 2 Cl 2 Me 3 (99:1:0.1)]; ν max /cm , 1460; 1 MR (500 Mz, CDCl 3 ) δ = 3.08 (td, J 9.0, 2.5, 1), (m, 1), (m, 1), (m, 1), (m, 5), (m, 6), (m, 2), (m, 1), (m, 2), 0.76 (t, J 7.5, 3); 13 C MR (125 Mz, CDCl 3 ) δ = 71.7, 53.4, 53.3, 34.6, 34.3, 34.25, 30.8, 30.2, 29.7, 28.4, 25.8, 21.9, 6.9; RMS (ES) Found: M C requires M +, ; LRMS m/z (ES) 194 (100%, M + ). S 2 Ph Preparation of product 15: Sodium-mercury amalgam (0.85 g, 1.80 mmol) was added to the amine 13 (200 mg, 0.60 mmol) and sodium hydrogen phosphate (350 mg, 2.40 mmol) in Me (2 ml) at 0 C. After 4 h, the mixture was filtered and washed with Me. The solvent was evaporated and the residue was purified by column chromatography, eluting with C 2 Cl 2 Me 3 (95:5:0.1), to give the product 15 (73 mg, 73%) as an oil; R f 0.26 [C 2 Cl 2 Me 3 (95:5:0.1)]; ν max /cm , 1455; 1 MR (500 Mz, CDCl 3 ) δ = 5.54 (ddd, J 17.0, 10.0, 9.0, 1), 5.04 (ddd, J 17.0, 2.0, 1.0, 1), 5.00 (ddd, J 10.0, 2.0, 0.5, 1), (m, 3), 2.11 (d, J 10.5, 1), 2.00 (br s, 1), (m, 1), (m, 3), (m, 5), (m, 3), 0.76 (t, J 7.5, 3); 13 C MR (125 Mz, CDCl 3 ) δ = 142.6, 115.0, 61.3, 39.6, 39.1, 36.1, 34.9, 32.5, 30.8, 26.1, 21.7, 20.6, 7.1; RMS (ES) Found: M +, C requires M +, ; LRMS m/z (ES) 194 (100%, M + ). SI 5

