Catalyst-free transformation of levulinic acid into pyrrolidinones with formic acid

Catalyst-free transformation of levulinic acid into pyrrolidinones with formic acid Yawen Wei, a Chao Wang,* a Xue Jiang, a Dong Xue, a Zhao-Tie Liu, a and Jianliang Xiao* a,b a Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education, School of Chemistry & Chemical Engineering, Shaanxi Normal University, Xi an, 710062, China b Department of Chemistry, University of Liverpool, Liverpool, L69 7ZD, UK Contents 1. General information... S2 2. Effect of different solvents.. S2 3. Effect of formic acid/triethylamine ratio on RA of LA in DMSO......S3 4. Deuterium labelling experiments.........s3 5. Procedures for RA of LA......S3-S4 6. Analytic data of products.....s5-s13 7. References..........S13 8. Traces of 1 H and 13 C NMR spectra of products S14-S46 S1

1. General information Unless otherwise specified, the chemicals were obtained commercially and used without further purification. NMR spectra were recorded on a Bruker 400 Hz NMR spectrometer with TMS as the internal standard. HRMS data were recorded on a Bruker Apex IV FTMS spectrometer using ESI method and Bruker Maxis with EI method. 2. Effect of different solvents Table S1 Effect of different solvents on RA of LA with benzylamine a Entry Solvent Conversion (%) b 1 DMSO 89 2 MeOH NR 3 H 2 O NR 4 EtOH NR 5 i-proh NR 6 n-buoh NR 7 DCM NR 8 DMF <5 9 THF 9 10 Toluene NR 11 1,4-dioxane NR 12 acetone NR 13 CH 3 CN 12 14 Sulfolane 24 15 Tetramethylene sulfoxide 63 a Reaction conditions: LA (1 mmol), amine (2 mmol), HCOOH (5 mmol), Et 3 N (1 mmol), Solvent (3 ml), 100 o C. b Determined by 1 H NMR with 1,3,5-trimethoxylbenzene as internal standard. S2

1.01 2.01 0.98 1.03 2.05 1.03 1.03 3. Effect of formic acid/triethylamine ratio on RA of LA in DMSO Figure S1 The effect of formic acid/triethylamine (F/T) ratio on RA of LA in DMSO. Reaction conditions: LA (1 mmol), benzylamine (2 mmol), DMSO (3 ml), HCOOH (5 mmol), 100 o C, 4 h. Conversions were determined by 1 H NMR with 1,3,5-trimethoxybenzene as internal standard. 4. Deuterium labelling experiments 1a, With HCOOH 4.0 3.9 3.8 3.7 3.6 3.5 3.4 3.3 3.2 3.1 3.0 2.9 2.8 2.7 2.6 2.5 2.4 2.3 2.2 2.1 2.0 1.9 1.8 1.7 1.6 1.5 ppm 1a, With DCOOH 4.0 3.9 3.8 3.7 3.6 3.5 3.4 3.3 3.2 3.1 3.0 2.9 2.8 2.7 2.6 2.5 2.4 2.3 2.2 2.1 2.0 1.9 1.8 1.7 1.6 1.5 ppm Scheme S1 Deuterium labelling experiments for RA of LA with benzylamine. Reaction conditions: LA (1 mmol), benzylamine (2 mmol), DCOOH (5 mmol), Et 3 N (1 mmol), DMSO (3 ml), 100 o C, 12 h. 5. Procedures for RA of LA 5.1 Typical procedure for screening reaction conditions Benzylamine (2 mmol), levulinic acid (1 mmol), and a magnetic stir bar were placed in a pressure tube. To the mixture was injected solvent (3 ml), HCOOH (5 mmol), and NEt 3 (1 S3

mmol). The mixture was bubbled with argon for 15 min, and then stirred at 100 C for 4 h. After cooling to room temperature, the reaction mixture was basified with saturated NaOH solution and 1,3,5-trimethoxybenzene (0.1 mmol) was added as internal standard. The resulting mixture was extracted with DCM (5 x 3 ml) and the organic layers were washed with brine, and dried over Na 2 SO 4. The organic solvent was removed under reduced pressure. The conversion was determined by 1 H NMR of the crude mixture. 5.2 General procedure for RA of LA with aliphatic amines Amine (2 mmol), levulinic acid (1 mmol), and a magnetic stir bar were placed in a pressure tube. To the mixture was injected DMSO (3 ml), HCOOH (5 mmol), and NEt 3 (1 mmol). The mixture was bubbled with argon for 15 min, and then stirred at 100 C for 4 h. After cooling to room temperature, the reaction was basified with saturated NaOH solution and extracted with DCM (5 x 3 ml). The organic layers were washed with brine, and dried over Na 2 SO 4. The organic solvent was removed under reduced pressure and the product was purified by flash chromatography using petroleum ether and ethyl acetate with 1% triethylamine as elute. Similar yield was obtained with freshly distilled DMSO and newly purchased reaction tube and stir bar. 5.3 General procedure for RA of LA with aromatic amines Amine (1.5 mmol), levulinic acid (1 mmol), and a magnetic stir bar were placed in a pressure tube. To the mixture was injected DMSO (3 ml), HCOOH (2.5 mmol), and NEt 3 (0.5 mmol). The mixture was bubbled with argon for 15 min, and then stirred at 100 C for 3 h. After cooling to 0 o C, a portion of amine (0.5 mmol), HCOOH (0.8 mmol), and NEt 3 (0.17 mmol) were added and the resulting mixture was stirred at 100 C for 3 h, which was repeated twice. After cooling to room temperature, the reaction was basified with saturated NaOH solution and extracted with DCM (5 x 3 ml). The organic layers were washed with brine, and dried over Na 2 SO 4. The organic solvent was removed under reduced pressure and the product was purified by flash chromatography using petroleum ether and ethyl acetate with 1% triethylamine as elute. S4

6. Analytic data of products 1-Benzyl-5-methylpyrrolidin-2-one 1a: [1] 161 mg, 87% yield; yellow oil; 1 H NMR (400 MHz, CDCl 3 ) δ (ppm): 7.32-7.21 (m, 5H), 4.95 (d, J = 15.2 Hz, 1H), 3.97 (d, J = 15.2 Hz, 1H), 3.51 (sextet, J = 6.2 Hz, 1H), 2.48-2.34 (m, 2H), 2.18-2.11 (m, 1H), 1.61-1.55 (m, 1H), 1.14 (d, J = 6.4 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ (ppm): 175.0, 136.8, 128.6, 128.0, 127.4, 52.9, 44.0, 30.3, 26.7, 19.6; HRMS (ESI) for C 12 H 15 NO [M+Na] + : calc.: 212.1051. Found: 212.1056. 1-(4-Methoxybenzyl)-5-methylpyrrolidin-2-one 1b: [1] 194 mg, 89% yield; yellow oil; 1 H NMR (400 MHz, CDCl 3 ) δ (ppm): 7.13 (d, J = 8.4 Hz, 2H), 6.81 (d, J = 8.8 Hz, 2H), 4.87 (d, J = 14.8 Hz, 1H), 3.99 (d, J = 14.8 Hz, 1H), 3.75 (s, 3H), 3.48 (sextet, J = 6.2 Hz, 1H), 2.50-2.31 (m, 2H), 2.15-2.06 (m, 1H), 1.59-1.50 (m, 1H), 1.13 (d, J = 6.2 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ (ppm): 174.9, 159.0, 129.3, 128.8, 114.0, 55.2, 52.7, 43.3, 30.2, 26.6, 19.6; HRMS (ESI) for C 13 H 17 NO 2 [M+Na] + : calc.: 242.1157. Found: 242.1164. 5-Methyl-1-(4-methylbenzyl)pyrrolidin-2-one 1c: 184 mg, 91% yield; yellow oil; 1 H NMR (400 MHz, CDCl 3 ) δ (ppm): 7.11 (s, 4H), 4.92 (d, J = 14.8 Hz, 1H), 3.92 (d, J = 14.8 Hz, 1H), 3.50 (sextet, J = 6.4 Hz, 1H), 2.52-2.36 (m, 2H), 2.31 (s, 3H), 2.17-2.08 (m, 1H), 1.61-1.52 (m, 1H), 1.14 (d, J = 6.2 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ (ppm): 174.8, 137.0, 133.8, 129.2, 128.0, 52.7, 43.6, 30.3, 26.6, 21.1, 19.6; HRMS (ESI) for C 13 H 17 NO [M+Na] + : calc.: 226.1208. Found: 226.1207. 1-(4-Fluorobenzyl)-5-methylpyrrolidin-2-one 1d: [3] 185 mg, 89% yield; yellow oil; 1 H NMR (400 MHz, CDCl 3 ) δ (ppm): 7.22-7.19 (m, 2H), 6.99 (t, J = 8.6 Hz, 2H), 4.87 (d, J = 15.0 Hz, 1H), 3.98 (d, J = 15.0 Hz, 1H), 3.51 (sextet, J = 6.2 Hz, 1H), 2.53-2.34 (m, 2H), S5

