VI. NMR spectra VI-1. Silyl enol ether of cyclic ketones (4a-4g) TMS silyl enol ether 4a I-4a/1 AVB- ZB Proton starting parameters. 6/11/3 RN TMS 9. 9. 8. 7. 6. 5. 4.5 4. 3. 2. 1..5. -.5 TMS silyl enol ether 4b I-4b/1 AVB- ZB Proton starting parameters. 6/11/3 RN 1 TMS 9 -. 9. 8. 7. 6. 5. 4.5 4. 3. 2. 1..5. -.5
TMS silyl enol ether 4c I-4c/1 AVB- ZB Proton starting parameters. 6/11/3 RN 1 TMS 1 9 -. 9. 8. 7. 6. 5. 4.5 4. 3. 2. 1..5. -.5 TMS silyl enol ether 4d I-4d/1 AV- Dual C-H probe proton starting parameters 7/23/3 RN. 1 TMS 1 1 9 -. 9. 8. 7. 6. 5. 4.5 4. 3. 2. 1..5. -.5 S-2
TMS silyl enol ether 4e I-198 AV- Dual C-H probe proton starting parameters 7/23/3 RN. 1 TMS 1 1 1 1 9 -. 9. 8. 7. 6. 5. 4.5 4. 3. 2. 1..5. -.5 TMS silyl enol ether 4f II-6 AV- Dual C-H probe proton starting parameters 7/23/3 RN. TMS 2 2 19 1 1 1 1 1 1 1 1 9 - -. 9. 8. 7. 6. 5. 4.5 4. 3. 2. 1..5. -.5 S-3
TMS silyl enol ether 4g II-7 AV- Dual C-H probe proton starting parameters 7/23/3 RN. TMS 2 2 1 1 1 1 -. 9. 8. 7. 6. 5. 4.5 4. 3. 2. 1..5. -.5 VI-1. Silyl enol ether of acyclic ketones (6a-6n) TMS silyl enol ether 6g II-24-sm AV- Dual C-H probe proton starting parameters 7/23/3 RN. 1 TMS 1 1 E/Z 2:1 1 9 -. 9. 8. 7. 6. 5. 4.5 4. 3. 2. 1..5. -.5 S-4
TMS silyl enol ether 6b I-18 AV- Dual C-H probe proton starting parameters 7/23/3 RN. TMS 65 E/Z 5:1 55 45 35 25 15 5-5. 9. 8. 7. 6. 5. 4.5 4. 3. 2. 1..5. -.5 TMS silyl enol ether 6c I-189 AV- Dual C-H probe proton starting parameters 7/23/3 RN. TMS 55 E/Z 2:1 45 35 25 15 5-5. 9. 8. 7. 6. 5. 4.5 4. 3. 2. 1..5. -.5 S-5
TMS silyl enol ether 6d II-1 AV- Dual C-H probe proton starting parameters 7/23/3 RN. 85 TMS CF 3 75 E/Z 1:1 65 55 45 35 25 15 5-5. 9. 8. 7. 6. 5. 4.5 4. 3. 2. 1..5. -.5 TMS silyl enol ether 6e TMS E/Z 2:1 S-6
TMS silyl enol ether 6f I-197 AV- Dual C-H probe proton starting parameters 7/23/3 RN. TMS 9 E/Z 3:1. 9. 8. 7. 6. 5. 4.5 4. 3. 2. 1..5. -.5 TMS silyl enol ether 6g I-23 AV- Dual C-H probe proton starting parameters 7/23/3 RN. 1 TMS 1 9 E/Z 3:1 -. 9. 8. 7. 6. 5. 4.5 4. 3. 2. 1..5. -.5 S-7
TMS silyl enol ether 6h I-24 AV- Dual C-H probe proton starting parameters 7/23/3 RN. TMS 9 E/Z 2:1. 9. 8. 7. 6. 5. 4.5 4. 3. 2. 1..5. -.5 TMS silyl enol ether 6i I-187 AV- Dual C-H probe proton starting parameters 7/23/3 RN. TMS 9 E/Z 3:1 -. 9. 8. 7. 6. 5. 4.5 4. 3. 2. 1..5. -.5 S-8