7 Br 16 Br Br 17 Preparation of product 17: The dibromide 16 (prepared in two steps according to S.E. Denmark, L.R. Marcin, J. rg. Chem. 1997, 62, ) (4.8 g, 19.8 mmol), ethylene glycol (1.2 ml, 21.7 mmol) and Ts 2 (188 mg, 1.2 mmol) in Ph (180 ml) were heated under reflux with a Dean-Stark to remove water. After 24 h, the solvent was evaporated and the residue was purified by column chromatography, eluting with petrol EtAc (98:2), to give the dibromoacetal (6.40 g, 86%) as an oil; R f 0.34 [petrol EtAc (95:5)]; ν max /cm , 2890, 1225, 1200; 1 MR (250 Mz, CDCl 3 ) δ = 3.95 (s, 4), (m, 4), (m, 4); 13 C MR (63 Mz, CDCl 3 ) δ = 109.8, 65.3, 41.1, 26.1; RMS (EI) Found: M +, C Br 2 requires M +, K t Bu (1.56 g, 13.2 mmol) was added slowly to this dibromoacetal (2.53 g, 8.8 mmol) in TF PhMe (1:1, 20 ml) at 0 C over 30 min. The mixture was allowed to warm to room temperature. After 1 h, saturated aqueous ammonium chloride solution (20 ml) was added, and the mixture was extracted with Et 2 (3 30 ml). The organic layers were dried (MgS 4 ), filtered and evaporated. Purification by column chromatography, eluting with petrol EtAc (98:2), gave the bromide 17 (1.50 g, 82%) as an oil; R f 0.45 [petrol EtAc (95:5)]; ν max /cm , 1405, 1200; 1 MR (250 Mz, CDCl 3 ) δ = 5.70 (dd, J 17.0, 10.5, 1), 5.38 (dd, J 17.0, 1.5, 1), 5.20 (dd, J 10.5, 1.5, 1), (m, 4), (m, 2), (m, 2); 13 C MR (63 Mz, CDCl 3 ) δ = 136.8, 116.4, 108.0, 64.7, 41.5, 26.3; RMS (EI) Found: M +, C Br requires M +, ; LRMS m/z (CI) 209 (42%, M + ( 81 Br)), 207 (42, M + ( 79 Br)), 181 (5), 179 (5), 99 (100). C Br Preparation of product 18: In the same way as the nitrile 2a, diisopropylamine (1.3 ml, 9.4 mmol) in TF (9 ml), n-butyllithium (3.6 ml, 8.9 mmol, 2.5 M in hexanes), butyronitrile (1.6 ml, 17.8 mmol) and the bromide 17 (923 mg, 4.5 mmol) in TF (5 ml) gave, after purification by column chromatography, eluting with petrol EtAc (95:5), the nitrile 18 (769 mg, 88%) as an oil; R f 0.20 [petrol EtAc (95:5)]; ν max /cm , 2885, 2235, 1460; 1 MR (250 Mz, CDCl 3 ) δ = 5.69 (dd, J 17.0, 10.5, 1), 5.36 (dd, J 17.0, 1.5, 1), 5.18 (dd, J 10.5, 1.5, 1), (m, 4), (m, 1), (m, 6), 1.06 (t, J 7.5, 3); 13 C MR (63 Mz, CDCl 3 ) δ = 137.2, 122.0, 116.1, 108.4, 64.7, 64.5, 35.5, 33.1, 25.8, 25.5, 11.6; RMS (ES) Found: M +, C requires M +, ; LRMS m/z (ES) 196 (100%, M + ). C C Cl Preparation of product 19: In the same way as the nitrile 2a, diisopropylamine (1.1 ml, 8 mmol) in TF (7.5 ml), n-butyllithium (3.1 ml, 7.6 mmol, 2.5 M in hexanes), nitrile 18 (746 mg, 3.82 mmol) and 1-bromo-3-chloropropane (0.8 ml, 7.6 mmol) gave, after purification by column chromatography, eluting with petrol EtAc (9:1), the nitrile 19 (1.00 g, 96%) as an oil; R f 0.43 [petrol EtAc (85:15)]; ν max /cm , 2230, 1460; 1 MR (250 Mz, CDCl 3 ) δ = 5.69 (dd, J 17.0, 10.5, 1), 5.35 (dd, J 17.0, 1.5, 1), 5.18 (dd, J 10.5, 1.5, 1), (m, 4), 3.55 (t, J 6.0, 2), (m, 10), 0.99 (t, J 7.5, 3); 13 C MR (63 Mz, CDCl 3 ) δ = 137.2, 123.3, 116.1, 108.3, 64.6 (2 C 2 ), 44.6, 40.2, 33.0, 32.5, 28.9 (2 C 2 ), 27.5, 8.6; RMS (ES) Found: M +, C Cl requires M +, ; LRMS m/z (ES) 274 (3%, M + ( 37 Cl)), 272 (100, M + ( 35 Cl)). SI 6