2.19-2.10 (m, 1H), 1.64-1.55 (m, 1H), 1.15 (d, J = 6.2 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ (ppm): 175.0, 162.2 (d, 1 J C-F = 244.1 Hz), 132.7 (d, 4 J C-F = 3.7 Hz), 129.6 (d, 3 J C-F = 8.0 Hz), 115.5 (d, 2 J C-F = 21.4 Hz), 53.0, 43.3, 30.2, 26.7, 19.6; HRMS (ESI) for C 12 H 14 FNO [M+Na] + : calc.: 230.0957. Found: 230.0964. 1-(4-Chlorobenzyl)-5-methylpyrrolidin-2-one 1e: 198 mg, 88% yield; yellow oil; 1 H NMR (400 MHz, CDCl 3 ) δ (ppm): 7.26 (d, J = 8.2 Hz, 2H), 7.16 (d, J = 8.2 Hz, 2H), 4.84(d, J = 15.2 Hz, 1H), 3.99 (d, J = 15.2 Hz, 1H), 3.50 (sextet, J = 6.4 Hz, 1H), 2.52-2.33 (m, 2H), 2.19-2.10 (m, 1H), 1.63-1.54 (m, 1H), 1.13 (d, J = 6.2 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ (ppm): 175.1, 135.4, 135.3, 129.3, 128.8, 53.0, 43.4, 30.2, 26.7, 19.6; HRMS (ESI) for C 12 H 14 ClNO [M+Na] + : calc.: 246.0662. Found: 246.0659. 5-Methyl-1-(4-(trifluoromethyl)benzyl)pyrrolidin-2-one 1f: 196 mg, 76% yield; yellow oil; 1 H NMR (400 MHz, CDCl 3 ) δ (ppm): 7.57 (d, J = 8.0 Hz, 2H), 7.35 (d, J = 8.0 Hz, 2H), 4.91 (d, J = 15.2 Hz, 1H), 4.11 (d, J = 15.2 Hz, 1H), 3.52 (sextet, J = 6.4 Hz, 1H), 2.54-2.36 (m, 2H), 2.22-2.14 (m, 1H), 1.66-1.57 (m, 1H), 1.15 (d, J = 6.0 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ (ppm): 175.2, 141.1, 129.8 (q, 2 J C-F = 32.0 Hz), 128.2, 125.6 (q, 3 J C-F = 3.6 Hz), 124.1 (q, 1 J C-F = 270.4 Hz), 53.2, 43.7, 30.1, 26.7, 19.7; HRMS (ESI) for C 13 H 14 F 3 NO [M+Na] + : calc.: 280.0925. Found: 280.0924. 1-(3-Methoxybenzyl)-5-methylpyrrolidin-2-one 1g: [3] 194 mg, 89% yield; yellow oil; 1 H NMR (400 MHz, CDCl 3 ) δ (ppm): 7.22 (t, J = 7.8 Hz, 1H), 6.81-6.76 (m, 3H), 4.93 (d, J = 15.2 Hz, 1H), 3.95 (d, J = 15.2 Hz, 1H), 3.78 (s, 3H), 3.54 (sextet, J = 6.4 Hz, 1H), 2.54-2.36 (m, 2H), 2.19-2.10 (m, 1H), 1.63-1.54 (m, 1H), 1.16 (d, J = 6.4 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ (ppm): 175.1, 159.9, 138.3, 129.6, 120.3, 113.7, 112.8, 55.2, 53.0, 43.9, 30.2, 26.6, 19.6; HRMS (ESI) for C 13 H 17 NO 2 [M+Na] + : calc.: 242.1153. Found: 242.1162. S6

1-(3-Fluorobenzyl)-5-methylpyrrolidin-2-one 1h: 153 mg, 74% yield; yellow oil; 1 H NMR (400 MHz, CDCl 3 ) δ (ppm): 7.29-7.24 (m, 1H), 7.00 (d, J = 7.6 Hz, 1H), 6.96-6.92 (m, 1H), 4.88 (d, J = 15.2 Hz, 1H), 4. 02 (d, J = 15.2 Hz, 1H), 3.54 (sextet, J = 6.4 Hz, 1H), 2.54-2.37 (m, 2H), 2.22-2.13 (m, 1H), 1.65-1.56 (m, 1H), 1.15 (d, J = 6.2 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ (ppm): 175.1, 163.0 (d, 1 J C-F = 245.0 Hz), 139.6 (d, 3 J C-F = 7.0 Hz), 130.1 (d, 3 J C-F = 8.1 Hz), 123.4 (d, 4 J C-F = 2.8 Hz), 114.7 (d, 2 J C-F = 21.4 Hz), 114.4 (d, 2 J C-F = 21.0 Hz), 53.1, 43.6 (d, 4 J C-F = 4.3 Hz), 30.1, 26.7, 19.6; HRMS (ESI) for C 12 H 14 FNO [M+Na] + : calc.: 230.0957. Found: 230.0957. 1-(2-Methoxybenzyl)-5-methylpyrrolidin-2-one 1i: [3] 199 mg, 91% yield; yellow oil; 1 H NMR (400 MHz, CDCl 3 ) δ (ppm): 7.24-7.17 (m, 2H), 6.91-6.83 (m, 2H), 4.80 (d, J = 15.2 Hz, 1H), 4.20 (d, J = 15.2 Hz, 1H), 3.81 (s, 3H), 3.53 (sextet, J = 6.4 Hz, 1H), 2.47-2.31 (m, 2H), 2.16-2.10 (m, 1H), 1.60-1.54 (m, 1H), 1.16 (d, J = 6.4 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ (ppm): 175.0, 157.3, 129.5, 128.5 124.9, 120.6, 110.3, 55.3, 53.4, 38.4, 30.3, 26.7, 19.6; HRMS (ESI) for C 13 H 17 NO 2 [M+Na] + : calc.: 242.1157. Found: 242.1161. 1-(2-Fluorobenzyl)-5-methylpyrrolidin-2-one 1j: 168 mg, 81% yield; yellow oil; 1 H NMR (400 MHz, CDCl 3 ) δ (ppm): 7.29 (d, J = 7.6 Hz, 1H), 7.25-7.21 (m, 1H), 7.08 (t, J = 7.4 Hz, 1H), 7.02 (t, J = 9.2 Hz, 1H), 4.85 (d, J = 15.2 Hz, 1H), 4.20 (d, J = 15.2 Hz, 1H), 3.54 (sextet, J = 6.6 Hz, 1H), 2.52-2.32 (m, 2H), 2.20-2.11 (m, 1H), 1.64-1.55 (m, 1H), 1.18 (d, J = 6.2 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ (ppm): 175.2, 160.8 (d, 1 J C-F = 244.4 Hz), 130.5 (d, 6 J C-F = 4.2 Hz), 129.2 (d, 4 J C-F = 8.1 Hz), 124.4 (d, 7 J C-F = 3.4 Hz), 123.8 (d, 3 J C-F = 14.7 Hz), 115.3 (d, 2 J C-F = 21.7 Hz), 53.2, 37.2 (d, 5 J C-F = 4.3 Hz), 30.1, 26.7, 19.6; HRMS (ESI) for C 12 H 14 FNO [M+Na] + : calc.: 230.0957. Found: 230.0958. 1-(3,4-Dichlorobenzyl)-5-methylpyrrolidin-2-one 1k: 185 mg, 72% yield; yellow oil; 1 H NMR (400 MHz, CDCl 3 ) δ (ppm): 7.37 (d, J = 8.4 Hz, 1H), 7.31 (d, J = 2.0 Hz, 1H), 7.07 (dd, J = 8.0, 2.0 Hz, 1H), 4.79 (d, J = 15.6 Hz, 1H), 4.00 (d, J = 15.2 Hz, 1H), 3.52 (sextet, J = 6.2 Hz, 1H), 2.53-2.35 (m, 2H), 2.22-2.13 (m, 1H), 1.65-1.56 (m, 1H), 1.15 (d, J = 6.2 Hz, 3H); S7

