ANNEXE 2 : SPECTRES DE RÉSONANCE MAGNÉTIQUE NUCLÉAIRE

ANNEXE 2 : SPECTRES DE RÉSONANCE MAGNÉTIQUE NUCLÉAIRE 175

4-Oxopentyl acetate (1-9) 27.56 17.91 63.49 39.76 29.86 22.66 2.82 2. 1.97 2.91 2.96 2.9 4. 3.98 3.96 2.47 2.44 2.42 2.7 1.95 1.86 1.84 1.82 1.79 1.77 176

177 4-Hydroxy-4-methylhex-5-en-1-yl acetate (1-1) 2.97 4. 2.17 1.8 1.2 1. 1. 1.23 1.56 1.57 1.58 3.52 3.54 3.54 3.56 3.56 3.57 3.68 4.97 4.98 5.1 5.1 5.13 5.13 5.18 5.19 5.79 5.82 5.84 5.88 7.26-1 1 2 3 4 5 6 7 8 9 1 11 12 13 14 15 16 17 18 19-1 1 2 3 4 5 6 7 8 9 1 11 12 13

4-Methyl-6-(trimethylsilyl)hex-4-en-1-yl acetate (1-11) 1 H-NMR spectrum 1 9 8 7 6 5 4 3 2 1 13 8. 7.5 7. C-NMR spectrum 6.5 6. 5.5 5. 4.5 4. 3.5 3. 2.5 2. 1.5 1..5. -.5 36 34 32 3 28 26 24 22 2 18 16 14 12 1 8 6 4 2-2 -4 19 18 17 16 15 14 13 12 11 1 9 8 7 6 5 4 3 2 1-1 178

179 4-Methyl-6-(trimethylsilyl)hex-4-en-1-ol (1-12) 8.66 1.81 1.88 4.58 2.12 2.12 1. -.3 1.37 1.4 1.55 1.6 1.63 1.65 1.65 1.68 1.68 1.7 1.72 2.1 2.3 2.4 2.5 2.7 2.8 3.59 3.6 3.61 3.62 3.63 3.64 5.13 5.16 5.17 5.17 5.2 5.2 5.23 5.23-1.74-1.7 15.69 18.32 18.61 23.3 27.69 3.75 31.8 36.17 62.8 63.7 12.71 12.99 131.92

18 N-(Cyanomethyl)-N-(4-methyl-6-(trimethylsilyl)hex-4-en-1-yl)formamide (1-15) 9. 2.12 2.1 3.21 2.1 2.6 2.4.85.9 -.1 1.34 1.37 1.4 1.43 1.56 1.69 1.72 1.73 1.74 1.75 1.99 2. 2.3 2.5 3.34 3.35 3.37 3.38 3.39 3.4 4.17 4.28 4.29 5.18 5.21 5.24 7.26 8.6 8.8-1.7-1.6 15.6 18.6 18.8 23. 25.9 26. 27.9 3. 3. 36.2 47.1 47.4 114.7 122.3 122.6 129.9 13. 162.3 162.3

181 2-(3-Methyl-3-vinylpiperidin-1-yl)acetonitrile (1-17).63 3.13.51 1.75 1.3 2.9 1.2 1.27 1.64 2.1.79.8.68.86.88.89 1.4 1.5 1.52 1.65 1.66 1.68 1.69 1.7 2.23 2.26 2.41 2.44 2.46 2.47 2.49 2.51 3.5 5.1 5.2 5.2 5.5 5.82 5.84 5.85 5.86 5.89 7.26 7.26 21.82 34.54 36.82 46.83 52.66 62.78 112.3 114.71 145.93

(2S,3R)-2-Benzyl-3-hydroxy-3-(4-nitrophenyl)propanal (1-31) 1 H-NMR spectrum.8 2.17 2.26 6.39 1. 2.43 2.42 9.78 9.78 8.25 8.23 7.54 7.52 7.34 7.32 7.31 7.28 7.26 7.24 7.18 7.16 5.1 3.12 3.1 3.8 3.5 3.3 3.1 2.99 2.93 2.92 2.89 2.87 2.85 2.83 182

183 (S)-3,5-Dibenzyl-6-(4-nitrophenyl)-3,6-dihydro-2H-1,3-oxazin-2-one (1-34) 2. 2.5 3. 3.5 4. 4.5 5. 5.5 6. 6.5 7. 7.5 8. 8.5 9. -1 1 2 3 4 5 6 7 8 9 1 11 12 13 14-3 -2-1 1 2 3 4 5 6 7 8 9 1 11 12 13 14 15 16 17 18 19 2-1 1 2 3 4 5 6 7 8 9 1E+5 1E+5 1E+5 1E+5 1E+5 2E+5 2E+5 2E+5 2E+5 2E+5 2E+5 2E+5

184 (S)-2-((R)-Hydroxy(phenyl)methyl)cyclohexanone (1-53).95 2.94 1.14.98 1.8.98.98.96 1. 4.51 1.22 1.25 1.26 1.46 1.49 1.49 1.5 1.51 1.53 1.54 1.55 1.99 2. 2.1 2.29 2.29 2.31 2.31 2.33 2.34 2.39 2.39 2.4 2.4 2.41 2.41 2.45 2.57 2.57 3.95 3.96 4.72 4.72 4.75 4.75 7.26 7.26 7.26 7.27 7.28

185 (S)-2-((R)-Phenyl(trityloxy)methyl)cyclohexanone (1-54)..5 1. 1.5 2. 2.5 3. 3.5 4. 4.5 5. 5.5 6. 6.5 7. 7.5 8. -2 2 4 6 8 1 12 14 16 18 2 22 24 26 1 2 3 4 5 6 7 8 9 1 11 12 13 14 15 16 17 18 19 2 21-2 2 4 6 8 1 12 14 16 18 2 22 24 26 28 3 32 34 36 38 4

(((R)-((R)-2-(Methoxymethylene)cyclohexyl)(phenyl)methoxy)methanetriyl)tribenzene (1-55) 1 H-NMR spectrum 1.45 19.13.85.74 2.73.73 2. 1.99 4.44 7.46 7.46 7.44 7.36 7.35 7.34 7.34 7.33 7.32 7.31 7.31 7.3 7.3 7.26 7.24 6.36 6.19 3.68 3.67 3.7 2.54 2.53 2.51 2.35 2.34 2.33 1.64 1.62 1.6 1.55 186

(S)-2-((R)-(Methoxymethoxy)(phenyl)methyl)cyclohexanone (1-64) 1 H-NMR spectrum 187

188 (S)-2-((R)-((Methylthio)methoxy)(phenyl)methyl)cyclohexanone (1-67) 1.7 1.99 3.26 3.7 1.17 1.5.98 1.3 1. 1. 5.29 1.3 1.31 1.51 1.51 1.52 1.54 1.55 1.55 1.57 1.58 1.76 1.77 1.79 1.8 1.81 1.82 1.83 1.85 1.86 1.88 2.12 2.43 2.53 2.56 2.58 2.6 2.62 2.73 2.73 2.75 2.75 2.76 2.78 2.79 2.79 2.81 4.22 4.26 4.57 4.61 5.9 5.12 7.26 7.28 7.3 7.3 7.31 7.32 7.32 7.34 14.2 23.6 28.6 3.6 41.5 57.1 72.6 76.8 76.9 77.2 77.6 128.1 128.4 128.7 138.7 211.7

189 (S)-2-((R)-Phenyl((phenylthio)methoxy)methyl)cyclohexanone (1-69)..5 1. 1.5 2. 2.5 3. 3.5 4. 4.5 5. 5.5 6. 6.5 7. 7.5 8. 8.5-1 1 2 3 4 5 6 7 8 9 1 11 12 13 14 15 16 17 1.9 2.12 3.22 1. 1.48 1.2.91.97.97 2.27 2.55 3.95 1.28 2.5 1.29 1.32 1.33 1.36 1.56 1.58 1.6 1.61 1.63 1.76 1.81 1.83 1.84 2.21 2.23 2.25 2.27 2.29 2.39 2.41 2.43 2.45 2.47 2.49 2.52 2.53 2.54 2.55 2.58 2.77 2.8 2.82 2.85 4.64 4.67 5.6 5.1 5.23 5.26 7.2 7.23 7.26 7.29 7.31 7.33 7.35 7.36 7.38 7.4 7.43 7.43 7.51 7.54 7.56 7.66 7.68 7.71 8.16 8.16 8.19 1 2 3 4 5 6 7 8 9 1 11 12 13 14 15 16 17 18 19 2 21-5 5 1 15 2 25 3 35 4 45 5 55 6 65 7 75 8 22.97 28.22 3. 4.94 57.15 72.87 126.36 128.11 128.38 128.59 128.85 128.89 128.91 129.31 13.56 134.58 136.12 138.13 162.37 211.44

19 (S)-2-((R)-Phenyl((phenylsulfonyl)methoxy)methyl)cyclohexanone (1-7) 1.34 2.32 3.14.99 2.7 1.21 1.8 1. 1.54 3.19 2.17 1.25 1.97.95 1.19 1.21 1.22 1.24 1.25 1.46 1.49 1.5 1.51 1.53 1.53 1.55 1.56 1.58 1.73 1.74 1.75 1.76 1.77 1.79 1.8 1.86 1.87 1.88 2.38 2.63 2.65 2.65 2.67 2.69 2.7 2.71 2.71 2.72 2.74 2.74 4.37 4.41 4.5 4.55 5.22 5.25 7.18 7.19 7.2 7.2 7.21 7.22 7.26 7.3 7.31 7.32 7.32 7.33 7.33 7.34 7.49 7.49 7.51 7.52 7.53 7.54 7.54 7.61 7.61 7.61 7.63 7.78 7.78 7.79 7.8 7.8 7.81 7.81 7.81 8.9 8.9 8.12 8.12 23.1 28.3 3.1 41. 57.3 73. 126.5 128.2 128.5 128.7 129. 129. 129. 129.4 13.7 134.7 136.2 138.2 162.5 211.6

(+)-N,S-Dimethylsulfoximine (1-81) 1 H-NMR spectrum.62.96 1..99 7.9 7.89 7.89 7.88 7.87 7.87 7.61 7.61 7.26 3.6 2.63 191