8 C C 19 Cl 20 Cl Preparation of product 20: To the nitrile 19 (585 mg, 2.14 mmol) in C 2 Cl 2 (21 ml) at 78 C was added DIBAL- (2.8 ml, 2.8 mmol, 1.0 M in hexanes). After 3 h, aqueous oxalic acid solution (2 ml, 0.5 M) was added and the mixture was allowed to warm to room temperature. Further aqueous oxalic acid solution (10 ml) and saturated sodium potassium tartrate solution (10 ml) were added, and the mixture was extracted with Et 2 (4 20 ml). The organic layers were dried (MgS 4 ), evaporated and the residue was purified by column chromatography, eluting with petrol EtAc (93:7), to give the aldehyde 20 (487 mg, 82%) as an oil; R f 0.30 [petrol EtAc (9:1)]; ν max /cm , 1720; 1 MR (500 Mz, CDCl 3 ) δ = 9.34 (s, 1), 5.68 (dd, J 17.0, 10.5, 1), 5.35 (dd, J 17.0, 2.0, 1), 5.17 (dd, J 10.5, 2.0, 1), (m, 4), (m, 2), (m, 10), 0.78 (t, J 7.5, 3); 13 C MR (125 Mz, CDCl 3 ) δ = 206.4, 137.2, 116.0, 108.6, 64.6 (2 C 2 ), 51.3, 42.4, 31.7, 28.3, 26.6, 24.7, 24.6, 7.8; RMS (ES) Found: M +, C Cl requires M +, ; LRMS m/z (ES) 277 (2%, M + ( 37 Cl)), 275 (100, M + ( 35 Cl)). 20 C Cl 21 Preparation of product 21: See Experimental Section in the main paper Preparation of product 1: The acetal 21 (174 mg, 0.69 mmol) in TF (4 ml) and aqueous Cl (4 ml, 2 M) was heated to 80 C. After 1 h, the mixture was cooled to room temperature and was basified by addition of aqueous sodium hydroxide solution (4 ml, 2 M). The mixture was extracted with C 2 Cl 2 (3 10 ml), dried (MgS 4 ) and evaporated. Purification by column chromatography, eluting with C 2 Cl 2 EtAc (95:5), gave the ketone 1 (127 mg, 88%) as an oil; R f 0.18 [C 2 Cl 2 EtAc (95:5)]; ν max /cm , 1700, 1460; 1 MR (500 Mz, CDCl 3 ) δ = (m, 2), 2.65 (ddd, J 9.0, 5.0, 1.5, 1), (m, 2), (m, 2), (m, 3), 1.79 (td, J 12.0, 2.5, 1), (m, 3), (m, 2), (m, 1), 1.09 (td, J 13.0, 4.5, 1), 0.76 (t, J 7.5, 3); 13 C MR (125 Mz, CDCl 3 ) δ = 208.4, 73.5, 53.2, 52.9, 48.1, 36.8, 34.7, 32.8, 30.0, 26.1, 21.3, 21.2, 7.1; RMS (ES) Found: M +, C requires M +, ; LRMS m/z (ES) 208 (100%, M + ); data consistent with the literature (R. Iyengar, K. Schildknegt, M. Morton, J. Aubé, J. rg. Chem. 2005, 70, ). + 1 aspidospermidine Preparation of aspidospermidine: The ketone 1 (115 mg, 0.55 mmol) in Ph (5 ml) and phenylhydrazine (0.07 ml, 0.67 mmol) was heated under reflux. After 2.5 h, the mixture was cooled to room temperature, the solvent was evaporated, the mixture was redissolved in acetic acid (5 ml) and was heated at 95 C. After 2.5 h, the mixture was cooled to room temperature, the solvent was evaporated and the mixture dissolved in TF (5 ml). SI 7