13 C NMR (100 MHz, CDCl 3 ) δ (ppm): 175.2, 137.3, 132.7, 131.6, 130.6, 129.8, 127.3, 53.2, 43.1, 30.0, 26.7, 19.7; HRMS (ESI) for C 12 H 13 Cl 2 NO [M+Na] + : calc.: 280.0272. Found: 280.0268. 5-Methyl-1-phenethylpyrrolidin-2-one 1l: 175 mg, 86% yield; yellow oil; 1 H NMR (400 MHz, CDCl 3 ) δ (ppm): 7.30-7.27 (m, 2H), 7.22-7.18 (m, 3H), 3.82 (ddd, J = 13.8, 9.2, 6.2 Hz, 1H), 3.52 (sextet, J = 6.2 Hz, 1H), 3.14 (ddd, J = 14.2, 8.8, 6.2 Hz, 1H), 2.91-2.73 (m, 2H), 2.43-2.24 (m, 1H), 2.16-2.07 (m, 1H), 1.57-1.49 (m, 1H), 1.15 (d, J = 6.2 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ (ppm): 174.9, 138.9, 128.7, 128.5, 126.4, 53.9, 41.8, 33.9, 30.2, 26.8, 19.7; HRMS (ESI) for C 13 H 17 NO [M+Na] + : calc.: 226.1208. Found: 226.1204. 1-Butyl-5-methylpyrrolidin-2-one 1m: 134 mg, 86% yield; Yellow oil; 1 H NMR (400 MHz, CDCl 3 ) δ (ppm): 3.64 (sextet, J = 6.2 Hz, 1H), 3.53 (ddd, J = 13.8, 9.0, 7.0 Hz, 1H), 2.86 (ddd, J = 13.8, 8.6, 5.2 Hz, 1H), 2.40-2.23 (m, 2H), 2.17-2.08 (m, 1H), 1.56-1.34 (m, 3H), 1.30-1.20 (m, 2H), 1.15 (d, J = 6.2 Hz, 3H), 0.87 (t, J = 7.2 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ (ppm): 174.9, 53.6, 40.0, 30.2, 29.5, 26.8, 20.2, 19.7, 13.7; HRMS (ESI) for C 9 H 17 NO [M+Na] + : calc.: 178.1208. Found: 178.1203. 5-Methyl-1-pentylpyrrolidin-2-one 1n: 152 mg, 90% yield; yellow oil; 1 H NMR (400 MHz, CDCl 3 ) δ (ppm): 3.68 (sextet, J = 6.2 Hz, 1H), 3.56 (ddd, J = 13.8, 9.0, 7.0 Hz, 1H), 2.90 (ddd, J = 13.8, 8.8, 5.2 Hz, 1H), 2.46-2.29 (m, 2H), 2.21-2.12 (m, 1H), 1.60-1.38 (m, 3H), 1.34-1.21 (m,4h), 1.18 (d, J = 6.4 Hz, 3H), 0.86 (t, J = 7.0 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ (ppm): 174.8, 53.4, 40.1, 30.3, 29.1, 27.0, 26.8, 22.3, 19.7, 13.9; HRMS (ESI) for C 10 H 19 NO [M+Na] + : calc.: 192.1364. Found: 192.1361. 1-Hexyl-5-methylpyrrolidin-2-one 1o: [3] 170 mg, 93% yield; yellow oil; 1 H NMR (400 MHz, CDCl 3 ) δ (ppm): 3.65 (sextet, J = 6.4 Hz, 1H), 3.55 (ddd, J = 13.8, 9.0, 7.0 Hz, 1H), 2.88 (ddd, J = 13.8, 9.0, 5.0 Hz, 1H), 2.41-2.24 (m, 2H), 2.19-2.10 (m, 1H), 1.58-1.37 (m, S8

3H), 1.25 (s, 6H), 1.17 (d, J = 6.4 Hz, 3H), 0.84 (t, J = 6.4 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ (ppm): 174.8, 53.5, 40.2, 31.5, 30.3, 27.4, 26.8, 26.6, 22.5, 19.7, 13.9; HRMS (ESI) for C 11 H 21 NO [M+N a] + : calc.: 206.1521. Found: 206.1517. 1-Octyl-5-methylpyrrolidin-2-one 1p: [3] 197 mg, 93% yield; yellow oil; 1 H NMR (400 MHz, CDCl 3 ) δ (ppm): 3.66 (sextet, J = 6.2 Hz, 1H), 3.55 (ddd, J = 13.8, 9.0, 7.0 Hz, 1H), 2.88 (ddd, J = 13.8, 9.0, 5.0 Hz, 1H), 2.44-2.27 (m, 2H), 2.20-2.11 (m, 1H), 1.59-1.46 (m, 2H), 1.44-1.36 (m, 1H), 1.26-1.24 (m, 10H), 1.18 (d, J = 6.2 Hz, 3H), 0.86-0.83 (m, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ (ppm): 174.6, 53.2, 40.0, 31.7, 30.3, 29.3, 29.1, 27.4, 27.0, 26.8, 22.6, 19.7, 14.0; HRMS (ESI) for C 13 H 25 NO [M+Na] + : calc.: 234.1834. Found: 234.1838. 1-Dodecyl-5-methylpyrrolidin-2-one 1q: [3] 234 mg; 88% yield; yellow oil; 1 H NMR (400 MHz, CDCl 3 ) δ (ppm): 3.67 (sextet, J = 6.4Hz, 1H), 3.56 (ddd, J = 13.8, 9.2, 7.0 Hz, 1H), 2.89 (ddd, J = 13.8, 9.0, 5.0 Hz, 1H), 2.43-2.26 (m, 2H), 2.20-2.11 (m, 1H), 1.59-1.48 (m, 2H), 1.45-1.39 (m, 1H), 1.21 (s, 18H), 1.18 (d, J = 6.2 Hz, 3H), 0.88-0.84 (m, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ (ppm): 174.8, 53.4, 40.2, 31.9, 30.3, 29.59, 29.58, 29.54, 29.51, 29.31, 29.29, 27.4, 27.0, 26.9, 22.6, 19.7, 14.0; HRMS (ESI) for C 17 H 33 NO [M+Na] + : calc.: 290.2460. Found: 290.2465. 1-Isopentyl-5-methylpyrrolidin-2-one 1r: 137 mg, 77% yield; yellow oil; 1 H NMR (400 MHz, CDCl 3 ) δ (ppm): 3.70-3.56 (m, 2H), 2.89 (ddd, J = 14.2, 9.2, 5.2 Hz, 1H), 2.43-2.25 (m, 2H), 2.19-2.10 (m, 1H), 1.59-1.48 (m, 2H), 1.42-1.27 (m, 1H), 1.18 (d, J = 6.2 Hz, 3H), 0.90 (d, J = 6.6 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ (ppm): 174.6, 53.2, 38.4, 36.1, 30.3, 26.8, 26.1, 22.6, 22.2, 19.7; HRMS (ESI) for C 10 H 19 NO [M+Na] + : calc.: 192.1364. Found: 192.1356. S9