192 (S)-2-((R)-Phenyl((triethylsilyl)oxy)methyl)cyclohexanone (1-82) 4.9 6.8 24.3 28.3 3.2 42.1 59.6 73.3 126.5 127.2 127.5 127.9 128.1 143. 211.6 6.15 9.47 4.6 1.7 2.11.99 1. 4.38.45.47.48.48.49.51.52.79.82.82.85 1.56 1.56 1.57 1.58 1.69 1.71 1.72 1.75 1.91 2.37 2.39 2.39 2.41 2.66 2.66 2.67 2.67 2.69 2.69 5.1 5.13 7.26 7.29 7.29 7.3 7.31 7.31

193 (E)-((R)-2-((R)-Phenyl((triethylsilyl)oxy)methyl)cyclohexylidene)methyl-N-methyl-Sphenylsulfoximine (1-83) 5.39 8.67 5.14 1.81.97 2.93.98 1..97 5.47 3.9 2.1.11.14.16.19.59.62.65 1.27 1.31 1.42 1.42 1.45 1.46 1.5 1.51 1.54 1.7 1.86 1.88 1.97 2.37 2.38 2.4 2.67 3.45 3.49 4.71 4.75 6.27 7.18 7.2 7.21 7.23 7.24 7.25 7.25 7.26 7.27 7.54 7.54 7.54 7.9 7.91 7.92 7.92 7.93 7.93 4.73 6.76 21.71 25.82 27.83 29.36 3.4 54.43 74.9 125.83 125.89 126.88 127.82 128.32 128.92 129.13 132.14 141.18 143.5 16.44

194 Triethyl ((3R,3aR)-3-phenyl-3,3a,4,5,6,7-hexahydroisobenzofuran-1-yl)silane (1-85) 6.42 9.7 2.9 1.94.91.84 1.86 1. 5.95.71.71.74.76.76.79.79.87 1.1 1.3 1.6 1.27 1.28 1.3 1.81 1.81 1.82 1.83 1.83 2.6 2.52 2.57 2.63 2.65 2.66 4.88 4.91 7.25 7.25 7.26 7.26 7.27 7.28 7.28 7.28 7.29 7.31 7.32 7.33 7.34 7.35 7.35 7.36 7.36 7.37 7.38 7.38 7.47 3.4 7.6 7.6 24.9 25.6 27.8 34.4 54.9 88.7 125.5 127.2 128.5 128.6 144.3 144.3 148.3

195 Ethyl (3-hydroxypropyl)((trimethylsilyl)methyl)carbamate (1-15) -.5..5 1. 1.5 2. 2.5 3. 3.5 4. 4.5 5. 5.5 6. 6.5 7. 7.5 8. 8.5-5 5 1 15 2 25 3 35 4 45 5 55 6 65 7 75 8 85 9-1 1 2 3 4 5 6 7 8 9 1 11 12 13 14 15 16-4 -2 2 4 6 8 1 12 14 16 18 2 22 24 26 28 3 32 34 36-1.8 14.5 29.7 3.7 37.8 38.7 45.4 45.8 58.3 59.3 61.1 156.1 157.

Ethyl (3-oxopropyl)((trimethylsilyl)methyl)carbamate (1-16) 45 4 35 3 25 2 15 1 5 11. 1.5 1. 9.5 9. 8.5 8. 7.5 7. 6.5 6. 5.5 5. 4.5 4. 3.5 3. 2.5 2. 1.5 1..5. -.5 1 9 8 7 6 5 4 3 2 1-1 21 2 19 18 17 16 15 14 13 12 11 1 9 8 7 6 5 4 3 2 1-1 196

Ethyl ((3R,4S)-5-((R)-2-benzyl-5-oxopyrrolidin-1-yl)-3-hydroxy-4-methyl-5-oxopentyl)((trimethylsilyl)methyl)carbamate (1-17) 4 35 3 25 2 15 1 5 7.5 7. 6.5 6. 5.5 5. 4.5 4. 3.5 3. 2.5 2. 1.5 1..5. -.5 11 1 9 8 7 6 5 4 3 2 1 19 18 17 16 15 14 13 12 11 1 9 8 7 6 5 4 3 2 1-1 197

Ethyl ((3R,4S)-3-hydroxy-5-(methoxy(methyl)amino)-4-methyl-5-oxopentyl) ((trimethylsilyl)methyl)carbamate (1-18) 1E+5 1E+5 1E+5 1E+5 9 8 7 6 5 4 3 2 1-1 5.5 5. 4.5 4. 3.5 3. 2.5 2. 1.5 1..5. -.5 85 8 75 7 65 6 55 5 45 4 35 3 25 2 15 1 5 19 18 17 16 15 14 13 12 11 1 9 8 7 6 5 4 3 2 1-1 198

199 Ethyl ((3R,4S)-3-hydroxy-4-methyl-5-oxopentyl)((trimethylsilyl)methyl)carbamate (1-19)..5 1. 1.5 2. 2.5 3. 3.5 4. 4.5 5. 5.5 6. 6.5 7. 7.5 8. 8.5 9. 9.5 1. -5 5 1 15 2 25 3 35 4 45 5 55 6 65 7 75 8 1 2 3 4 5 6 7 8 9 1 11 12 13 14 15 16 17 18 19 2 21-2 2 4 6 8 1 12 14 16 18 2 22 24 26 28 3

2 Ethyl (R)-(2-(2,2-diisopropyl-5-methyl-4H-1,3,2-dioxasilin-4-yl)ethyl)((trimethylsilyl)methyl)carbamate (1-121)..5 1. 1.5 2. 2.5 3. 3.5 4. 4.5 5. 5.5 6. 6.5 7. -5 5 1 15 2 25 3 35 4 45 5 55 6 65 7 75 8 9. 15.82 3.33 2.9 1.13.97 2.6.62 1.5.98 2.5.95.91 16.62 34.68 35.87 37.12 348.25 355.31 435.33 467.17 485.35 57.3 576.22 582.88 589.19 81.4 825.87 828.16 843.65 928.55 968.51 982.29 991.69 116.18 129.94 1198.65 125.7 1212.75 1219.81 138.37 1314.21 188.56 1881.98 1883.4 1 2 3 4 5 6 7 8 9 1 11 12 13 14 15 16-2 2 4 6 8 1 12 14 16 18 2 22 24 26 28 3 32 34

Allyl (3-hydroxypropyl)((trimethylsilyl)methyl)carbamate (1-15b) 75 7 65 6 55 5 45 4 35 3 25 2 15 1 5-5 7. 6.5 6. 5.5 5. 4.5 4. 3.5 3. 2.5 2. 1.5 1..5. -.5 7 65 6 55 5 45 4 35 3 25 2 15 1 5-5 19 18 17 16 15 14 13 12 11 1 9 8 7 6 5 4 3 2 1-1 21

22 Allyl (3-oxopropyl)((trimethylsilyl)methyl)carbamate (1-123) -.5..5 1. 1.5 2. 2.5 3. 3.5 4. 4.5 5. 5.5 6. 6.5 7. 7.5 8. 8.5 9. 9.5 1. 1.5 11. -1 1 2 3 4 5 6 7 8 9 1 11 12 13 14 15 16 17 18 19-1 1 2 3 4 5 6 7 8 9 1 11 12 13 14 15 16 17 18 19 2 21 2 4 6 8 1 12 14 16 18 2 22 24 26

23 Allyl ((3R,4S)-5-((R)-2-benzyl-5-oxopyrrolidin-1-yl)-3-hydroxy-4-methyl-5-oxopentyl) ((trimethylsilyl)methyl)carbamate (1-124)..5 1. 1.5 2. 2.5 3. 3.5 4. 4.5 5. 5.5 6. 6.5 7. 7.5 5 1 15 2 25 3 35 4 45 9.64 3.21 2.25 2.12 1.6 1.11 2.23 2.19 1.11 2.17 2.21 1.1 1.3 1.5 1. 5.3.6.7.7 1.17 1.19 1.52 1.55 1.59 1.61 1.64 1.66 1.68 2.76 3.22 3.29 3.34 3.53 3.68 3.71 3.73 4.19 4.22 4.32 4.38 4.5 4.51 4.52 4.69 5.15 5.17 5.2 5.25 5.3 5.87 5.89 5.9 5.92 5.93 5.94 5.94 5.98 7.21 7.22 7.23 7.23 7.26 7.28 7.28 7.29 7.29 7.3 7.3-1 1 2 3 4 5 6 7 8 9 1 11 12 13 14 15 16 17 18 19-1 1 2 3 4 5 6 7 8 9 1E+5 1E+5

Allyl ((3R,4S)-3-hydroxy-5-(methoxy(methyl)amino)-4-methyl-5-oxopentyl)((trimethylsilyl)methyl)carbamate (1-125) 1E+5 9 8 7 6 5 4 3 2 1 7. 6.5 6. 5.5 5. 4.5 4. 3.5 3. 2.5 2. 1.5 1..5. 24

25 Allyl ((3R,4S)-3-hydroxy-4-methyl-5-oxopentyl)((trimethylsilyl)methyl)carbamate (1-126)..5 1. 1.5 2. 2.5 3. 3.5 4. 4.5 5. 5.5 6. 6.5 7. 7.5 8. 8.5 9. 9.5 1. 1.5-1 1 2 3 4 5 6 7 8 9 1E+5 1E+5-1 1 2 3 4 5 6 7 8 9 1 11 12 13 14 15 16 17 18 19 2 21-2 -1 1 2 3 4 5 6 7 8 9 1 11 12 13 14

26 Allyl (R)-(2-(2,2-diisopropyl-5-methyl-4H-1,3,2-dioxasilin-4-yl)ethyl)((trimethylsilyl)methyl)carbamate (1-127) -1 1 2 3 4 5 6 7 8 9 1 11 12 13 14 15 16 17 18 19 1 2 3 4 5 6 7 8 9 1 11 12 13 -.5..5 1. 1.5 2. 2.5 3. 3.5 4. 4.5 5. 5.5 6. 6.5 7. -2 2 4 6 8 1 12 14 16 18 2 22 24 26 28