TMS silyl enol ether 6j II-5 AV- Dual C-H probe proton starting parameters 7/23/3 RN. TMS 9 E/Z 3:1.2 -. 9. 8. 7. 6. 5. 4.5 4. 3. 2. 1..5. -.5 TMS silyl enol ether 6k II-2 AV- Dual C-H probe proton starting parameters 7/23/3 RN. 32 TMS 28 F 3 C E/Z 3:1 26 24 22 18 16 14 12 8 6 4 2-2. 9. 8. 7. 6. 5. 4.5 4. 3. 2. 1..5. -.5 S-9
TMS silyl enol ether 6i I-6l/1 AV- Dual C-H probe proton starting parameters 7/23/3 RN. TMS 85 75 E/Z 1:1 65 55 45 35 25 15 5-5. 9. 8. 7. 6. 5. 4.5 4. 3. 2. 1..5. -.5 TMS silyl enol ether 6m I-182 AVQ- loaner probe 1 TMS 1 Et E/Z 1:1 9 -. 9. 8. 7. 6. 5. 4.5 4. 3. 2. 1..5. -.5 S-1
TMS silyl enol ether 6n 9.8 2..59.7 3.25 4. 13.29 7.48 7.45 7.31 7.31 7.3 7.29 7.29 7.28 7.27 7.26 7.26 CDCl3 7.26 7.24 7.23 7.23 7.22 7.21 7.2 5.3 5.23 4.46 4.44 4.34 4.32 2.27 2.25 2.24 2.22 2.21 2.2 2.19 2.2 2. 1.97 1.76 1.65 1.64 4 HD 1.7 1.2 1.1.99.87.84.71.68 S-11
V-1-1. Cyclic Ketones 2-Phenyl cyclohexanone (5a) V-1. NMR spectra of Ketones I-5a/1 AV- Dual C-H probe proton starting parameters 7/23/3 RN. 45 35 25 15 5. 9. 8. 7. 6. 5. 4.5 4. 3. 2. 1..5. -.5 S-12
2-(4-thoxyphenyl) cyclcohexanone (5b) a) 1 H NMR spectrum b) 13 C NMR spectrum I-5b/2 AV- Dual C-H probe Carbon starting parameters 7/23/3 RN 2 19 1 1 1 1 1 1 1 1 9-22 21 19 18 17 16 15 14 13 12 11 9 8 7 6 5 4 3 2 1 S-13
2-(4-thyiphenyl) cyclcohexanone (5c) a) 1H NMR spectrum I-5c-PT/1 AV- Dual C-H probe proton starting parameters 7/23/3 RN. 45 35 25 15 5. 9. 8. 7. 6. 5. 4.5 4. 3. 2. 1..5. -.5 b) 13 C NMR spectrum I-5c-PT/2 AV- Dual C-H probe Carbon starting parameters 7/23/3 RN 2 1 22 21 19 18 17 16 15 14 13 12 11 9 8 7 6 5 4 3 2 1 S-14
2-(2Naphthyl) cyclohexanone (5d) a) 1 H NMR spectrum I-5d/1 AV- Dual C-H probe proton starting parameters 7/23/3 RN. 7.8 7.77 7.74 7 7.45 7.43 7.42 7.41 7.4 7.38 7.26 7.26 7.24 7.23 3.77 3.76 3.73 3.71 7 6 2.49 2.47 2.43 2.41 2.34 2.33 2.31 2.27 2.19 2.17 2.17 2.15 2.11 2.1 2.7 2.3 2.1 1.99 1.96 1.94 1.91 1.89 1.82 1.79 1.76 1.74 -.13 35 25 15 5 3. 1. 2.3 1.1.94 1.95 1.6 2.99 2.1. 9. 8. 7. 6. 5. 4.5 4. 3. 2. 1..5. -.5 b) 13 C NMR spectrum I-5d/2 AV- Dual C-H probe Carbon starting parameters 7/23/3 RN 29 136.49 134 132.61 127.9 127.82 127.72 127.8 125.98 125.7 11.4 56 42.35 35.16 27.93 25.43 1 9 22 21 19 18 17 16 15 14 13 12 11 9 8 7 6 5 4 3 2 1 S-15
2-Phenylcycloheptanone (5e) I-5e/1 AVB- ZB Proton starting parameters. 6/11/3 RN 45 35 25 15 5. 9. 8. 7. 6. 5. 4.5 4. 3. 2. 1..5. -.5 2-thyl-1-tetralone (5f) I-155-sm AV- Dual C-H probe proton starting parameters 7/23/3 RN. 45 35 25 15 5.5 1. 9. 8. 7. 6. 5. 4.5 4. 3. 2. 1. S-16