5-Methyl-1-(pentan-3-yl)pyrrolidin-2-one 1s: 148 mg, 87% yield; yellow oil; 1 H NMR (400 MHz, CDCl 3 ) δ (ppm): 3.72-3.57 (m, 2H), 2.51-2.42 (m, 1H), 2.33-2.25 (m, 1H), 2.19-2.10 (m, 1H), 1.69-1.48 (m, 5H), 1.22 (d, J = 6.4 Hz, 3H), 0.89 (t, J = 7.4 Hz, 3H), 0.82 (t, J = 7.4 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ (ppm): 175.6, 56.6, 53.3, 30.4, 27.7, 27.2, 24.6, 21.8, 11.42, 11.37; HRMS (ESI) for C 10 H 19 NO [M+Na] + : calc.: 192.1364. Found: 192.1360. 1-(2-Ethylhexyl)-5-methylpyrrolidin-2-one 1t: mixture of isomers; 193 mg, 91% yield; yellow oil; 1 H NMR (400 MHz, CDCl 3 ) δ (ppm): 3.59 (sextet, J = 6.4Hz, 1H), 3.52-3.43 (m, 1H), 2.77-2.70 (m, 1H), 2.39-2.23 (m, 2H), 2.16-2.07 (m, 1H), 1.56-1.47 (m, 2H), 1.32-1.16 (m, 6H), 1.13 (d, J = 6.2 Hz, 3H), 0.86-0.77 (m, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ (ppm): 174.8, 174.7, 52.2, 51.9, 43.4, 43.2, 36.9, 36.6, 30.7, 30.4, 30.2, 28.9, 28.4, 26.71, 26.68, 24.2, 23.5, 23.0, 19.41, 19.36, 13.9, 10.9, 10.2; HRMS (ESI) for C 13 H 25 NO [M+Na] + : calc.: 234.1834. Found: 234.1830. 1-Cyclohexyl-5-methylpyrrolidin-2-one 1u: 162 mg, 85% yield; yellow oil; 1 H NMR (400 MHz, CDCl 3 ) δ (ppm): 3.80-3.65 (m, 2H), 2.49-2.41 (m, 1H), 2.30-2.22 (m, 1H), 2.16-2.06 (m, 1H), 1.82-1.69 (m, 3H), 1.67-1.42 (m, 5H), 1.39-1.25 (m, 2H), 1.22 (d, J = 6.2 Hz, 3H), 1.16-1.04 (m, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ (ppm): 174.5, 53.0, 52.6, 31.8, 30.3, 30.1, 27.5, 26.0, 25.9, 25.6, 22.3; HRMS (ESI) for C 11 H 19 NO [M+Na] + : calc.: 204.1364. Found: 204.1359. 5-Methyl-1-phenylethyl)pyrrolidin-2-one 1v: mixture of isomers; 178 mg, 88% yield; yellow oil; 1 H NMR (400 MHz, CDCl 3 ) δ (ppm): 7.38-7.22 (m, 12.5H), 5.47-5.38 (m, 2.5H), 3.85-3.78 (m, 1H), 3.41-3.33 (m, 1.5H), 2.55-2.46 (m, 2.6H), 2.38-2.29 (m, 3H), 2.19-2.10 (m, 1H), 2.08-1.98 (m, 1.5H), 1.64-1.60 (m, 8H), 1.57-1.49 (m, 2.5H), 1.14 (d, J = 6.2 Hz, 4.5H), 0.76 (d, J = 6.2 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ (ppm): 175.0, 174.9, 142.2, 139.8, 128.4, 128.2, 127.4, 127.1, 127.0, 52.8, 52.6, 50.2, 49.1, 30.3, 30.2, 27.5, 27.4, 22.2, 21.4, 18.3, 16.1; HRMS (ESI) for C 13 H 17 NO [M+Na] + : calc.: 226.1208. Found: 226.1205. S10

1-(4-Methoxyphenyl)-5-methylpyrrolidin-2-one 2a: [1] 143 mg, 70% yield; white solid; mp. = 59~60 o C; 1 H NMR (400 MHz, CDCl 3 ) δ (ppm): 7.22 (d, J = 8.9 Hz, 2H), 6.91 (d, J = 8.9 Hz, 2H), 4.17 (sextet, J = 6.4 Hz, 1H), 3.79 (s, 3H), 2.64-2.47 (m, 2H), 2.40-2.31 (m, 1H), 1.77-1.72 (m, 1H), 1.17 (d, J = 6.0 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ (ppm) 174.3, 157.7, 130.4, 126.1, 114.4, 56.1, 55.4, 31.1, 26.8, 20.3; HRMS (ESI) for C 12 H 15 NO 2 [M+Na] + : calc.: 228.1000. Found: 228.1005. 5-methyl-1-p-tolylpyrrolidin-2-one 2b: [1] 83 mg, 44% yield; white solid; mp. = 75~76 o C; 1 H NMR (400 MHz, CDCl 3 ) δ (ppm): 7.23 (d, J = 8.4 Hz, 2H), 7.18 (d, J = 8.4 Hz, 2H), 4.24 (sextet, J = 6.0 Hz, 1H), 2.66-2.48 (m, 2H), 2.40-2.34 (m, 4H), 1.78-1.71 (m, 1H), 1.19 (d, J = 6.0 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ (ppm): 174.2, 135.6, 135.0, 129.6, 124.2, 55.8, 31.3, 26.8, 21.0, 20.2; HRMS (ESI) for C 12 H 15 NO [M+Na] + : calc.: 212.1051. Found: 212.1052. 1-(3, 4-Dimethylphenyl)-5-methylpyrrolidin-2-one 2c: 153 mg, 75% yield; white solid; mp. = 85~87 o C; 1 H NMR (400 MHz, CDCl 3 ) δ (ppm): 7.14-7.11 (m, 2H), 7.02 (dd, J = 8.0, 2.0 Hz, 1H), 4.21 (td, J = 7.2, 6.0 Hz, 1H), 2.65-2.47 (m, 2H), 2.39-2.32 (m, 1H), 2.26 (s, 3H), 2.23(s, 3H), 1.77-1.68 (m, 1H), 1.18 (d, J = 6.4 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ (ppm): 174.2, 137.3 135.2, 134.5, 130.1, 125.9, 121.9, 55.9, 31.3, 26.9, 20.3, 19.9, 19.3; HRMS (ESI) for C 13 H 17 NO [M+Na] + : calc.: 226.1208. Found: 226.1212. 1-(3,4-Dimethoxyphenyl)-5-methylpyrrolidin-2-one 2d: 167 mg, 71% yield; yellow oil; 1 H NMR (400 MHz, CDCl 3 ) δ (ppm): 6.97 (d, J = 2.2 Hz, 1H), 6.86 (d, J = 8.6 Hz, 1H), 6.77 (dd, J = 8.6, 2.4 Hz, 1H), 4.18 (sextet, J = 6.2 Hz, 1H), 3.87 (s, 3H), 3.86 (s, 3H), 2.65-2.48 (m, 2H), 2.40-2.31 (m, 1H), 1.78-1.69 (m, 1H), 1.18 (d, J = 6.2 Hz, 3H); 13 C NMR (100 MHz, S11