9 LiAl 4 (211 mg, 5.55 mmol) was added and the mixture was heated under reflux. After 13 h, the mixture was cooled to 0 C, water (3 ml) was added, the suspension was filtered through celite and was washed with EtAc (3 5 ml). The mixture was dried (a 2 S 4 ) and evaporated. Purification by column chromatography, eluting with EtAc, gave aspidospermidine (66 mg, 42%) as an oil which crystallised on standing; m.p C; R f 0.43 [C 2 Cl 2 Me (9:1)]; ν max /cm , 2930, 1610, 1480, 1465; 1 MR (500 Mz, CDCl 3 ) δ = 7.07 (d, J 7.5, 1), 7.00 (td, J 7.5, 1.0, 1), 6.71 (td, J 7.5, 1.0, 1), 6.62 (d, J, 7.5, 1), 3.50 (dd, J 11.0, 6.0, 1), (br s, 1 ), (m, 1), (m, 1), (m, 3), (s, 2), (m, 1), (m, 2), (m, 4), (m, 2), (m, 1), 0.63 (t, J 7.5, 3); 13 C MR (125 Mz, CDCl 3 ) δ = 149.4, 135.7, 127.1, 122.8, 119.0, 110.3, 71.3, 65.6, 53.8, 53.4, 53.0, 38.8, 35.6, 34.5, 30.0, 28.1, 23.0, 21.7, 6.8; RMS (ES) Found: M +, C requires M +, ; LRMS m/z (ES) 283 (100%, M + ); data consistent with the literature (R. Iyengar, K. Schildknegt, M. Morton, J. Aubé, J. rg. Chem. 2005, 70, ). In addition the indole shown above (12 mg, 8%) was isolated as an oil; R f 0.17 [C 2 Cl 2 Me (9:1)]; ν max /cm , 2930, 1640, 1480, 1465; 1 MR (500 Mz, CDCl 3 ) δ = 7.62 (br s, 1), 7.42 (d, J 7.5, 1), 7.24 (d, J 8.5, 1), (m, 2), (m, 1), (m, 2), 2.81 (br d, J 15.5, 1), 2.46 (d, J 15.5, 1), (m, 1), 2.10 (q, J 9.0, 1), (m, 4), (m, 1), (m, 1), (m, 1), (m, 1), (m, 1), 0.80 (t, J 7.5, 3); 13 C MR (125 Mz, CDCl 3 ) δ = 136.8, 135.6, 128.3, 120.8, 118.9, 118.1, 110.2, 106.8, 72.6, 55.1, 53.8, 36.2, 33.9, 32.9, 30.2, 28.0, 23.4, 22.1, 7.5; RMS (ES) Found: M +, C requires M +, ; LRMS m/z (ES) 281 (100%, M + ); data consistent with the literature (R. Iyengar, K. Schildknegt, M. Morton, J. Aubé, J. rg. Chem. 2005, 70, ). Ac Me 1 aspidospermine Preparation of aspidospermine: o-methoxyphenylhydrazine (131 mg, 0.74 mmol) was added to the ketone 1 (127 mg, 0.61 mmol) and sodium carbonate (78 mg, 0.74 mmol) in Et (5 ml) at room temperature. After 3 h, the mixture was filtered through celite, the solid was washed with Et (10 ml) and the solvent was evaporated. Water was further removed using a benzene water azeotrope. Purification through a short column of silica, eluting with petrol EtAc (85:15) gave the hydrazone (158 mg) as an oil. Ac (5 ml) was added and the mixture was heated at 95 C. After 1 h, the mixture was cooled to room temperature and the solvent was evaporated. The mixture was dissolved in C 2 Cl 2 and was washed with saturated aqueous sodium hydrogen carbonate solution (6 ml). The organic layer was dried (a 2 S 4 ) and evaporated. Purification through a short column of silica, eluting with CCl 3 Me (98:2), gave an oil (127 mg). This oil was dissolved in TF (5 ml) and LiAl 4 (47 mg, 1.23 mmol) was added at 45 C. After 16 h water (1 ml) was added and the suspension was filtered through celite. The solid was washed with EtAc (10 ml) and the solvent was evaporated. Purification through a short column of silica, eluting with CCl 3 Me (98:2), gave deacetylaspidospermine as an oil (44 mg). This was dissolved in pyridine (0.5 ml) and acetic anhydride (0.5 ml) at room temperature. After 3 h, the suspension was filtered through celite, the solid was washed with C 2 Cl 2 (10 ml) and evaporated. C 2 Cl 2 (5 ml) was added and the solution was washed with brine and aqueous saturated ammonia solution (1:1, 5 ml), dried (a 2 S 4 ) and evaporated to give a yellow solid. Purification by column chromatography, eluting with CCl 3 Me (98:2) gave aspidospermine (62 mg, 29% over 4 steps) as a colourless solid; m.p C; R f 0.21 [CCl 3 Me (98:2)]; ν max /cm , 1640, 1455, 1385; 1 MR (500 Mz, CDCl 3 ) δ = 7.04 (t, J 8.0, 1), (m, 2), 4.62 (br s, 1 ), 3.85 (s, 3), 3.09 (td, J 9.0, 2.5, 1), 3.00 (br d, J 9.5, 1), (m, 5), (m, 4), (m, 1), (m, 3), 1.29 (m, 1), (m, 1), (m, 2), (m, 1), 0.58 (t, J 7.5, 3); 13 C MR (125 Mz, CDCl 3 ) δ = 171.6, 149.4, 143.7, 129.3, 126.0, 115.5, 111.0, 71.1, 69.5, 55.4, 53.6 (2 C 2 ), 52.5, 38.0, 35.5, 34.2, 30.0, 24.8, 23.1, 23.0, 21.6, 6.8; RMS (ES) Found: M +, C requires M +, ; LRMS m/z (ES) 355 (100%, M + ); data consistent with the literature (Y. Fukuda, M. Shindo, K. Shishido, rg. Lett. 2003, 5, ). 1 quebrachamine Preparation of quebrachamine: Phenylhydrazine (0.08 ml, 0.81 mmol) was added to the ketone 1 (140 mg, 0.68 mmol) in Ph (5 ml) and the mixture was heated under reflux. After 2 h, the mixture was cooled to room temperature, the solvent was evaporated, acetic acid (5 ml) was added and the mixture was SI 8