27 (R)-N-(2-(2,2-diisopropyl-5-methyl-4H-1,3,2-dioxasilin-4-yl-)ethyl)-N-((trimethylsilyl)methyl)formamide (1-129) 8.99 16.13 1.56 2.99 2.84 1.13.8.4.81.83 1.15 1.1.62.96.98.1.11 1.3 1.25 1.44 1.46 1.59 1.6 1.61 1.96 1.97 1.98 2. 2.1 2.4 2.65 2.7 2.79 2.8 2.97 3.2 3.35 3.36 3.38 3.39 3.46 3.49 3.51 3.53 4.27 4.3 4.36 4.39 5.3 6.23 8. 8.8-2.1-1.4 12. 12.8 13. 15.4 15.5 16.4 16.4 16.6 16.6 16.6 17. 32.9 34. 34.1 39.1 42. 45.5 71.6 72.6 113.8 114.3 137.3 137.7 161.9 162.2

28 Allyl ((3R,4R)-5-((R)-2-benzyl-5-oxopyrrolidin-1-yl)-3-hydroxy-4-methyl-5-oxopentyl)((trimethylsilyl)methyl)carbamate (1-133) -.5..5 1. 1.5 2. 2.5 3. 3.5 4. 4.5 5. 5.5 6. 6.5 7. 7.5 8. 8.5-1 1 2 3 4 5 6 7 8 9 1 11 12 13 14 15 16 17 18 19-1 1 2 3 4 5 6 7 8 9 1 11 12 13 14 15 16 17 18 19-4 -2 2 4 6 8 1 12 14 16 18 2 22 24 26 28 3 32 34 36

Allyl ((3R,4S)-3,5-dihydroxy-4-methylpentyl)((trimethylsilyl)methyl)carbamate (1-134) 6 55 5 45 4 35 3 25 2 15 1 5-5 7. 6.5 6. 5.5 5. 4.5 4. 3.5 3. 2.5 2. 1.5 1..5. 4E+5 3E+5 3E+5 3E+5 3E+5 3E+5 2E+5 2E+5 2E+5 2E+5 2E+5 1E+5 1E+5 1E+5 8 6 4 2-2 17 16 15 14 13 12 11 1 9 8 7 6 5 4 3 2 1 29

21 Allyl ((3R,4R)-3-hydroxy-4-methyl-5-oxopentyl)((trimethylsilyl)methyl)carbamate (1-134) -1 1 2 3 4 5 6 7 8 9 1 11 12 13 14 15 16 17 18 19 2 21 5 1 15 2 25 3 -.5..5 1. 1.5 2. 2.5 3. 3.5 4. 4.5 5. 5.5 6. 6.5 7. 7.5 8. 8.5 9. 9.5 1. 1.5 11. 11.5-2 2 4 6 8 1 12 14 16 18 2 22 24 26 28 3 32 34 36 9.27 2.86 1.6 1.15 1.75 1.76.93.8.65 2.7 2.5 1..88.8.9 1.11 1.14 1.16 1.5 1.78 1.82 1.86 2.44 2.47 2.49 2.93 2.98 3.2 3.71 3.89 3.93 3.96 4.4 4.59 4.6 5.23 5.26 5.3 5.35 5.89 5.91 5.92 5.93 5.94 5.97 5.98 5.98 6. 6.2 9.81 O N OH TMS O O

211 (S)-4-Benzyl-3-(hept-6-enoyl)oxazolidin-2-one (2-9) 2.12 2.17 2.8 1. 2.7 1.3 2.5 1.1 2. 1. 5.19 1.69 1.71 1.74 1.74 1.76 1.77 2.9 2.12 2.14 2.17 2.78 2.8 2.83 2.92 2.95 2.95 2.97 2.98 3.28 3.29 3.32 3.33 4.18 4.19 4.19 4.21 4.67 4.68 4.69 4.7 4.97 5. 5.2 5.8 5.8 5.77 5.79 5.81 5.82 5.83 5.85 5.86 5.87 5.88 5.91 7.21 7.23 7.24 7.26 7.27 7.29 7.29 7.3 7.31 7.33 7.35 7.37 7.38 23.73 28.32 33.48 35.37 37.93 55.13 66.17 114.72 127.33 128.94 129.42 135.34 138.43 173.2

212 Allyl (5-phenylpent-1-en-3-yl) carbonate (2-13) 2.6 2.8 2.12 1. 4.15 2.4 3.8 2.33 1.92 1.93 1.93 1.95 1.95 1.96 1.96 1.98 2. 2.1 2.3 2.3 2.4 2.5 2.6 2.6 2.8 2.8 2.11 2.66 2.68 2.68 2.69 2.7 2.71 2.73 4.62 4.63 4.63 4.64 4.65 4.65 5.7 5.9 5.11 5.13 5.24 5.27 5.27 5.3 5.3 5.34 5.34 5.35 5.35 5.36 5.36 5.4 5.4 5.4 7.17 7.2 7.22 7.22 7.26 7.27 7.29

213 5-Phenylpent-1-en-3-ol (2-14) 1.8 2.5 2.8 1. 1. 1.2.98 5.13 1.64 1.88 1.88 1.9 1.9 1.91 1.93 1.93 2.72 2.74 2.77 2.79 4.13 4.15 4.17 4.2 5.15 5.15 5.16 5.18 5.19 5.19 5.25 5.25 5.3 5.31 5.31 5.88 5.9 5.92 5.94 5.94 5.96 5.98 6. 7.22 7.23 7.25 7.28 7.3 7.32 7.32

214 (4S)-4-Benzyl-3-(5-hydroxyhept-6-enoyl)oxazolidin-2-one (2-17) 2.41 3.16 1.7 2.15 1.6 3.18 1..96.95.87 5.3 1.6 1.62 1.63 1.65 1.68 1.78 1.79 1.8 1.81 1.83 2.73 2.76 2.76 2.79 2.97 2.98 2.99 3. 3.27 3.28 3.3 3.31 4.65 4.65 4.66 4.67 4.68 4.69 5.11 5.14 5.23 5.24 5.28 5.28 5.84 5.86 5.87 5.88 5.9 5.91 5.93 7.19 7.21 7.26 7.26 7.27 7.29 7.31 7.33 7.35

215 Allyl (7-((S)-4-benzyl-2-oxooxazolidin-3-yl)-7-oxohept-1-en-3-yl)carbonate (2-18) 4.2 1. 1.98.99 2. 2.97.98 3.87 1.94 5.5 1.76 1.78 1.79 1.81 2.74 2.77 2.79 2.82 2.94 2.95 2.97 3. 3.26 3.27 3.3 3.31 4.17 4.18 4.21 4.62 4.62 4.63 4.63 4.64 5.23 5.26 5.32 5.37 5.39 5.39 5.77 5.8 5.81 5.83 5.85 5.87 5.9 5.93 5.95 5.99 7.19 7.22 7.22 7.3 7.31 7.34

216 Allyl ((3R,4R)-7-(((allyloxy)carbonyl)oxy)-4-((S)-4-benzyl-2-oxooxazolidine-3-carbonyl)-3- hydroxynon-8-en-1-yl)((trimethylsilyl)methyl)carbamate (2-19) 9.58 6.3 1.97 1.17 1.4 2.22 1.1 1. 1.12 1.17 2.17 2.16 1.99 1.15 6.19 3.1 5.6.6 1.59 1.61 1.62 2.5 2.5 2.51 2.51 2.52 2.77 3.8 3.33 3.35 4.32 4.47 4.48 4.48 4.49 4.5 4.5 4.59 4.59 4.61 4.61 4.72 4.73 5.22 5.23 5.23 5.23 5.27 5.29 5.29 5.86 5.9 5.92 5.92 5.93 5.94 5.95 5.96 7.29 7.31-1.54 24.52 24.66 31.47 31.58 37.8 38.23 45.71 47.84 55.6 55.67 65.91 66.35 68.38 78.63 117.96 118.35 118.85 118.9 127.22 128.93 129.44 131.59 132.95 135.21 135.33 135.6 153.5 154.3 154.32 175.43 175.56

217 Allyl ((3R,4R)-7-(((allyloxy)carbonyl)oxy)-3-hydroxy-4-(methoxy(methyl)carbamoyl)non-8-en-1- yl)((trimethylsilyl)methyl)carbamate (2-2) 11.44.61 6.1 1..94 2.39 2.7.64 1.37 2.4 1.3 1.53.76 2.57 2.74 4.22 5.76 4..6.7 1.34 1.36 1.37 1.38 1.52 1.57 1.58 1.68 1.7 1.71 1.72 1.73 1.75 1.76 1.78 2.28 2.3 2.62 2.67 2.7 2.75 2.79 3.17 3.2 3.25 3.32 3.63 3.67 3.86 3.87 3.89 3.9 4.12 4.15 4.42 4.43 4.44 4.51 4.51 5.1 5.1 5.3 5.4 5.4 5.5 5.17 5.69 5.72 5.85 5.85 5.85 7.1 7.1 7.11 7.11 7.14 7.15 7.16-1.9 31.24 31.5 31.62 32.19 32.99 34.47 34.54 39.24 43.71 44.12 45.66 45.85 46.6 56.66 6.62 6.65 62.4 62.13 65.67 65.78 67.57 67.61 67.76 67.79 69.52 74.37 77.35 77.9 78.8 78.52 116.44 116.66 116.73 116.87 117.1 117.34 117.39 117.65 117.67 124.32 124.64 124.96 131.95 133.4 135.72 135.75 137.5 138.12 15.12 154.34 154.42 154.49 155.51 17.71 17.75

218 Allyl ((3R,4R)-7-(((allyloxy)carbonyl)oxy)-4-formyl-3-hydroxynon-8-en-1-yl)((trimethylsilyl)methyl)carbamate (2-21) 9.71 6.34.83.98 1.8 2.6.76 4.25 1.5 6.4 1.5 1.99 1.1.5 1.61 1.62 1.63 1.65 1.67 1.7 1.76 1.77 1.77 1.79 1.81 2.27 2.46 2.51 2.9 2.95 3.71 3.85 3.89 3.93 4.41 5.2 5.2 5.23 5.23 5.26 5.27 5.32 5.71 5.73 5.75 5.76 5.77 5.87 5.91 5.93 5.96 9.71 9.72-1.56 21.69 21.81 31.62 31.73 32.62 38.14 45.34 56.55 56.68 66.53 67.63 68.39 78.54 78.73 117.87 118.5 118.91 131.56 132.77 135.38 154.33 154.36 157.51 24.75