CDCl 3 ) δ (ppm): 174.3, 149.2, 147.3, 130.8, 116.7, 111.2, 109.0, 56.2, 56.0, 55.9, 31.2, 26.8, 20.3; HRMS (ESI) for C 13 H 17 NO 3 [M+Na] + : calc.: 258.1106. Found: 258.1102. 1-(4-Aminophenyl)-5-methylpyrrolidin-2-one 2e: 104 mg, 55% yield; grayish purple solid; mp. = 112~113 o C; 1 H NMR (400 MHz, CDCl 3 ) δ (ppm): 7.04 (d, J = 8.6 Hz, 2H), 6.66 (d, J = 8.6 Hz, 2H), 4.10 (sextet, J = 6.2 Hz, 1H), 3.69 (brs, 2H), 2.61-2.44 (m, 2H), 2.36-2.28 (m, 1H), 1.74-1.65 (m, 1H), 1.14 (d, J = 6.2 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ (ppm): 174.3, 144.9, 128.5, 126.3, 115.5, 56.3, 31.1, 26.9, 20.3; HRMS (ESI) for C 11 H 14 N 2 O [M+Na] + : calc.: 213.1004. Found: 213.0999. 1-(3-Methoxyphenyl)-5-methylpyrrolidin-2-one 2f: 53 mg, 26% yield; yellow oil; 1 H NMR (400 MHz, CDCl 3 ) δ (ppm): 7.28 (d, J = 8.0 Hz, 1H), 7.03-7.02 (m, 1H), 6.93 (d, J = 8.6 Hz, 1H), 6.75 (dd, J = 8.2, 2.4 Hz, 1H), 4.27 (sextet, J = 6.4 Hz, 1H), 3.80 (s, 3H), 2.67-2.48 (m, 2H), 2.40-2.31 (m, 1H), 1.78-1.70 (m, 1H), 1.21 (d, J = 6.2 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ (ppm): 174.2, 160.1, 138.8, 129.6, 116.0, 111.3, 110.1, 55.7, 55.3, 31.4, 26.7, 20.1; HRMS (ESI) for C 12 H 15 NO 2 [M+Na] + : calc.: 228.1000. Found: 228.1005. 5-Methyl-1-phenylpyrrolidin-2-one 2g: [1] 59 mg, 34% yield; white solid; mp. = 49~50 o C; 1 H NMR (400 MHz, CDCl 3 ) δ (ppm): 7.37-7.34 (m, 4H), 7.20-7.18 (m, 1H), 4.28 (sextet, J = 6.4 Hz, 1H), 2.67-2.48 (m, 2H), 2.40-2.31 (m, 1H), 1.78-1.72 (m, 1H), 1.19 (d, J = 6.0 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ (ppm): 174.2, 137.6, 129.0, 125.7, 124.0, 55.6, 31.3, 26.8, 20.2; HRMS (ESI) for C 11 H 13 NO [M+Na] + : calc.: 198.0895. Found: 198.0894. 1-(4-Fluorophenyl)-5-methylpyrrolidin-2-one 2h: [1] 54 mg, 28% yield; white solid; mp. = 74~75 o C; 1 H NMR (400 MHz, CDCl 3 ) δ (ppm): 7.33-7.30 (m, 2H), 7.10-7.06 (m, 2H), 4.23 (sextet, J = 6.4 Hz, 1H), 2.67-2.49 (m, 2H), 2.42-2.33 (m, 1H), 1.80-1.73 (m, 1H), 1.19 (d, J = 6.0 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ (ppm): 174.2, 160.4 (d, 1 J C-F = 243.8 Hz), 133.6 (d, 4 J C-F = 3.0 Hz), 126.0 (d, 3 J C-F = 8.1 Hz), 115. 8 (d, 2 J C-F = 22.4 Hz), 55.8, 31.1, 26.8, 20.1; HRMS (ESI) for C 11 H 12 FNO [M+Na] + : calc.: 216.0800. Found: 216.0802. S12

1-(4-Chlorophenyl)-5-methylpyrrolidin-2-one 2i: [2] 27 mg, 13% yield; yellow oil; 1 H NMR (400 MHz, CDCl 3 ) δ (ppm): 7.33 (s, 4H), 4.26 (sextet, J = 6.4 Hz, 1H), 2.67-2.47 (m, 2H), 2.40-2.31 (m, 1H), 1.79-1.74 (m, 1H), 1.19 (d, J = 6.2 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ (ppm): 174.2, 136.2, 130.9, 129.0, 124.9, 55.4, 31.2, 26.6, 20.0; HRMS (ESI) for C 11 H 12 ClNO [M+Na] + : calc.: 232.0505. Found: 232.0511. 1-(4-Bromophenyl)-5-methylpyrrolidin-2-one 2j: 21 mg, 8% yield; yellow oil; 1 H NMR (400 MHz, CDCl 3 ) δ (ppm): 7.49 (d, J = 8.8 Hz, 1H), 7.28 (d, J = 8.8 Hz, 1H), 4.27 (sextet, J = 6.4 Hz, 1H), 2.67-2.47 (m, 2H), 2.40-2.32 (m, 1H), 1.79-1.74 (m, 1H), 1.20 (d, J = 6.0 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ (ppm): 174.1, 136.7, 132.0, 125.2, 118.6, 55.3, 31.2, 26.6, 20.0; HRMS (ESI) for C 11 H 12 BrNO [M+Na] + : calc.: 276.0000. Found: 276.0006. 5-Methyl-1-(4-(trifluoromethoxy)phenyl)pyrrolidin-2-one 2k: 67 mg, 23% yield; yellow oil; 1 H NMR (400 MHz, CDCl 3 ) δ (ppm): 7.42 (d, J = 9.2 Hz, 2H), 7.22 (d, J = 8.8 Hz, 2H), 4.28 (sextet, J = 6.4 Hz, 1H), 2.68-2.48 (m, 2H), 2.41-2.32 (m, 1H), 1.80-1.75 (m, 1H), 1.21 (d, J = 6.0 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ (ppm): 174.2, 146.3, 136.2, 124.9, 121.5, 120.4 (q, J C-F = 255.6 Hz), 55.5, 31.2, 26.6, 20.0; HRMS (ESI) for C 12 H 13 F 3 NO 2 [M+Na] + : calc.: 282.0718. Found: 282.0727. 7. References 1. Yao-Bing Huang, Jian-Jun Dai, Xiao-Jian Deng, Yan-Chao Qu, Qing-Xiang Guo, and Yao Fu, Chemsuschem 2011, 4, 1578-1581. 2. Xian-Long Du, Lin He, She Zhao, Yong-Mei Liu, Yong Cao, He-Yong He, and Kang-Nian Fan, Angew. Chem. Int. Ed. 2011, 50, 7815-7818. 3. Ya-Wen Wei, Chao Wang, Xue Jiang, Jia Li, Dong Xue, and Jian-Liang Xiao, Chem. Commun. 2013, 49, 5408-5410. S13

175.03 136.79 127.41 127.98 128.61 76.73 77.05 77.37 52.91 43.97 26.67 30.27 19.59 2.49 2.24 1.02 1.03 2.05 1.03 1.03 3.12 1.135 1.151 1.548 1.552 1.558 1.566 1.572 1.576 1.580 1.584 1.590 1.598 1.604 1.607 1.793 2.106 2.110 2.115 2.124 2.130 2.134 2.138 2.142 2.148 2.156 2.161 2.165 2.180 2.337 2.356 2.380 2.398 2.403 2.422 2.440 2.442 2.455 2.457 2.464 2.466 2.479 2.482 3.484 3.499 3.518 3.533 3.955 3.993 4.928 4.966 7.209 7.226 7.229 7.282 7.296 7.300 7.313 7.317 7.321 8. Traces of 1 H and 13 C NMR spectra of products S14