10 heated at 95 C. After 2 h, the mixture was cooled to room temperature, the solvent was evaporated and methanolic K (25 ml, 1% K in Me) was added. KB 4 (372 mg, 6.75 mmol) was added and the mixture was heated under reflux. After 13 h, the mixture was cooled to room temperature and the solvent was evaporated. Purification by column chromatography, eluting with EtAc Me (95:5), gave quebrachamine (75 mg, 39%), which recrystallised from Me as needles; m.p C; R f 0.33 [C 2 Cl 2 Me (95:5)]; ν max /cm , 2920, 2855, 2775, 1610, 1460; 1 MR (500 Mz, CDCl 3 ) δ = 7.68 (br s, 1), (m, 1), (m, 1), (m, 2), 7.25 (br d, J 12.0, 1), 2.95 (ddd, J 14.5, 11.5, 4.5, 1), 2.85 (ddd, J 14.5, 4.5, 3.0, 1), (m, 2), (m, 2), 2.34 (td, J 11.5, 4.5, 1), 2.26 (td, J 11.0, 3.0, 1), 1.93 (ddd, J 14.0, 7.5, 1.5, 1), (m, 2), 1.51 (d, J 12.0, 1), (m, 5), 0.86 (t, J 7.5, 3); 13 C MR (125 Mz, CDCl 3 ) δ = 139.9, 134.8, 128.9, 120.2, 118.7, 117.4, 110.0, 108.7, 56.7, 55.1, 53.2, 37.1, 34.8, 33.5, 32.1, 22.7, 22.4, 22.0, 7.8; RMS (ES) Found: M +, C requires M +, ; LRMS m/z (ES) 283 (100%, M + ); data consistent with the literature (S.A. Kozmin, T. Iwama, Y. uang, V.. Rawal, J. Am. Chem. Soc. 2002, 124, ). X-Ray crystal structures of the following 7 compounds: (i) and (ii) The Cl salt of the products formed by reduction of the esters 4 and 5 (LiAl 4, TF, 0 C) followed by conversion to their p- bromobenzoates (p-bromobenzoyl chloride, Et 3, DMAP, C 2 Cl 2 ). (iii) and (iv) The products formed by reducing the bond (Zn, Ac, 2, 70 C) followed by diacylation (p-bromobenzoyl chloride, Et 3, DMAP, C 2 Cl 2 ) of the isoxazolidines 6 and 7. (v) and (vi) The tricyclic amine sulfone 12 and 13. (vii) The tricyclic amine 21. i) The Cl salt of the product formed by reducing the ester 4 followed by acylation with p-bromobenzoyl chloride: Detailed results are deposited at the Cambridge Crystallographic Data Centre. Structure umber CCDC ii) The Cl salt of the product formed by reducing the ester 5 followed by acylation with p-bromobenzoyl chloride: Detailed results are deposited at the Cambridge Crystallographic Data Centre. Structure umber CCDC iii) The product formed by reducing the bond followed by diacylation with p-bromobenzoyl chloride of the isoxazolidine 6: Detailed results are deposited at the Cambridge Crystallographic Data Centre. Structure umber CCDC iv) The product formed by reducing the bond followed by diacylation with p-bromobenzoyl chloride of the isoxazolidine 7: Detailed results are deposited at the Cambridge Crystallographic Data Centre. Structure umber CCDC v) The tricyclic amine 12: Detailed results are deposited at the Cambridge Crystallographic Data Centre. Structure umber CCDC vi) The tricyclic amine 13: Detailed results are deposited at the Cambridge Crystallographic Data Centre. Structure umber CCDC vii) The tricyclic amine 21: Detailed results are deposited at the Cambridge Crystallographic Data Centre. Structure umber CCDC and 13 C MR spectra for the tricyclic products 4 10, (and 15), 21 and 1, plus the spectra for the aldehyde 20 and the alkaloids aspidospermidine, aspidospermine and quebrachamine. SI 9