219 Allyl ((3R,4S)-7-(((allyloxy)carbonyl)oxy)-3-hydroxy-4-(hydroxymethyl)non-8-en-1-yl)((trimethylsilyl)methyl)carbamate (2-22) 7.99 1.77 2.83 2.58.94 1..88 1.91 1.77 3.51 2.68 3.44 2.53.6 1.5 1.51 1.53 1.55 1.66 1.68 1.72 2.11 2.12 2.13 2.14 2.53 2.58 2.76 2.77 2.81 2.82 3.1 3.55 3.57 3.58 3.72 3.73 4.43 4.43 4.44 4.45 4.45 4.48 4.5 4.97 4.97 5.1 5.2 5.2 5.5 5.5 5.6 5.12 5.12 5.17 5.18 5.23 5.23 5.29 5.29-1.58 2.65 2.75 3.64 32.3 38.6 43.74 45.74 64.43 64.55 66.46 68.29 7.79 78.98 79.34 117.69 117.8 117.93 118.78 131.61 132.81 135.69 154.39 157.47

Allyl (7-hydroxyhept-1-en-3-yl) carbonate (2-24) 1 H-NMR spectrum 2.4 4.3.98 2.8 2. 4.3 3.21 5.94 5.92 5.88 5.8 5.77 5.76 5.74 5.38 5.33 5.27 5.27 5.24 5.23 5.19 5.7 4.62 4.6 3.66 3.64 3.62 1.74 1.73 1.71 1.68 1.65 1.61 1.59 1.56 1.46 22

221 Allyl ((3R,4R)-7-(((allyloxy)carbonyl)oxy)-4-((S)-4-benzyl-2-oxooxazolidine-3-carbonyl)-3- ((trimethylsilyl)oxy)non-8-en-1-yl)((trimethylsilyl)methyl)carbamate (2-28) 9. 8.57 6.5 3.9 3.1.95 3.1 1.9 2.14 1.8 2.46 4.74 3.6 5.54.9.17.17 1.62 1.64 1.66 1.7 1.74 1.76 1.79 1.84 2.71 2.75 2.8 2.85 3.33 4.7 4.14 4.15 4.17 4.18 4.2 4.23 4.52 4.62 4.63 4.63 5.25 5.28 5.31 5.33 5.37 5.38 5.81 5.83 5.84 5.87 5.88 5.88 5.9 5.9 5.91 5.93 5.95 7.23 7.26 7.28 7.29 7.32 7.34 7.36 7.38-1.5.4 1.3 21.5 32. 38.2 46. 46.7 55.3 55.4 65.8 66.1 68.3 7.6 78.8 117.9 118.2 118.8 127.4 129. 129.4 131.6 133.3 135.4 153.1 153.1 154.3 154.3 155.7 173.4

222 Allyl (2-((4R)-5-(3-(((allyloxy)carbonyl)oxy)pent-4-en-1-yl)-2,2-diisopropyl-4H-1,3,2-dioxasilin-4- yl)ethyl)((trimethylsilyl)methyl)carbamate (2-3) 8.23 14.37 4.85 2.52 1.96 2.1 4.98 2.98 3.93 1.79 1.33 1..13 1.1 1.11 1.12 1.14 1.67 1.68 1.7 1.77 1.78 1.86 2.11 2.12 2.12 2.13 2.14 2.85 2.85 2.86 3.46 3.48 3.49 3.51 3.56 3.57 3.59 3.61 4.42 4.43 4.44 4.45 4.55 4.56 4.58 5.1 5.2 5.2 5.6 5.6 5.22 5.68 5.69 5.73 5.73 5.75 6.23 6.24 6.27-1.56 12.18 12.85 16.36 16.41 16.72 16.76 17.21 17.46 25.52 32.88 33.63 34.6 38.78 39.32 45.85 46.43 65.78 68.33 71.32 78.14 78.62 116.91 117.46 117.74 118.19 118.84 131.59 133.41 135.41 135.66 138.45 154.29 154.33 155.79

223 N-(2-((4R)-5-(3-Hydroxypent-4-en-1-yl)-2,2-diisopropyl-4H-1,3,2-dioxasilin-4-yl)ethyl)-N- ((trimethylsilyl)methyl)formamide (2-32) 8.85 15.18 7.51.65 1.23.69 1.84.98.91 2.6.99.84 1..8.11.12.13.17 1. 1.4 1.27 1.57 1.58 1.59 1.6 1.62 1.63 1.65 1.92 1.95 2.65 2.7 2.81 3. 3.5 3.37 3.39 3.4 3.5 3.53 3.55 4.9 4.11 4.13 4.37 5.8 5.82 5.84 5.86 5.88 5.88 5.9 5.92 5.93 6.3 6.31 6.31 7.28 8.1 8.9-2.7-1.38 12.1 12.16 12.82 16.38 16.45 16.71 16.77 25.66 25.72 34.11 34.23 34.25 35.48 35.53 35.72 39.27 42.2 42.25 45.73 7.35 7.48 72.24 72.69 76.61 77.3 77.45 114.88 115.25 117.86 118. 138.44 138.46 14.73 14.94 162.1

224 (R)-N-(2-(2,2-Diisopropyl-5-(3-oxopent-4-en-1-yl)-4H-1,3,2-dioxasilin-4-yl)ethyl)-N- ((trimethylsilyl)methyl)formamide (2-33) 8.43 14.51 1.79 2.94 2.57.41.7.84 1.9.95.96 2.77 1..12.13 1.3 1.69 2.5 2.13 2.14 2.16 2.17 2.19 2.64 2.66 2.69 2.81 3.2 3.7 3.38 3.39 3.4 3.41 3.49 3.51 3.54 3.56 4.3 4.33 4.43 4.45 5.84 5.85 5.87 5.89 6.2 6.26 6.3 6.33 6.36 6.39 6.42 8.2 8.1-2.5-1.37 12.9 12.8 16.36 16.42 16.68 16.72 16.76 23.78 24.9 29.7 33.18 34.4 34.23 38.42 39.13 42.19 45.64 7.31 71.46 117.53 117.67 128.29 128.42 136.3 138.68 138.83 161.98 162.2 199.4

225 Allyl (cyanomethyl)(3-hydroxypropyl)carbamate (2-35).5 1. 1.5 2. 2.5 3. 3.5 4. 4.5 5. 5.5 6. 6.5 7. 7.5 8. -2 2 4 6 8 1 12 14 16 18 2 22 24 26 28 3 32 34 1 2 3 4 5 6 7 8 9 1 11 12 13 14 15 16 17 18 19-1 1 2 3 4 5 6 7 8 9 1 11 12 13 3.11 3.68 35.84 45.5 58.62 59.12 67.9 115.97 118.36 131.95 155.39

226 Allyl (cyanomethyl)(3-oxopropyl)carbamate (2-36)..5 1. 1.5 2. 2.5 3. 3.5 4. 4.5 5. 5.5 6. 6.5 7. 7.5 8. 8.5 9. 9.5 1. -1 1 2 3 4 5 6 7 8 9 1E+5 1E+5 1E+5 1E+5 1E+5 2E+5 2E+5 1 2 3 4 5 6 7 8 9 1 11 12 13 14 15 16 17 18 19 2 21 22 23-1 1 2 3 4 5 6 7 8 9 1E+5 1E+5

227 Allyl ((3R,4R)-7-(((allyloxy)carbonyl)oxy)-4-((S)-4-benzyl-2-oxooxazolidine-3-carbonyl)-3- hydroxynon-8-en-1-yl)(cyanomethyl)carbamate (2-37) 6.14 1. 1.9 2.16 1.2 1.1.97 3.3 4.8 1.15 1.1 1.2 5.93 2.9 5.11 1.61 1.62 1.65 1.7 1.78 1.8 1.81 1.82 1.84 2.81 2.84 2.86 2.88 3.1 3.12 3.43 3.44 3.46 3.81 3.98 4.12 4.13 4.15 4.16 4.36 4.36 4.59 4.59 4.61 4.61 5.22 5.22 5.23 5.23 5.29 5.29 5.3 5.89 5.89 5.91 5.92 5.93 5.95 7.26 7.27 7.28 7.29 7.31 7.32 7.33 7.33 7.35 14.4 24.39 24.5 31.41 31.47 33.17 36.23 37.79 45.46 47.61 47.79 55.63 55.7 66.17 67.13 68.38 68.4 7.32 7.53 78.51 115.95 118.2 118.35 118.48 118.87 118.91 127.33 128.95 129.42 131.58 132. 135.14 135.22 153.59 153.77 154.28 175.14 175.31

228 Allyl ((3R,4R)-7-(((allyloxy)carbonyl)oxy)-4-((S)-4-benzyl-2-oxooxazolidine-3-carbonyl)-3- ((trimethylsilyl)oxy)non-8-en-1-yl)(cyanomethyl)carbamate (2-38) 7.81.71 5.97 1.1 1.54 2.27 1.6 1.95 2.32 3.96 1.2 1.6 5.9 2.93 5..14.14 1.9 1.11 1.14 1.63 1.74 1.76 2.5 2.51 2.51 2.52 2.85 2.86 2.89 3.16 3.17 3.41 3.43 4.13 4.15 4.16 4.18 4.19 4.31 4.33 4.35 4.36 4.57 4.59 4.61 4.61 5.1 5.85 5.87 5.89 5.91 5.91 5.93 5.95 7.26 7.26 7.32 7.34.3 21.9 22.9 31.78 31.94 35.87 38.16 38.2 48.5 48.46 55.41 55.48 66.7 66.12 67.1 68.36 68.38 7.52 78.6 78.7 115.82 117.94 118.39 118.83 118.88 127.4 128.99 129.36 131.6 132.1 135.29 135.33 153.17 153.27 154.29 154.32