174.90 158.97 128.86 129.27 114.00 76.77 77.09 77.40 52.74 55.23 43.30 26.61 30.29 19.57 1.99 1.99 0.98 2.93 1.05 2.09 1.03 1.03 2.93 6.801 6.823 7.122 7.143 7.260 1.542 1.545 1.550 1.559 1.568 1.574 1.591 2.057 2.073 2.076 2.081 2.091 2.096 2.100 2.103 2.108 2.114 2.123 2.128 2.146 2.310 2.328 2.352 2.371 2.394 2.420 2.434 2.443 2.459 2.477 2.486 2.500 3.440 3.455 3.471 3.488 3.504 3.520 3.754 3.869 3.906 4.852 4.889 S15

174.85 127.96 129.25 133.76 137.00 76.84 77.16 77.47 52.70 43.57 26.62 30.30 19.57 21.06 3.81 0.96 0.96 3.08 2.22 1.13 0.99 2.97 7.108 7.259 1.136 1.152 1.525 1.542 1.549 1.558 1.565 1.573 1.581 1.589 1.596 1.613 2.079 2.098 2.102 2.112 2.118 2.120 2.135 2.145 2.152 2.168 2.313 2.337 2.355 2.360 2.379 2.398 2.402 2.421 2.444 2.459 2.468 2.483 2.501 2.510 2.524 3.462 3.478 3.494 3.511 3.526 3.542 3.900 3.937 4.905 4.942 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 0.0-0.5 ppm S16

175.039 160.946 163.387 129.580 129.660 132.646 132.677 115.366 115.581 76.708 77.026 77.343 52.953 43.299 26.688 30.186 19.625 1.95 1.93 1.01 2.02 1.02 1.05 3.03-0.008 1.143 1.159 1.563 1.566 1.572 1.580 1.587 1.590 1.594 1.598 1.604 1.613 1.618 1.621 1.637 1.730 2.120 2.124 2.129 2.138 2.144 2.148 2.151 2.156 2.162 2.171 2.176 2.179 2.194 2.338 2.356 2.361 2.380 2.398 2.404 2.422 2.449 2.463 2.473 2.488 2.506 2.515 3.482 3.498 3.516 3.531 3.966 4.004 4.856 4.894 6.970 6.991 7.013 7.187 7.201 7.208 7.222 7.257 S17

175.096 128.788 129.349 133.277 135.457 76.718 77.035 77.353 53.046 43.417 26.721 30.193 19.660 1.95 2.15 0.97 0.98 2.34 1.01 2.95 7.146 7.167 7.254 7.260 7.274 1.124 1.140 1.540 1.557 1.564 1.573 1.579 1.587 1.596 1.605 1.611 1.628 2.100 2.119 2.123 2.133 2.138 2.142 2.156 2.165 2.170 2.188 2.332 2.351 2.355 2.374 2.393 2.416 2.440 2.454 2.463 2.479 2.497 2.506 2.520 3.458 3.473 3.489 3.506 3.522 3.538 3.967 4.005 4.822 4.859 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 0.0-0.5 ppm S18

175.23 122.71 125.54 125.58 125.61 125.65 128.17 129.31 129.63 129.95 130.28 141.11 76.70 77.01 77.33 53.22 43.70 26.75 30.09 19.67 2.01 2.02 0.99 2.14 1.08 1.10 3.10 7.260 7.339 7.359 7.556 7.576 1.144 1.159 1.573 1.592 1.595 1.611 1.622 1.628 1.644 1.662 2.136 2.155 2.158 2.174 2.191 2.206 2.224 2.360 2.381 2.402 2.424 2.445 2.465 2.481 2.487 2.504 2.523 2.530 2.545 3.500 3.516 3.532 3.548 3.564 4.093 4.131 4.892 4.930 S19

175.06 159.90 138.32 129.62 120.29 112.81 113.67 76.71 77.03 77.23 77.35 52.98 55.23 43.95 26.66 30.20 19.56 0.98 2.92 0.98 2.99 2.02 1.01 3.02 1.147 1.163 1.558 1.562 1.567 1.576 1.582 1.585 1.590 1.593 1.600 1.608 1.614 1.617 1.632 2.119 2.122 2.127 2.137 2.142 2.146 2.150 2.154 2.160 2.169 2.174 2.178 2.193 2.358 2.376 2.382 2.401 2.419 2.424 2.443 2.461 2.475 2.484 2.500 3.513 3.529 3.547 3.563 3.779 3.930 3.968 4.907 4.945 6.765 6.768 6.780 6.785 6.798 6.806 6.814 7.197 7.217 7.237 7.260 S20

175.084 161.781 164.231 139.528 139.598 114.253 114.462 114.642 114.856 123.443 123.471 130.093 130.174 76.710 77.027 77.346 53.073 43.569 43.583 26.725 30.143 19.629 1.16 1.98 0.95 0.99 2.18 1.01 3.02 6.917 6.939 6.960 6.965 6.993 7.012 7.239 7.260 7.274 7.293 1.143 1.159 1.562 1.579 1.585 1.595 1.602 1.611 1.618 1.627 1.633 1.651 2.130 2.148 2.152 2.163 2.167 2.175 2.185 2.195 2.199 2.218 2.369 2.388 2.410 2.430 2.453 2.468 2.485 2.506 2.528 2.546 3.500 3.515 3.531 3.547 3.563 3.579 4.004 4.042 4.859 4.897 S21

175.07 157.35 120.64 124.89 128.53 129.49 110.35 76.75 77.06 77.38 53.35 55.34 38.38 26.70 30.28 19.62 2.02 1.98 1.01 1.01 3.05 2.03 1.02 1.01 3.06 1.151 1.166 1.544 1.548 1.554 1.562 1.568 1.571 1.576 1.579 1.585 1.593 1.600 1.603 2.102 2.105 2.110 2.120 2.126 2.129 2.133 2.137 2.144 2.152 2.158 2.160 2.314 2.331 2.338 2.356 2.374 2.380 2.398 2.426 2.441 2.448 2.466 3.503 3.519 3.536 3.551 3.813 4.179 4.217 4.780 4.818 6.834 6.854 6.873 6.891 6.910 7.166 7.185 7.196 7.200 7.217 7.236 7.239 7.260 S22

175.162 159.600 162.044 115.214 115.431 123.720 123.867 124.367 124.401 129.135 129.216 130.509 130.551 76.709 77.027 77.345 53.242 37.151 37.194 26.718 30.137 19.587 0.97 1.03 0.92 0.78 0.99 1.03 2.23 1.06 1.08 3.03 1.174 1.190 1.564 1.567 1.573 1.581 1.588 1.591 1.596 1.599 1.605 1.613 1.619 2.123 2.127 2.132 2.140 2.147 2.151 2.155 2.159 2.164 2.174 2.179 2.182 2.323 2.341 2.365 2.383 2.389 2.407 2.434 2.449 2.458 2.473 2.491 2.500 3.512 3.528 3.545 3.561 4.186 4.224 4.832 4.870 6.995 7.019 7.041 7.066 7.085 7.104 7.205 7.209 7.223 7.242 7.247 7.260 7.284 7.303 S23