2-thyl-1-indanone (5g) I-5g/1 AV- Dual C-H probe proton starting parameters 7/23/3 RN. 85 75 65 55 45 35 25 15 5-5. 9. 8. 7. 6. 5. 4.5 4. 3. 2. 1..5. -.5 S-17
V-1-1. Acyclic Ketones 2-Phenylpropiophenone (7a) a) 1 H NMR spectrum b) 13 C NMR spectrum S-18
2-(4-thoxyphenyl)propiophenene (7b) a) 1 H NMR spectrum b) 13 C NMR spectrum S-19
2-(4-thylphenyl)propiophenene (7c) a) 1 H NMR spectrum I-177 AV- Dual C-H probe proton starting parameters 7/23/3 RN. 85 75 65 55 45 35 25 15 5-5. 9. 8. 7. 6. 5. 4.5 4. 3. 2. 1..5. -.5 b) 13 C NMR spectrum I-177 AV- Dual C-H probe Carbon starting parameters 7/23/3 RN 3 2 1 22 21 19 18 17 16 15 14 13 12 11 9 8 7 6 5 4 3 2 1 S-2
2-(4-Trifluoromethylphenyl)propiophenene (7d) a) 1 H NMR spectrum I-7d/2 AV- Dual C-H probe proton starting parameters 7/23/3 RN. CF 3 75 65 55 45 35 25 15 5-5. 9. 8. 7. 6. 5. 4.5 4. 3. 2. 1..5. -.5 b) 13 C NMR spectrum I-7d/1 AV- Dual C-H probe Carbon starting parameters 7/23/3 RN CF 3 6 5 4 3 2 1 22 21 19 18 17 16 15 14 13 12 11 9 8 7 6 5 4 3 2 1 S-21
2-(2-Naphthyl)propiophenene (7e) a) 1 H NMR spectrum I-16 AV- Dual C-H probe proton starting parameters 7/23/3 RN. 1 9-1. 1. 9. 8. 7. 6. 5. 4.5 4. 3. 2. 1..5. b) 13 C NMR spectrum I-16 AV- Dual C-H probe Carbon starting parameters 7/23/3 RN 1 1 1 1 1 1 1 1 9 22 21 19 18 17 16 15 14 13 12 11 9 8 7 6 5 4 3 2 1 S-22
2-(1-Naphthyl)propiophenone (7f) a) 1 H NMR spectrum I-181-rc AV- Dual C-H probe proton starting parameters 7/23/3 RN. 75 65 55 45 35 25 15 5 1. 1. 9. 8. 7. 6. 5. 4.5 4. 3. 2. 1..5. -.5 b) 13 C NMR spectrum I-181-rc AV- Dual C-H probe Carbon starting parameters 7/23/3 RN 3 3 2 2 2 2 1 1 1 1 22 21 19 18 17 16 15 14 13 12 11 9 8 7 6 5 4 3 2 1 S-23
2-(2-thoxyphenyl)propiophenone (7g) a) 1 H NMR spectrum I-21 AV- Dual C-H probe proton starting parameters 7/23/3 RN. 1 1 9-1. 1. 9. 8. 7. 6. 5. 4.5 4. 3. 2. 1..5. -.5 b) 13 C NMR spectrum I-21 AV- Dual C-H probe Carbon starting parameters 7/23/3 RN 4 3 2 1 22 21 19 18 17 16 15 14 13 12 11 9 8 7 6 5 4 3 2 1 S-24
2-(2-thylphenyl)propiophenone (7h) a) 1 H NMR spectrum I-22 AV- Dual C-H probe proton starting parameters 7/23/3 RN. 1 1 1 1 1 9-1. 1. 9. 8. 7. 6. 5. 4.5 4. 3. 2. 1..5. -.5 b) 13 C NMR spectrum I-22 AV- Dual C-H probe Carbon starting parameters 7/23/3 RN 1 1 1 1 1 1 1 1 9 22 21 19 18 17 16 15 14 13 12 11 9 8 7 6 5 4 3 2 1 S-25