229 Allyl ((3R,4S)-7-(((allyloxy)carbonyl)oxy)-3-hydroxy-4-(hydroxymethyl)non-8-en-1- yl)(cyanomethyl)carbamate (2-39) 4.37 6.8 1.16 6.12 1.15 1. 3.78 6.35 1.67 9.26 4.74.87 1.39 1.41 1.42 1.45 1.68 1.7 1.89 1.9 1.92 3.48 3.5 3.52 3.53 3.55 3.58 3.73 3.75 3.76 3.94 3.95 3.98 3.99 4.17 4.34 4.37 4.37 4.61 4.61 4.62 5.21 5.24 5.24 5.24 5.3 5.31 5.36 5.36 5.9 5.91 5.92 5.95 5.95 5.96 5.97 5.99 23.55 23.79 31.26 31.35 31.8 33.27 36.44 4.16 44.34 45.34 65.39 65.45 67.5 68.38 68.47 73.92 78.49 78.61 79.1 116.3 117.8 118.11 118.31 118.41 118.9 119.1 131.49 131.6 132.9 135.17 135.27 135.62 154.3 154.33

23 Allyl ((3R,4R)-7-(((allyloxy)carbonyl)oxy)-4-formyl-3-hydroxynon-8-en-1-yl)(cyanomethyl)carbamate (2-4) 4.62 2.7 1.27.68 1.18 1.72 2.1 4.9 1.4 5.93 1.6 1.94 1. 1.67 1.69 1.72 1.84 1.86 2.35 3.3 3.56 3.84 4.18 4.21 4.6 4.62 4.66 5.25 5.28 5.38 5.38 5.72 5.74 5.75 5.78 5.8 5.81 5.83 5.86 5.87 5.88 5.89 5.9 5.9 5.9 5.92 5.92 5.94 5.95 5.95 5.96 5.96 5.97 5.98 5.99 9.72 9.73 21.53 21.61 31.45 31.52 32.85 35.91 45.3 56.39 56.5 67.5 67.75 68.44 78.38 115.56 118.1 118.11 118.88 118.97 131.5 131.7 135.2 154.3 154.34 155.69 24.42

231 N-(Cyanomethyl)-N-(2-((4R)-5-(3-hydroxypent-4-en-1-yl)-2,2-diisopropyl-4H-1,3,2-dioxasilin-4- yl)ethyl)formamide (2-41) 14.85 2.97 2.7 1.25.93 1. 1.78 1.7 4.9 1.8 6.3 1.9 2.3.98 1.2 1.68 1.71 1.73 1.84 1.87 2.1 2.3 3.46 3.48 3.51 3.53 3.59 3.61 3.62 3.64 3.66 3.67 3.69 4.15 4.21 4.29 4.38 4.41 4.45 5.2 5.21 5.22 5.23 5.25 5.27 5.31 5.33 5.36 5.87 5.89 5.91 5.93 5.95 5.96 6.25 12.8 12.77 12.78 13.6 16.3 16.37 16.67 16.72 17.6 17.19 25.36 32.82 34.9 36.18 36.25 44.47 66.94 68.33 7.88 78.9 78.45 115.81 115.84 117. 117.75 118.17 118.27 118.83 131.57 132.15 135.29 135.56 138.74 154.26 154.29

232 N-(Cyanomethyl)-N-(2-((4R)-5-(3-hydroxypent-4-en-1-yl)-2,2-diisopropyl-4H-1,3,2-dioxasilin-4- yl)ethyl)formamide (2-42) 15.45 1.13 2.44 2.88 2.8 1.46 1.18 1.4 1.34 1.42 2.14 2.4 1.17 1. 1.2 1.3 1.63 1.65 1.68 1.7 1.71 1.72 1.73 2.8 2.8 2.11 2.12 2.12 2.13 2.14 2.15 3.49 3.51 3.52 3.53 3.55 3.74 3.75 3.76 3.78 4.16 4.22 4.23 4.25 4.35 4.38 4.41 5.11 5.12 5.12 5.15 5.24 5.25 5.81 5.83 5.84 5.85 5.87 6.29 6.3 8.12 8.13 12.2 12.75 12.76 16.33 16.41 16.56 16.66 16.7 16.74 17. 25.34 25.76 3.44 3.46 33.95 34.4 35.8 35.81 44.3 44.36 69.69 7. 72.35 72.47 114.71 114.91 114.95 115.12 115.2 117.59 117.67 138.63 138.67 14.52 14.89 161.8 162.68 162.69

233 (R)-N-(Cyanomethyl)-N-(2-(2,2-diisopropyl-5-(3-oxopent-4-en-1-yl)-4H-1,3,2-dioxasilin-4- yl)ethyl)formamide (2-43) 14.93 2.45 2.7 1.88 1.5 1.23 3.13 1.5 2.85 1. 1.1 1.2 1.6 1.64 1.66 1.67 1.68 1.69 1.7 2.64 2.67 2.69 3.53 3.55 3.56 3.57 3.71 3.73 3.74 3.76 3.78 4.25 4.27 4.3 4.33 4.35 4.4 5.82 5.83 5.86 5.86 6.18 6.24 6.24 6.3 6.33 6.36 6.39 8.13 12.2 12.76 16.34 16.42 16.66 16.75 23.49 3.36 33.94 38.58 44.14 69.87 114.99 117.36 128.6 136.26 139.8 162.71 199.59

234 (S,E)-Methyl 8-(4-benzyl-2-oxooxazolidin-3-yl)-8-oxooct-2-enoate (2-44) 1.99 2.4 2.1 1.5 2.5 1.1 3.3 2.12 1.2 1..97 5.2 1.54 1.56 1.59 1.71 1.73 1.74 1.75 1.76 2.23 2.25 2.26 2.28 2.28 2.78 2.82 2.93 2.94 2.96 3.26 3.27 3.3 3.31 3.72 4.17 4.18 4.21 4.64 4.66 4.67 4.68 4.69 4.7 5.83 5.83 5.87 5.88 5.88 6.92 6.95 6.97 6.98 7. 7.19 7.22 7.22 7.27 7.29 7.29 7.29 7.3 7.3 7.31 7.33 7.33 7.36 23.65 27.37 31.85 35.15 37.81 51.31 55.3 66.2 121.22 127.26 128.87 129.38 135.31 148.86 153.41 166.89 172.79

235 Allyl ((3R,4R)-4-((S)-4-benzyl-2-oxooxazolidine-3-carbonyl)-3-hydroxynon-8-en-1- yl)(cyanomethyl)carbamate (2-48) 26.42 28.76 31.81 33.63 36.24 37.8 45.18 48.17 55.65 66.12 67.13 7.42 115.3 115.96 118.46 127.35 128.96 129.42 132.2 135.28 138.3 153.58 175.86 2.44 1.36 1.76 1.13 2.5 1.1.98 2.27 1.12.96 1. 2.8 1.9 1.92 1. 1.2.97 1.3 4.7.91 1.31 1.33 1.36 1.63 1.65 1.66 1.68 1.83 1.98 1.99 2. 2.1 2.3 2.6 2.82 2.84 2.86 2.89 3.11 3.12 3.44 3.47 3.52 4.11 4.12 4.14 4.15 4.32 4.35 4.36 4.37 4.59 4.59 4.6 4.61 4.61 4.62 4.74 4.76 4.96 4.97 5.78 5.8 5.89 5.91 5.93 5.95 7.3 7.3

236 Allyl (cyanomethyl)((3r,4s)-3-hydroxy-4-(hydroxymethyl)non-8-en-1-yl)carbamate (2-5) 1.8 3.4 1.65 2.65 4.17.79 2.8 1.84 1.86.84.97.95 1. 1.18 1.21 1.23 1.42 1.43 1.55 1.66 1.67 2.4 2.1 3.35 3.44 3.47 3.49 3.5 3.51 3.53 3.55 3.58 3.61 3.64 3.67 3.68 3.71 3.75 4.3 4.5 4.7 4.22 4.25 4.65 4.66 4.67 4.98 4.98 5.3 5.24 5.28 5.3 5.7 5.72 5.73 5.74 5.75 5.78 5.79 5.81 5.83 5.88 5.9 5.91 5.93 5.95 5.97 5.99 7.26 25.93 26.5 26.76 27.38 27.53 33.2 33.69 33.79 34. 36.49 4.26 4.38 44.62 45.49 62.73 65.83 66.14 66.87 66.97 7.49 74.16 74.22 114.51 115.13 116.7 118.22 118.28 132.13 137.92 138.71 154.63 155.55

237 Allyl (cyanomethyl)((3r,4r)-4-formyl-3-hydroxynon-8-en-1-yl)carbamate (2-51) 2.9 4.1 1.17 2.4.99.71 1.6 1.95 2.49 2.37 2.21 1.9 1.6 1.3 1..95 1.38 1.4 1.42 1.44 1.62 1.68 1.71 1.72 1.73 1.76 1.78 1.83 1.84 1.86 1.87 1.88 1.88 1.89 1.91 1.92 3.31 3.45 3.49 3.55 3.82 4.12 4.16 4.22 4.26 5.26 5.28 5.32 5.36 5.7 5.72 5.72 5.73 5.74 5.76 5.77 5.78 5.78 5.89 5.9 5.92 5.93 7.26 9.7 9.71 25.5 26.2 27.9 32.8 33.5 36. 45.2 57.2 67.2 68. 115.1 116. 118.4 131.9 137.9 155.5 171.6 25.2

238 (R)-Allyl (cyanomethyl)(2-(2,2-diisopropyl-5-(pent-4-en-1-yl)-4h-1,3,2-dioxasilin-4- yl)ethyl)carbamate (2-52) 18.21 2.62 3.36 3.61 1.14 1.4 2.19.82 2.23 2.25 1.5.99 1.2.95 1.3.98.98.99 1. 1.2 1.4 1.37 1.42 1.45 1.71 1.73 1.76 1.78 1.8 2. 2.1 2.2 2.3 2.3 2.5 3.45 3.47 3.48 3.5 3.52 3.61 3.62 3.63 3.64 3.65 3.67 3.68 4.18 4.22 4.31 4.39 4.41 4.63 4.64 4.96 5. 5.1 5.22 5.25 5.34 5.73 5.74 5.74 5.75 5.77 5.79 6.24 7.26 26.42 28.76 33.63 36.24 37.8 48.17 55.65 66.12 67.13 7.42 115.3 115.96 118.46 127.35 128.96 129.42 132.2 135.28 138.3 153.58 175.86

239 Methyl (R,E)-5-(4-(2-(N-(cyanomethyl)formamido)ethyl)-2,2-diisopropyl-4H-1,3,2-dioxasilin-5- yl)pent-2-enoate (2-56) -1 1 2 3 4 5 6 7 8 9 1 11 12 13 14 15 16 17 18 19 1 2 3 4 5 6 7 8 9 1E+5 1E+5..5 1. 1.5 2. 2.5 3. 3.5 4. 4.5 5. 5.5 6. 6.5 7. 7.5 8. 8.5 9. 9.5-5 5 1 15 2 25 3 35 4 45 5 55 6 65 7 75 8 85

24 Methyl (6R,6aS)-6a-formyl-6-((hydroxydiisopropylsilyl)oxy)-31,4,5,6,6a,7,8,8a-octahydrocyclopenta[h,i]indolizine-1-carboxylate (2-66)..5 1. 1.5 2. 2.5 3. 3.5 4. 4.5 5. 5.5 6. 6.5 7. 7.5 8. 8.5 9. 9.5 1. -5 5 1 15 2 25 3 35 4 45 5 55 6 12.4 12.7 17.2 17.2 27.2 29.7 29.7 31.1 4.7 45.2 5.3 63. 63.9 66.9 12.5 15.6 166.7 22.