175.19 127.31 129.80 130.63 131.57 132.73 137.35 76.70 77.01 77.33 53.19 43.10 26.74 30.05 19.71 0.95 1.01 1.05 1.04 2.10 1.05 1.04 3.20 1.137 1.152 1.562 1.577 1.581 1.586 1.595 1.601 1.605 1.609 1.613 1.619 1.628 1.633 1.637 1.652 2.131 2.145 2.149 2.154 2.163 2.169 2.173 2.177 2.181 2.187 2.196 2.201 2.204 2.219 2.344 2.363 2.368 2.387 2.406 2.410 2.429 2.446 2.460 2.469 2.485 2.512 3.498 3.514 3.532 3.548 3.983 4.021 4.769 4.808 7.060 7.065 7.080 7.085 7.258 7.309 7.314 7.359 7.380 S24

174.922 138.909 126.438 128.502 128.714 76.712 77.030 77.347 53.898 41.826 26.828 30.168 33.890 19.689 3.00 2.14 1.03 1.07 1.08 2.04 1.02 1.02 3.11 1.142 1.158 1.519 1.525 1.528 1.533 1.536 1.542 2.100 2.106 2.110 2.114 2.124 2.258 2.282 2.300 2.305 2.323 2.348 2.363 2.372 2.388 2.762 2.766 2.778 2.784 2.800 2.837 2.852 2.860 2.875 3.111 3.126 3.133 3.146 3.160 3.167 3.499 3.515 3.532 3.548 3.782 3.798 3.805 3.817 3.821 3.832 3.840 3.855 7.186 7.189 7.204 7.222 7.260 7.267 7.274 7.283 7.299 7.303 S25

174.95 76.68 77.00 77.31 53.58 39.97 26.81 29.48 30.25 19.72 20.16 13.74 0.97 0.94 1.94 0.93 2.93 2.85 2.04 2.96 0.850 0.868 0.886 1.143 1.159 1.226 1.244 1.263 1.282 1.355 1.372 1.376 1.393 1.409 1.413 1.428 1.431 1.441 1.450 1.463 1.474 1.493 1.498 1.506 1.513 1.516 1.520 1.524 1.530 1.544 2.116 2.121 2.124 2.139 2.152 2.274 2.292 2.297 2.316 2.321 2.337 2.345 2.346 2.362 2.866 2.878 2.887 3.494 3.512 3.517 3.529 3.534 3.546 3.551 3.569 3.614 3.630 3.647 3.663 S26

174.79 76.71 77.03 77.35 53.43 40.10 19.73 22.35 26.79 27.06 29.09 30.26 13.92 1.12 1.07 2.07 1.08 3.14 3.21 4.13 3.07 0.841 0.859 0.876 1.164 1.179 1.205 1.210 1.227 1.245 1.259 1.274 1.290 1.294 1.307 1.313 1.315 1.323 1.404 1.408 1.423 1.426 1.444 1.485 1.493 1.508 1.512 1.517 1.526 1.532 1.536 1.540 1.543 1.549 2.135 2.140 2.144 2.158 2.288 2.307 2.311 2.330 2.334 2.350 2.358 2.375 2.880 2.892 3.506 3.523 3.528 3.540 3.546 3.558 3.563 3.632 3.648 3.666 3.681 7.260 S27

174.83 76.70 77.02 77.34 53.47 40.17 13.95 19.74 22.51 26.61 26.80 27.35 30.27 31.49 0.99 0.99 2.07 1.15 3.28 3.09 6.13 3.09 0.830 0.846 0.862 1.161 1.177 1.250 1.377 1.382 1.394 1.411 1.416 1.432 1.462 1.476 1.490 1.497 1.508 1.514 1.523 1.531 1.547 1.555 1.562 2.115 2.122 2.132 2.139 2.144 2.155 2.170 2.261 2.285 2.303 2.307 2.327 2.332 2.347 2.356 2.371 2.841 2.854 2.863 2.876 2.888 2.898 2.910 3.509 3.526 3.531 3.543 3.549 3.561 3.565 3.583 3.629 3.644 3.661 3.677 7.260 S28

174.57 76.73 77.05 77.25 77.36 53.23 14.00 19.75 22.57 26.79 26.95 27.41 29.15 29.26 30.30 31.73 40.01 0.91 1.16 2.06 2.94 2.84 9.66 1.47 2.91 0.828 0.846 0.862 1.168 1.184 1.236 1.244 1.382 1.386 1.399 1.404 1.409 1.416 1.421 1.438 1.481 1.491 1.501 1.515 1.519 1.524 1.533 1.539 1.542 1.547 1.550 1.556 1.565 1.571 1.574 2.142 2.147 2.151 2.165 2.310 2.329 2.333 2.352 2.358 2.373 2.382 2.398 2.862 2.872 2.884 2.896 2.906 3.509 3.526 3.532 3.543 3.549 3.561 3.566 3.640 3.655 3.673 3.689 7.260 S29

174.76 76.71 77.03 77.34 14.05 19.74 22.63 26.81 26.97 27.41 29.30 29.31 29.51 29.54 29.58 29.59 30.29 31.87 40.15 53.42 0.99 1.96 3.43 18.17 1.08 2.06 3.05 0.844 0.862 0.878 1.176 1.192 1.237 1.395 1.408 1.425 1.429 1.447 1.490 1.499 1.506 1.521 1.524 1.530 1.538 1.545 1.548 1.552 1.555 1.562 1.576 1.579 2.137 2.146 2.152 2.155 2.159 2.170 2.183 2.186 2.302 2.320 2.325 2.344 2.350 2.365 2.374 2.390 2.868 2.877 2.890 2.902 2.912 3.519 3.536 3.541 3.553 3.559 3.570 3.575 3.593 3.643 3.660 3.676 3.692 7.260 S30

174.59 76.72 77.03 77.35 53.24 19.73 22.25 22.64 26.07 26.77 30.29 36.12 38.40 2.00 2.04 1.07 2.01 2.08 3.06 6.14 0.891 0.907 1.169 1.185 1.306 1.323 1.330 1.339 1.345 1.355 1.362 1.368 1.373 1.386 1.501 1.518 1.524 1.535 1.542 1.546 1.551 1.556 1.564 1.570 1.573 2.128 2.138 2.143 2.147 2.151 2.161 2.174 2.270 2.294 2.313 2.318 2.336 2.347 2.362 2.369 2.371 2.386 2.867 2.878 2.889 2.902 2.912 3.563 3.580 3.586 3.597 3.604 3.614 3.621 3.639 3.655 3.672 3.688 7.261 S31

175.617 76.705 77.022 77.340 53.334 56.652 21.791 24.566 27.169 27.691 30.435 11.371 11.425 1.95 1.12 1.03 5.01 3.06 3.02 2.94 7.260 1.550 1.569 1.586 1.597 1.604 1.623 1.641 1.650 1.653 1.658 1.672 1.690 2.097 2.116 2.129 2.140 2.147 2.159 2.171 2.190 2.251 2.265 2.275 2.292 2.306 2.316 2.330 2.424 2.443 2.465 2.485 2.507 3.572 3.591 3.610 3.629 3.649 3.657 3.673 3.685 3.687 3.703 3.719 S32

174.72 174.78 76.81 77.13 77.45 10.22 10.90 13.95 19.36 19.41 22.97 23.53 24.19 26.68 26.71 28.38 28.93 30.21 30.37 30.73 36.61 36.94 43.18 43.38 52.95 53.19 0.96 0.99 2.00 0.96 1.96 5.72 5.31 5.95 0.775 0.793 0.812 0.820 0.830 0.838 0.856 1.120 1.136 1.156 1.165 1.180 1.189 1.223 1.234 1.276 1.283 1.290 1.298 1.317 1.474 1.476 1.490 1.495 1.497 1.506 1.511 1.519 1.529 1.537 1.543 2.089 2.105 2.107 2.112 2.120 2.127 2.143 2.275 2.293 2.307 2.316 2.322 2.329 2.346 2.695 2.729 2.739 2.759 2.772 3.429 3.454 3.465 3.489 3.500 3.581 3.597 3.613 3.628 S33