1-(4-thoxyphenyl)-2-phenylpropan-1-one (7i) a) 1 H NMR spectrum I-186 AV- Dual C-H probe proton starting parameters 7/23/3 RN. 65 55 45 35 25 15 5-5 1. 1. 9. 8. 7. 6. 5. 4.5 4. 3. 2. 1..5. -.5 b) 13 C NMR spectrum I-7i-13C/1 AV- Dual C-H probe Carbon starting parameters 7/23/3 RN 3 3 2 2 2 2 1 1 1 1 22 21 19 18 17 16 15 14 13 12 11 9 8 7 6 5 4 3 2 1 S-26
1-(4-thylphenyl)-2-phenylpropan-1-one (7j) a) 1 H NMR spectrum I-26 AV- Dual C-H probe proton starting parameters 7/23/3 RN. 9 1. 1. 9. 8. 7. 6. 5. 4.5 4. 3. 2. 1..5. -.5 b) 13 C NMR spectrum I-26 AV- Dual C-H probe Carbon starting parameters 7/23/3 RN 3 2 1 22 21 19 18 17 16 15 14 13 12 11 9 8 7 6 5 4 3 2 1 S-27
1-(4-Trifluoromethylphenyl)-2-phenylpropan-1-one (7k) a) 1 H NMR spectrum I-25 AV- Dual C-H probe proton starting parameters 7/23/3 RN. 1 9 F 3 C - 1. 1. 9. 8. 7. 6. 5. 4.5 4. 3. 2. 1..5. -.5 b) 13 C NMR spectrum I-25 AV- Dual C-H probe Carbon starting parameters 7/23/3 RN F 3 C 2 19 1 1 1 1 1 1 1 1 9 22 21 19 18 17 16 15 14 13 12 11 9 8 7 6 5 4 3 2 1 S-28
2,2-Dimethyl-4-phenylpentan-3-one (7l) a) 1 H NMR spectrum II-16-unknown AV- Dual C-H probe proton starting parameters 7/23/3 RN. 3 2 1. 9. 8. 7. 6. 5. 4.5 4. 3. 2. 1..5. -.5 b) 13 C NMR spectrum II-16-unknown AV- Dual C-H probe Carbon starting parameters 7/23/3 RN 2 2 19 1 1 1 1 1 1 1 1 9 22 21 19 18 17 16 15 14 13 12 11 9 8 7 6 5 4 3 2 1 S-29
2-Phenyl butyrophenone (7m) a) 1 H NMR spectrum I-178 AV- Dual C-H probe proton starting parameters 7/23/3 RN. 85 75 Et 65 55 45 35 25 15 5-5. 9. 8. 7. 6. 5. 4.5 4. 3. 2. 1..5. -.5 b) 13 C NMR spectrum I-178 AV- Dual C-H probe Carbon starting parameters 7/23/3 RN Et 3 3 3 3 2 2 2 2 1 1 1 1-22 21 19 18 17 16 15 14 13 12 11 9 8 7 6 5 4 3 2 1 S-3
2-thyl butyrophenone (7n) a) 1 H NMR Spectrum Et 7.98 7.97 7.97 7.96 7.95 7.94 7.94 9 8 8 6 6 5 4 3 3 7.49 7.49 7.48 7.47 7.46 7.46 7.45 7.44 7.44 7.26 CDCl3 2. 1.3 2.2 1.6 1.15 3.46 3.44 3.41 3.39 3.37 3.35 1.91 1.89 1.88 1.86 1.86 1.84 1.84 1.83 1.82 1.81 1.79 1.79 1.77 1.6 6 4 2 HD 1 HD 1.49 HD 1.47 1.47 1.45 1.42 1.29 1.2 1.19 1.18 1.17 1.14 3.25 3.24.94.92.89.88 b) 13 C NMR Spectrum 24.57 136.93 132.92 128.73 128.36 78 77.15 76.73 42.25 26.8 16.9 11.93 Et S-31
VII. HPLC data S-32
(5b) S-33
(5c) S-34
(5d) S-35
S-36
(5f) S-37
S-38
(7a) S-39
S-4
(7c) S-41
S-42
S-43
S-44
S-45
S-46
S-47
S-48
F 3 C (7k) S-49
S-5
S-51
S-52