241 Benzyl 2-(((allyloxy)carbonyl)(3-hydroxypropyl)amino)acetate (3-43) 2.9 2.13 2.48 2. 1.99 4.27 1.5 5.44 1.65 1.67 1.69 1.71 1.74 1.76 3.42 3.45 3.47 3.54 3.56 3.58 3.6 3.98 4.5 4.49 4.51 4.57 4.59 5.1 5.13 5.16 5.19 5.22 5.22 5.31 5.71 5.73 5.74 5.76 5.78 5.8 5.82 5.84 5.85 5.86 5.88 5.9 5.92 5.94 7.31 3.56 31.23 45.42 45.54 49.35 49.6 58.64 59.37 66.35 66.42 66.47 66.86 66.9 117.39 117.57 128.21 128.3 128.37 128.46 128.59 132.41 132.64 135.34 135.42 156.59 169.55 169.77

Benzyl 2-(((allyloxy)carbonyl)(3-oxopropyl)amino)acetate (3-44) 1 H-NMR spectrum.95 6.26 1.15 4.6 2. 1.82 1.85 1.63 9.75 7.35 7.26 5.96 5.94 5.92 5.89 5.87 5.85 5.83 5.81 5.79 5.77 5.76 5.24 5.18 5.16 5.12 4.64 4.62 4.54 4.52 4.13 4.11 3.65 3.63 3.61 2.86 2.84 2.82 242

243 (S)-4-Benzyl-3-(hex-5-enoyl)oxazolidin-2-one (3-46) 2.19 2.5 1.13 2.34 1.14 2.28 1.15 2.4 1. 5.89 1.81 1.81 1.83 1.84 1.86 1.88 2.15 2.18 2.2 2.22 2.76 2.79 2.8 2.83 2.94 2.97 2.99 3.3 3.31 3.34 3.35 4.17 4.18 4.2 4.2 4.23 4.26 4.68 4.7 4.71 4.72 5.2 5.5 5.6 5.12 5.12 5.79 5.81 5.82 5.83 5.84 5.86 5.88 5.89 5.9 5.92 7.22 7.25 7.25 7.28 7.29 7.3 7.31 7.32 7.32 7.33 7.34 7.36 7.39 7.39 23.39 33.2 34.84 37.9 55.12 66.18 115.34 127.33 128.94 129.43 135.34 137.82 153.44 173.11

244 Methyl (6R,7R,E)-9-(((allyloxy)carbonyl)(2-(benzyloxy)-2-oxoethyl)amino)-6-((S)-4-benzyl-2- oxooxazolidine-3-carbonyl)-7-hydroxynon-2-enoate (3-48) 1.94 1.77 1.84 1. 1.63 1.12 2.6 1.61 4.97 1. 4.49 1.89.9 11.95 1.27 1.72 1.73 1.89 1.92 1.94 1.96 2.3 2.2 2.22 2.25 2.68 2.71 2.73 2.76 3.27 3.29 3.3 3.34 3.35 3.39 3.4 3.52 4.52 4.54 4.6 4.62 4.66 4.68 4.69 5.12 5.15 5.16 5.18 5.24 5.75 5.76 5.79 5.82 5.84 5.88 5.9 6.85 6.87 6.89 6.91 6.92 6.94 7.24 7.26 7.3 7.33 7.34

245 Methyl (6R,7R,E)-9-(((allyloxy)carbonyl)(2-(benzyloxy)-2-oxoethyl)amino)-6-((S)-4-benzyl-2- oxooxazolidine-3-carbonyl)-7-((trimethylsilyl)oxy)non-2-enoate (3-49) 8.72 2.95 1.11 2.14 1.1 3.7 2.89 6.1 1.9 1.5 3.79 1.95 1.6 1.88 35.12 37.65 523.54 528.15 535.58 546.77 57.29 578.49 586.8 6. 61.19 644.82 647.72 651.71 798.77 82.18 86.92 811.7 82.6 991.23 1.82 15.78 121.59 128.73 135.75 119.8 1228.75 1242.26 1246.5 1248.78 1339.51 1344.84 136.61 1366.4 1529.57 1539.76 1547.27 1557.92 1573.63 1715.82 1726.46 1736.5 1741.75 1747.13 1751.78 1758.63 1769.4 257.14 263.93 271.82 279.52 286.14 2165.87 218.13 2192.69 22.94.32 24.28 3.43 3.51 31.63 38.7 45.53 48.86 49.4 49.59 49.84 51.44 55.35 66.14 66.42 66.89 66.95 7.3 7.55 117.23 117.62 121.44 121.47 128.29 128.34 128.59 128.96 129. 129.35 135.42 148.29 148.44 153.6 155.48 156.21 166.79 166.83 169.59 169.65 173.29 173.34

246 Methyl (6S,7R,E)-9-(((allyloxy)carbonyl)(2-(benzyloxy)-2-oxoethyl)amino)-7-hydroxy-6- (hydroxymethyl)non-2-enoate (3-5) 1.7 3.42 1.11 2.22 2.58 3.75 1.66 3.84 2.42 4.57 2.2 1. 5.73 1.3 1.32 1.34 1.42 1.6 1.96 1.98 2.15 2.18 2.2 2.23 2.25 2.29 3.48 3.49 3.64 3.65 3.66 3.69 3.72 3.97 4. 4.1 4.3 4.5 4.6 4.12 4.52 4.57 4.61 4.63 5.12 5.16 5.16 5.18 5.23 5.27 5.28 5.8 5.85 6.84 6.86 6.88 6.89 6.91 6.93 7.33 7.34 24.36 24.91 25.85 26.65 27.92 29.53 29.61 33.45 33.72 45.81 49.65 49.75 51.44 56.32 57.1 66.7 66.76 67.5 67.11 67.45 117.62 117.68 121.67 128.31 128.56 128.64 132.2 135.24 148.1 157.11 166.88 169.5 171.23 24.63

247 Methyl (6R,7R,E)-9-(((allyloxy)carbonyl)(2-(benzyloxy)-2-oxoethyl)amino)-6-formyl-7- hydroxynon-2-enoate (3-51) 1.24 2.45 1.3 3.21.8 3.6 4.98 1.55.48 3.98 2.1.96 5.31.97 1.24 1.5 1.52 1.54 1.55 1.65 1.68 1.7 1.72 1.84 1.86 1.87 1.88 1.89 1.9 2.17 2.2 2.23 2.25 2.27 2.29 3.2 3.4 3.6 3.7 3.7 3.89 3.97 4.1 4.9 4.15 4.54 4.56 4.61 5.16 5.17 5.19 5.25 5.77 5.79 5.81 5.83 5.86 6.85 6.88 6.9 6.9 6.93 7.33 7.34 9.71 9.72 24.4 29.5 33.4 45.8 49.8 51.4 56.3 66.8 67.1 67.4 117.7 121.7 128.3 128.6 128.6 132.2 135.2 148.1 157.1 166.9 169.5 24.6

248 Methyl (R,E)-5-(4-(2-(((allyloxy)carbonyl)(2-(benzyloxy)-2-oxoethyl)amino)ethyl)-2,2-diisopropyl- 4H-1,3,2-dioxasilin-5-yl)pent-2-enoate (3-52) 14.95 1.67 2.77 2.56 1.9 1.32 3.27 2.23.95 2. 4.11 1.9.94.9 5. 1. 1.2 1.5 1.7 1.64 1.66 1.68 1.69 1.71 1.72 1.74 1.75 1.95 1.96 1.99 2.2 2.4 2.21 2.24 2.27 2.31 2.31 3.63 3.68 3.74 4.6 4.7 4.1 4.17 4.4 4.42 4.55 4.57 4.64 4.66 5.19 5.21 5.21 5.24 5.27 5.3 5.35 5.36 5.81 5.87 6.27 6.87 6.89 6.91 6.92 6.94 7.37 12.1 12.8 16.3 16.4 16.7 17.1 28.5 28.6 3.9 3.9 34.2 34.7 45.3 46.2 5. 51.4 66.2 66.4 66.9 66.9 7.9 71. 117.2 117.6 121.6 128.2 128.4 128.4 128.6 132.7 132.7 135.4 138.7 148.1 148.2 155.6 156.4 166.8 169.7

249 Methyl (R,E)-5-(4-(2-(N-(2-(benzyloxy)-2-oxoethyl)formamido)ethyl)-2,2-diisopropyl-4H-1,3,2- dioxasilin-5-yl)pent-2-enoate (3-53) 15.6 1.74 2.8 2.24 1.8 3.71 2.1 1.8 2.24 1. 1.4 1. 5.41 1.2.96.98 1. 1.25 1.58 1.6 1.63 1.88 1.91 1.93 1.97 2.17 2.2 2.22 2.29 2.3 2.31 3.43 3.45 3.46 3.47 3.65 3.66 3.68 3.71 4.4 4.6 4.1 4.12 4.15 4.2 4.4 4.42 5.17 5.19 5.21 5.79 5.81 5.84 5.86 6.25 6.27 6.85 6.87 6.9 6.9 6.93 6.95 7.26 7.32 7.35 7.36 7.43 7.44 7.46 7.47 8.7 8.21 12. 12.8 16.3 16.4 16.6 16.7 28.4 3.9 31. 33.3 34.6 41.4 44.7 44.8 49.8 51.4 67.2 67.4 69.8 71. 117.2 121.7 128.3 128.5 128.6 128.7 135.2 139. 148. 148.1 163.3 163.4 166.8 168.4

25 (1S,31S,6R,6aS,8aR)-2-Benzyl 1-methyl 6a-formyl-6-((hydroxydiisopropylsilyl)oxy)decahydrocyclopenta[h,i]indolizine-1,2-dicarboxylate (3-54) 15.78 6.89 1.3 2.2 1.26 2.77 1.18 1. 1.18.9 1.1 1.1 6.13.9.98 1. 1.69 1.7 1.73 1.75 1.76 1.77 1.8 1.9 1.91 2.84 2.91 2.92 2.93 2.94 2.96 2.97 3.5 3.64 3.71 3.89 3.91 4.5 4.8 4.51 4.52 4.53 5.8 5.12 5.14 5.18 7.33 7.34 7.36 7.36 7.37 9.58 12.4 12.7 16.9 17.2 28.5 29.3 31.4 4.6 43.3 51.8 55.3 63. 63.3 66.3 66.9 68.8 128.3 128.5 128.6 135.8 17.2 172.2 24.