11

12

13

14

15

16

17

18

19

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21 Me Current Data Parameters AME 400 h EXP 1 PRC 1 F2 - Acquisition Parameters Date_ Time ISTRUM drx500 PRBD 5 mm BBI 1-BB PULPRG zg30 TD SLVET CDCl3 S 32 DS 4 SW z FIDRES z AQ sec RG 128 DW usec DE 6.00 usec TE K D sec TD0 1 ======== CAEL f1 ======== UC1 1 P usec PL db SF Mz F2 - Processing parameters SI SF Mz WDW no SSB 0 LB 0.00 z GB 0 PC ppm

22 Me Current Data Parameters AME 400 c EXP 1 PRC 1 F2 - Acquisition Parameters Date_ Time ISTRUM drx500 PRBD 5 mm BBI 1-BB PULPRG zgdc30 TD SLVET CDCl3 S 513 DS 4 SW z FIDRES z AQ sec RG DW usec DE 6.00 usec TE K D sec d sec TD0 1 ======== CAEL f1 ======== UC1 13C P usec PL db SF Mz ======== CAEL f2 ======== CPDPRG2 waltz16 UC2 1 PCPD usec PL db PL db SF Mz F2 - Processing parameters SI SF Mz WDW EM SSB 0 LB 2.00 z GB 0 PC ppm

23 Ph Current Data Parameters AME 399 h EXP 1 PRC 1 F2 - Acquisition Parameters Date_ Time ISTRUM drx500 PRBD 5 mm BBI 1-BB PULPRG zg30 TD SLVET CDCl3 S 32 DS 4 SW z FIDRES z AQ sec RG 128 DW usec DE 6.00 usec TE K D sec TD0 1 ======== CAEL f1 ======== UC1 1 P usec PL db SF Mz F2 - Processing parameters SI SF Mz WDW no SSB 0 LB 0.00 z GB 0 PC ppm

24 Ph Current Data Parameters AME 399 c EXP 1 PRC 1 F2 - Acquisition Parameters Date_ Time ISTRUM drx500 PRBD 5 mm BBI 1-BB PULPRG zgdc30 TD SLVET CDCl3 S 8571 DS 4 SW z FIDRES z AQ sec RG DW usec DE 6.00 usec TE K D sec d sec TD0 1 ======== CAEL f1 ======== UC1 13C P usec PL db SF Mz ======== CAEL f2 ======== CPDPRG2 waltz16 UC2 1 PCPD usec PL db PL db SF Mz F2 - Processing parameters SI SF Mz WDW EM SSB 0 LB 2.00 z GB 0 PC ppm

25 S 2Ph Current Data Parameters AME 144 cis EXP 1 PRC 1 F2 - Acquisition Parameters Date_ Time ISTRUM drx500 PRBD 5 mm BBI 1-BB PULPRG zg30 TD SLVET DMS S 32 DS 4 SW z FIDRES z AQ sec RG 100 DW usec DE 6.00 usec TE K D sec MCREST sec MCWRK sec ======== CAEL f1 ======== UC1 1 P usec PL db SF Mz F2 - Processing parameters SI SF Mz WDW no SSB 0 LB 0.00 z GB 0 PC ppm

26 S 2Ph Current Data Parameters AME 144 cis c EXP 1 PRC 1 F2 - Acquisition Parameters Date_ Time 9.02 ISTRUM drx500 PRBD 5 mm BBI 1-BB PULPRG jmod TD SLVET CDCl3 S 615 DS 4 SW z FIDRES z AQ sec RG DW usec DE 6.00 usec TE K CST CST D sec d sec DELTA sec MCREST sec MCWRK sec ======== CAEL f1 ======== UC1 13C P usec p usec PL db SF Mz ======== CAEL f2 ======== CPDPRG2 waltz16 UC2 1 PCPD usec PL db PL db SF Mz F2 - Processing parameters SI SF Mz WDW EM SSB 0 LB 2.00 z GB 0 PC ppm