Methyl (6R,7R,E)-9-(((allyloxy)carbonyl)(cyanomethyl)amino)-6-((S)-4-benzyl-2-oxazolidi-ne-3- carbonyl)-7-hydroxynon-2-enoate (3-55) 14 13 12 11 1 9 8 7 6 5 4 3 2 1-1 8. 7.5 7. 6.5 6. 5.5 5. 4.5 4. 3.5 3. 2.5 2. 1.5 1..5 251

Methyl (6R,7R,E)-9-(((allyloxy)carbonyl)(cyanomethyl)amino)-6-((S)-4-benzyl-2-oxazolidine-3- carbonyl)-7-((trimethylsilyl)oxy)non-2-enoate (3-56) 5 45 4 35 3 25 2 15 1 5 8. 7.5 7. 6.5 6. 5.5 5. 4.5 4. 3.5 3. 2.5 2. 1.5 1..5. -.5 252

Methyl (6S,7R,E)-9-(((allyloxy)carbonyl)(cyanomethyl)amino)-7-hydroxy-6-(hydroxymethyl)non- 2-enoate (3-57) 18 17 16 15 14 13 12 11 1 9 8 7 6 5 4 3 2 1-1 7.5 7. 6.5 6. 5.5 5. 4.5 4. 3.5 3. 2.5 2. 1.5 1..5. 22 2 18 16 14 12 1 8 6 4 2-2 19 18 17 16 15 14 13 12 11 1 9 8 7 6 5 4 3 2 1 253

254 Methyl (6R,7R,E)-9-(((allyloxy)carbonyl)(cyanomethyl)amino)-6-formyl-7-hydroxynon-2-enoate (3-58) 1 2 3 4 5 6 7 8 9 1 11 12 13 14 15 16 17 18 19 2 21-5 5 1 15 2 25 3 35 4 45 -.5..5 1. 1.5 2. 2.5 3. 3.5 4. 4.5 5. 5.5 6. 6.5 7. 7.5 8. 8.5 9. 9.5 1. 1.5 11. -5 5 1 15 2 25 3 35 4 45 5 55

255 Methyl (E)-5-(4-(2-(((allyloxy)carbonyl)(cyanomethyl)amino)ethyl)-2,2-diisopropyl-4H-1,3,2- dioxasilin-5-yl)pent-2-enoate (3-59) 1 2 3 4 5 6 7 8 9 1 11 12 13 14 15 16 17 18 19-5 5 1 15 2 25 3 35 4 45 5 55 6 65 7 75 8..5 1. 1.5 2. 2.5 3. 3.5 4. 4.5 5. 5.5 6. 6.5 7. 7.5 8. 8.5-1 1 2 3 4 5 6 7 8 9 1 11

256 Methyl (4S,4aS,4a1S,6aR,11aR)-4-cyano-2,2-diisopropyl-4a1,5,6,6a,11,11a-hexahydro-4H,1Hcyclopenta[h,i][1,3,2]dioxasilino[4,5-g]indolizine-7-carboxylate (3-6) -1 1 2 3 4 5 6 7 8 9 1 11 12 13 14 15 16 17 18 19-2 -1 1 2 3 4 5 6 7 8 9 1 11 12 13 14 15 16 17 18 19 2 21..5 1. 1.5 2. 2.5 3. 3.5 4. 4.5 5. 5.5 6. 6.5 7. 7.5 8. 8.5 9. -5 5 1 15 2 25 3 35 4 45 5 55 6

Methyl (31S,6R,6aS,8aR)-6a-formyl-6-hydroxy-31,4,5,6,6a,7,8,8a-octahydrocyclopenta[h,i]indolizine-1-carboxylate (3-66) 15 14 13 12 11 1 9 8 7 6 5 4 3 2 1-1 1. 9.5 9. 8.5 8. 7.5 7. 6.5 6. 5.5 5. 4.5 4. 3.5 3. 2.5 2. 1.5 1..5. 257

258 Methyl (31S,6R,6aS,8aR)-6a-formyl-6-((4-nitrobenzoyl)oxy)-31,4,5,6,6a,7,8,8a-octahydrocyclopenta[h,i]indolizine-1-carboxylate (3-67) -1 1 2 3 4 5 6 7 8 9 1 11 12 13 14 15 16 17 18 19 2 21 22 23-5 5 1E+5 2E+5 2E+5 2E+5 3E+5 4E+5 4E+5 4E+5 5E+5 6E+5..5 1. 1.5 2. 2.5 3. 3.5 4. 4.5 5. 5.5 6. 6.5 7. 7.5 8. 8.5 9. 9.5 1. 5 1 15 2 25 3 35 4 45

COSY NMR for compound 3-66 : 259

ANNEXE 3 : COORDONNÉES DE DIFFRACTION DES RAYONS-X DU COMPOSÉ 3-67 26

ORTEP IMAGE OF 3-67: 261

Experimental : A clear intense orange Needle-like specimen of C2H2N2O7, approximate dimensions.5 mm x.12 mm x.4 mm, was used for the X-ray crystallographic analysis. The X-ray intensity data were measured on a Bruker Apex DUO system equipped with a Cu Kα ImuS micro focus source with MX optics (λ = 1.54186 Å). The total exposure time was 7.2 hours. The frames were integrated with the Bruker SAINT software package using a wide-frame algorithm. The integration of the data using a monoclinic unit cell yielded a total of 516 reflections to a maximum θ angle of 71.6 (.82 Å resolution), of which 364 were independent (average redundancy 1.666, completeness = 97.4%, Rint = 5.52%, Rsig = 8.57%) and 253 (82.57%) were greater than 2σ(F 2 ). The final cell constants of a = 11.134(8) Å, b = 6.1744(4) Å, c = 14.512(1) Å, β = 96.477(3), volume = 957.16(12) Å 3, are based upon the refinement of the XYZcentroids of 7188 reflections above 2 σ(i) with 6.33 < 2θ < 141.4. Data were corrected for absorption effects using the multi-scan method (SADABS). The ratio of minimum to maximum apparent transmission was.649. The calculated minimum and maximum transmission coefficients (based on crystal size) are.7159 and.9566. The structure was solved and refined using the Bruker SHELXTL Software Package, using the space group P 1 21 1, with Z = 2 for the formula unit, C2H2N2O7. The final anisotropic full-matrix leastsquares refinement on F 2 with 275 variables converged at R1 = 4.86%, for the observed data and wr2 = 13.65% for all data. The goodness-of-fit was.958. The largest peak in the final difference electron density synthesis was.238 e - /Å 3 and the largest hole was -.281 e - /Å 3 with an RMS deviation of.6 e - /Å 3. On the basis of the final model, the calculated density was 1.389 g/cm 3 and F(), 42 e -. 262

Table 1. Sample and crystal data for Belanger_PB6115F1. Identification code Belanger_PB6115F1 Chemical formula C 2 H 2 N 2 O 7 Formula weight Temperature Wavelength Crystal size Crystal habit Crystal system 4.38 g/mol 173(2) K 1.54186 Å.5 x.12 x.4 mm clear intense orange Needle monoclinic Space group P 1 21 1 Unit cell dimensions a = 11.134(8) Å α = 9 b = 6.1744(4) Å β = 96.477(3) c = 14.512(1) Å γ = 9 Volume 957.16(12) Å3 Z 2 Density (calculated) Absorption coefficient 1.389 g/cm3.895 mm 1 F() 42 263

Table 2. Data collection and structure refinement for Belanger_PB6115F1. Diffractometer Bruker Apex DUO ImuS micro focus source with MX Radiation source optics, Cu Kα Theta range for data collection 4.82 to 71.6 Index ranges 12<=h<=13, 6<=k<=7, 17<=l<=17 Reflections collected 516 Independent reflections 364 [R(int) =.552] Coverage of independent reflections 97.4% Absorption correction multi scan Max. and min. transmission.9566 and.7159 Structure solution technique direct methods Structure solution program SHELXS 97 (Sheldrick, 28) Refinement method Full matrix least squares on F2 Refinement program SHELXL 97 (Sheldrick, 28) Function minimized Σ w(fo2 Fc2)2 Data / restraints / parameters 364 / 1 / 275 Goodness of fit on F2.958 Final R indices 253 data; I>2σ(I) all data Weighting scheme w=1/[σ2(fo2)+(.833p)2+.p] where P=(Fo2+2Fc2)/3 Absolute structure parameter.(3) Largest diff. peak and hole.238 and.281 eå 3 R.M.S. deviation from mean.6 eå 3 R1 =.486, wr2 =.1235 R1 =.63, wr2 =.1365 264