27 S 2Ph Current Data Parameters AME 144 trans EXP 1 PRC 1 F2 - Acquisition Parameters Date_ Time ISTRUM drx500 PRBD 5 mm BBI 1-BB PULPRG zg30 TD SLVET CD32 S 32 DS 4 SW z FIDRES z AQ sec RG 64 DW usec DE 6.00 usec TE K D sec MCREST sec MCWRK sec ======== CAEL f1 ======== UC1 1 P usec PL db SF Mz F2 - Processing parameters SI SF Mz WDW no SSB 0 LB 0.00 z GB 0 PC ppm

28 S 2Ph Current Data Parameters AME 144 trans c EXP 1 PRC 1 F2 - Acquisition Parameters Date_ Time ISTRUM drx500 PRBD 5 mm BBI 1-BB PULPRG zgdc30 TD SLVET CDCl3 S 186 DS 4 SW z FIDRES z AQ sec RG DW usec DE 6.00 usec TE K D sec d sec MCREST sec MCWRK sec ======== CAEL f1 ======== UC1 13C P usec PL db SF Mz ======== CAEL f2 ======== CPDPRG2 waltz16 UC2 1 PCPD usec PL db PL db SF Mz F2 - Processing parameters SI SF Mz WDW EM SSB 0 LB 2.00 z GB 0 PC ppm

29 Current Data Parameters AME 161 cis EXP 1 PRC 1 F2 - Acquisition Parameters Date_ Time ISTRUM drx500 PRBD 5 mm BBI 1/D- PULPRG zg30 TD SLVET CDCl3 S 32 DS 4 SW z FIDRES z AQ sec RG 100 DW usec DE 6.00 usec TE K D sec TD0 1 ======== CAEL f1 ======== UC1 1 P usec PL db SF Mz F2 - Processing parameters SI SF Mz WDW no SSB 0 LB 0.00 z GB 0 PC ppm

30 Current Data Parameters AME AB161 cis c EXP 1 PRC 1 F2 - Acquisition Parameters Date_ Time ISTRUM drx500 PRBD 5 mm BBI 1/D- PULPRG zgdc30 TD SLVET CDCl3 S 2490 DS 4 SW z FIDRES z AQ sec RG DW usec DE 6.00 usec TE K D sec d sec TD0 1 ======== CAEL f1 ======== UC1 13C P usec PL db SF Mz ======== CAEL f2 ======== CPDPRG2 waltz16 UC2 1 PCPD usec PL db PL db SF Mz F2 - Processing parameters SI SF Mz WDW EM SSB 0 LB 2.00 z GB 0 PC ppm

31 Current Data Parameters AME AB161 cis EXP 1 PRC 1 F2 - Acquisition Parameters Date_ Time ISTRUM drx500 PRBD 5 mm BBI 1/D- PULPRG zg30 TD SLVET CDCl3 S 32 DS 4 SW z FIDRES z AQ sec RG 100 DW usec DE 6.00 usec TE K D sec TD0 1 ======== CAEL f1 ======== UC1 1 P usec PL db SF Mz F2 - Processing parameters SI SF Mz WDW no SSB 0 LB 0.00 z GB 0 PC ppm

32 Current Data Parameters AME AB161 cis c EXP 1 PRC 1 F2 - Acquisition Parameters Date_ Time ISTRUM drx500 PRBD 5 mm BBI 1/D- PULPRG zgdc30 TD SLVET CDCl3 S 544 DS 4 SW z FIDRES z AQ sec RG DW usec DE 6.00 usec TE K D sec d sec TD0 1 ======== CAEL f1 ======== UC1 13C P usec PL db SF Mz ======== CAEL f2 ======== CPDPRG2 waltz16 UC2 1 PCPD usec PL db PL db SF Mz F2 - Processing parameters SI SF Mz WDW EM SSB 0 LB 2.00 z GB 0 PC ppm

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