Table 3. Atomic coordinates and equivalent isotropic atomic displacement parameters (Å2) for Belanger_PB6115F1. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. x/a y/b z/c U(eq) C1.9744(3).298(4).86(2).274(6) C2.928(3).1742(4).7942(2).313(7) C3.1611(3).2446(5).7126(2).367(7) C4.1828(3).4889(5).7176(2).352(7) C5.72(3).6886(4).6372(2).314(6) C6.8878(3).721(4).6454(2).315(6) C7.8579(3).6245(4).7385(2).296(6) C8.7787(3).4177(4).726(2).343(7) C9.874(3).2351(4).7232(2).314(6) C1.984(3).5478(4).7866(2).284(6) C11.9318(3).2429(5).896(2).355(7) C12.893(3).831(4).573(2).343(7) C13.696(4).9454(7).5225(3).555(1) C14.2561(3).914(4).9164(2).32(6) C15.3252(3).1791(4).49(2).287(6) C16.41(3).458(4).561(2).346(7) C17.4747(3).1178(5).14(2).353(7) C18.4542(3).327(5).172(2).317(6) C19.3723(3).4644(4).122(2).356(7) C2.37(3).3895(4).373(2).327(6) N1.683(2).69(4).71653(17).31(5) N2.5234(3).489(5).2586(2).422(6) O1.1658(18).2249(3).8855(14).312(4) O2.2784(2).9239(3).87814(16).398(5) O3.8957(2).3695(4).95151(17).491(7) O4.8396(2).916(4).5148(16).468(6) O5.6919(2).8374(3).5938(16).399(5) O6.5781(2).2786(5).31228(19).567(7) O7.5214(2).648(4).2736(2).546(7) 265

Table 4. Bond lengths (Å) for Belanger_PB6115F1. C1 C11 1.51(4) C1 C2 1.532(4) C1 C9 1.545(4) C1 C1 1.56(3) C2 O1 1.468(4) C2 C3 1.59(5) C3 C4 1.528(4) C4 N1 1.446(4) C5 N1 1.351(4) C5 C6 1.357(4) C6 C12 1.436(4) C6 C7 1.57(4) C7 C8 1.549(4) C7 C1 1.558(4) C8 C9 1.523(4) C1 N1 1.47(4) C11 O3 1.24(4) C12 O4 1.215(4) C12 O5 1.369(4) C13 O5 1.441(4) C14 O2 1.24(3) C14 O1 1.338(3) C14 C15 1.488(4) C15 C16 1.389(4) C15 C2 1.399(4) C16 C17 1.383(5) C17 C18 1.387(4) C18 C19 1.377(4) C18 N2 1.474(4) C19 C2 1.381(5) N2 O6 1.217(4) N2 O7 1.228(4) 266

Table 5. Bond angles ( ) for Belanger_PB6115F1. C11 C1 C2 17.2(2) C11 C1 C9 16.5(2) C2 C1 C9 114.3(2) C11 C1 C1 111.6(2) C2 C1 C1 114.5(2) C9 C1 C1 12.5(2) O1 C2 C3 19.3(2) O1 C2 C1 13.3(2) C3 C2 C1 114.2(2) C2 C3 C4 19.9(2) N1 C4 C3 19.7(3) N1 C5 C6 113.1(3) C5 C6 C12 121.9(3) C5 C6 C7 19.3(3) C12 C6 C7 128.8(3) C6 C7 C8 113.7(3) C6 C7 C1 12.7(2) C8 C7 C1 15.7(2) C9 C8 C7 13.9(2) C8 C9 C1 14.2(2) N1 C1 C7 14.6(2) N1 C1 C1 111.3(2) C7 C1 C1 16.5(2) O3 C11 C1 126.1(3) O4 C12 O5 121.6(3) O4 C12 C6 126.1(3) O5 C12 C6 112.3(3) O2 C14 O1 124.8(3) O2 C14 C15 124.9(3) O1 C14 C15 11.3(2) C16 C15 C2 119.8(3) C16 C15 C14 118.2(2) C2 C15 C14 122.(3) C17 C16 C15 12.5(3) C16 C17 C18 118.2(3) C19 C18 C17 122.7(3) C19 C18 N2 118.(3) C17 C18 N2 119.3(3) C18 C19 C2 118.6(3) C19 C2 C15 12.2(3) C5 N1 C4 124.(3) C5 N1 C1 11.(3) C4 N1 C1 12.8(2) O6 N2 O7 124.2(3) 267

Table 6. Torsion angles ( ) for Belanger_PB6115F1. C11 C1 C2 O1 49.7(3) C9 C1 C2 O1 167.6(2) C1 C1 C2 O1 74.7(3) C11 C1 C2 C3 168.3(3) C9 C1 C2 C3 73.9(3) C1 C1 C2 C3 43.9(4) O1 C2 C3 C4 6.9(3) C1 C2 C3 C4 54.2(4) C2 C3 C4 N1 56.7(4) N1 C5 C6 C12 173.7(2) N1 C5 C6 C7 5.8(3) C5 C6 C7 C8 19.4(3) C12 C6 C7 C8 71.2(4) C5 C6 C7 C1 4.3(3) C12 C6 C7 C1 175.2(3) C6 C7 C8 C9 87.3(3) C1 C7 C8 C9 24.6(3) C7 C8 C9 C1 4.4(3) C11 C1 C9 C8 77.4(3) C2 C1 C9 C8 164.4(2) C1 C1 C9 C8 39.9(3) C6 C7 C1 N1 1.5(3) C8 C7 C1 N1 117.9(2) C6 C7 C1 C1 119.4(2) C8 C7 C1 C1.(3) C11 C1 C1 N1 157.1(3) C2 C1 C1 N1 35.(4) C9 C1 C1 N1 89.3(3) C11 C1 C1 C7 89.5(3) C2 C1 C1 C7 148.4(2) C9 C1 C1 C7 24.1(3) C2 C1 C11 O3 134.2(3) C9 C1 C11 O3 13.(4) C1 C1 C11 O3 8.1(5) C5 C6 C12 O4 3.8(5) C7 C6 C12 O4 175.5(3) C5 C6 C12 O5 177.6(2) C7 C6 C12 O5 3.(4) O2 C14 C15 C16 1.3(4) O1 C14 C15 C16 169.4(3) O2 C14 C15 C2 169.8(3) O1 C14 C15 C2 1.6(4) C2 C15 C16 C17 1.4(4) C14 C15 C16 C17 178.6(3) C15 C16 C17 C18 1.2(5) C16 C17 C18 C19.1(5) C16 C17 C18 N2 179.(3) C17 C18 C19 C2.9(5) N2 C18 C19 C2 18.(3) C18 C19 C2 C15.7(4) C16 C15 C2 C19.4(4) C14 C15 C2 C19 179.5(3) C6 C5 N1 C4 159.5(3) C6 C5 N1 C1 4.8(3) C3 C4 N1 C5 97.8(3) C3 C4 N1 C1 54.3(4) C7 C1 N1 C5 1.7(3) C1 C1 N1 C5 112.9(3) C7 C1 N1 C4 157.4(2) C1 C1 N1 C4 42.7(4) C19 C18 N2 O6 166.4(3) C17 C18 N2 O6 14.5(4) C19 C18 N2 O7 13.2(4) C17 C18 N2 O7 165.9(3) O2 C14 O1 C2 5.3(4) C15 C14 O1 C2 175.(2) C3 C2 O1 C14 79.1(3) C1 C2 O1 C14 159.(2) O4 C12 O5 C13 2.(4) C6 C12 O5 C13 179.4(3) 268

Table 7. Anisotropic atomic displacement parameters (Å2) for Belanger_PB6115F1. The anisotropic atomic displacement factor exponent takes the form: -2π 2 [ h 2 a* 2 U11 +... + 2 h k a* b* U12 ] U11 U22 U33 U23 U13 U12 C1.335(15).21(11).28(14).13(1).52(12).1(1) C2.4(17).248(12).285(15).43(11).14(13).5(11) C3.41(18).38(15).33(17).43(13).122(14).61(14) C4.346(16).49(14).37(16).14(12).7(13).29(13) C5.449(18).228(12).272(15).2(1).68(13).46(12) C6.444(17).21(11).312(15).17(11).14(13).11(11) C7.366(16).225(11).314(15).6(11).19(13).12(11) C8.349(16).249(11).438(18).54(12).72(13).1(12) C9.359(16).2(11).372(17).5(11).9(13).47(11) C1.395(17).195(12).272(15).32(1).8(13).18(11) C11.392(17).274(13).41(18).65(13).98(15).28(13) C12.487(19).252(12).31(16).8(12).9(14).4(12) C13.54(2).64(2).47(2).192(18).11(17).122(18) C14.322(16).267(12).333(15).36(11).15(13).16(11) C15.36(15).249(12).319(15).31(11).95(12).13(11) C16.397(17).266(13).389(17).37(12).16(14).32(12) C17.33(16).329(14).44(17).84(13).57(13).42(12) C18.289(15).342(13).331(15).15(12).76(13).25(12) C19.42(18).269(13).396(17).16(12).119(14).29(12) C2.383(16).283(13).325(15).32(11).8(12).61(12) N1.381(14).266(11).297(13).11(1).1(11).49(1) N2.366(15).52(16).46(16).45(13).71(12).1(13) O1.363(11).267(9).34(11).1(8).34(9).7(8) O2.454(13).314(1).43(13).65(1).75(1).96(1) O3.648(17).472(12).39(13).26(1).217(13).13(11) O4.564(15).513(12).342(13).125(11).113(11).42(12) O5.431(13).415(11).357(12).9(9).71(1).62(1) O6.565(16).676(17).445(15).54(13).14(13).214(14) O7.556(17).5(14).563(16).151(12).18(13).22(12) 269

Table 8. Hydrogen atomic coordinates and isotropic atomic displacement parameters (Å2) for Belanger_PB6115F1. x/a y/b z/c U(eq) H3A.1138.27.658.44 H3B.2397.1677.7164.44 H4A.2357.5251.777.42 H4B.2242.5357.6622.42 H5.439.7244.5814.38 H8A.2698.3993.784.41 H8B.2768.4235.6657.41 H9A.13.2254.6594.38 H9B.1656.943.7384.38 H11.662.945.914.43 H13A.3636 1.951.5152.83 H13B.4721.9453.5427.83 H13C.3915.8694.4612.83 H16.4236.96 1.334.42 H17.5317.264 1.176.42 H19.361.676 1.1423.43 H2.2494.4813 1.21.39 H2.8(3).9(5).796(2).26(8) H7.185(3).737(6).776(3).42(9) H1.7(3).62(5).853(2).34(9) 27