174.52 76.75 77.07 77.39 52.63 52.97 22.34 25.55 25.91 25.97 27.50 30.09 30.32 31.80 1.87 0.98 1.05 3.06 5.05 1.05 3.12 2.00 1.087 1.120 1.218 1.234 1.291 1.307 1.316 1.324 1.340 1.474 1.482 1.505 1.513 1.536 1.546 1.559 1.569 1.578 1.582 1.590 1.592 1.601 1.612 1.620 1.634 1.643 1.659 1.722 1.727 1.761 1.769 1.776 1.785 1.794 1.802 1.807 1.811 1.815 2.088 2.111 2.142 2.221 2.232 2.263 2.273 2.287 2.298 2.409 2.431 2.453 2.473 3.683 3.692 3.754 3.761 3.765 3.770 3.774 7.260 S34

174.87 175.06 139.79 142.17 127.02 127.07 127.36 128.20 128.43 76.82 77.14 77.46 49.12 50.21 52.63 52.78 16.07 18.29 21.41 22.16 27.42 27.50 30.20 30.35 12.93 2.46 1.47 2.62 3.03 1.50 1.13 2.54 7.95 4.48 3.07 0.758 0.774 1.137 1.153 1.519 1.531 1.533 1.535 1.543 1.554 1.555 1.604 1.619 1.637 2.026 2.057 2.304 2.315 2.328 2.333 2.342 2.346 2.357 2.366 2.370 2.462 2.464 2.484 2.487 2.503 2.506 2.526 2.529 5.403 5.421 5.433 5.451 7.224 7.242 7.268 7.274 7.278 7.290 7.294 7.303 7.309 7.311 7.327 7.333 7.343 7.345 7.348 7.353 7.359 7.363 7.366 7.372 7.373 7.377 S35

174.266 157.689 126.069 130.435 114.350 76.723 77.041 77.359 55.442 56.102 26.848 31.129 20.264 2.00 1.96 3.02 2.04 1.03 1.16 3.05 6.900 6.922 7.212 7.235 7.258 1.159 1.174 1.683 1.702 1.716 1.721 1.725 1.729 1.733 1.739 1.748 1.753 1.757 1.772 2.309 2.324 2.327 2.332 2.342 2.347 2.350 2.356 2.359 2.365 2.374 2.379 2.397 2.471 2.490 2.494 2.514 2.533 2.537 2.556 2.561 2.577 2.585 2.600 2.619 2.628 2.643 3.795 4.133 4.149 4.165 4.182 4.198 4.213 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 0.0-0.5 ppm S36

174.18 134.97 135.62 129.60 124.24 76.70 77.02 77.34 55.76 31.26 26.81 20.20 20.96 3.84 2.02 4.02 1.01 3.12 7.175 7.196 7.218 7.239 7.259 1.181 1.196 1.598 1.694 1.708 1.712 1.718 1.727 1.732 1.736 1.740 1.744 1.750 1.758 1.764 1.767 1.782 2.336 2.354 2.357 2.362 2.365 2.372 2.381 2.386 2.388 2.404 2.481 2.499 2.504 2.523 2.542 2.546 2.565 2.581 2.596 2.604 2.620 2.623 2.639 2.647 2.662 4.200 4.215 4.231 4.233 4.249 4.264 4.279 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 0.0-0.5-1.0 ppm S37

174.21 125.92 130.08 134.52 135.20 137.29 121.91 76.73 77.04 77.36 55.92 31.25 19.28 19.91 20.28 26.87 0.98 1.94 2.03 6.05 1.07 3.08 1.168 1.184 1.682 1.697 1.701 1.706 1.715 1.720 1.724 1.728 1.732 1.738 1.747 1.752 1.756 1.771 2.234 2.255 2.321 2.324 2.329 2.339 2.345 2.348 2.353 2.356 2.363 2.371 2.376 2.379 2.394 2.473 2.492 2.515 2.534 2.539 2.558 2.569 2.584 2.592 2.608 2.611 2.626 2.635 2.650 4.184 4.200 4.202 4.215 4.218 4.233 7.005 7.010 7.025 7.030 7.113 7.123 7.143 7.256 S38

174.31 147.29 149.19 130.75 116.71 108.99 111.26 76.73 77.04 77.36 55.97 56.05 56.24 31.21 26.81 20.26 0.88 0.97 0.97 5.68 2.02 0.98 1.23 2.80 1.176 1.191 1.690 1.704 1.708 1.714 1.722 1.728 1.732 1.736 1.740 1.746 1.754 1.760 1.763 1.778 2.312 2.327 2.330 2.335 2.346 2.351 2.353 2.359 2.362 2.369 2.377 2.382 2.384 2.401 2.479 2.497 2.502 2.521 2.539 2.544 2.563 2.568 2.583 2.591 2.607 2.626 2.634 2.649 3.864 3.866 4.159 4.174 4.192 4.207 6.757 6.763 6.779 6.784 6.848 6.869 6.966 6.971 7.260 S39

174.29 144.86 126.29 128.48 115.46 76.74 77.05 77.37 56.28 31.13 26.90 20.33 1.99 1.97 1.92 2.11 1.07 1.09 2.99 7.031 7.052 7.259 6.647 6.669 1.683 1.688 1.692 1.696 1.700 1.706 1.715 1.720 1.723 1.738 2.276 2.291 2.294 2.299 2.309 2.314 2.317 2.323 2.326 2.332 2.341 2.346 2.364 2.443 2.462 2.466 2.485 2.504 2.508 2.528 2.544 2.553 2.568 2.587 2.595 2.610 3.686 4.060 4.076 4.091 4.109 4.125 4.140 S40

174.17 160.10 138.83 129.58 110.06 111.32 116.01 76.76 77.08 77.39 55.31 55.72 31.37 26.66 20.09 0.90 1.02 0.91 0.98 2.92 2.04 1.04 1.04 3.15 1.205 1.220 1.697 1.711 1.714 1.721 1.728 1.734 1.738 1.742 1.746 1.752 1.760 1.766 1.769 1.783 2.309 2.326 2.332 2.343 2.349 2.357 2.365 2.366 2.375 2.381 2.398 2.482 2.500 2.506 2.525 2.543 2.549 2.566 2.591 2.607 2.615 2.631 2.650 2.658 2.674 3.802 4.250 4.266 4.283 4.299 6.740 6.747 6.761 6.767 6.917 6.920 6.940 7.017 7.023 7.028 7.260 7.281 7.300 S41

174.15 137.64 124.03 125.72 128.96 76.71 77.02 77.34 55.61 31.33 26.76 20.16 3.85 1.04 2.05 1.08 1.01 3.16 7.180 7.181 7.187 7.193 7.202 7.247 7.341 7.357 7.373 1.184 1.199 1.683 1.694 1.709 1.712 1.718 1.726 1.732 1.736 1.740 1.744 1.750 1.758 1.764 1.767 1.782 2.312 2.330 2.336 2.346 2.354 2.360 2.369 2.378 2.383 2.401 2.480 2.498 2.503 2.523 2.541 2.546 2.565 2.587 2.602 2.610 2.626 2.645 2.653 2.668 4.244 4.259 4.275 4.292 4.308 4.323 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 0.0-0.5 ppm S42

174.24 159.21 161.65 133.56 133.59 125.94 126.02 115.68 115.90 76.73 77.05 77.25 77.36 55.84 31.12 26.75 20.11-0.03 1.93 1.91 2.07 1.02 3.05 1.183 1.198 1.579 1.709 1.723 1.727 1.732 1.742 1.747 1.751 1.755 1.759 1.765 1.773 1.779 1.782 1.797 2.332 2.350 2.356 2.366 2.371 2.374 2.379 2.382 2.389 2.397 2.402 2.405 2.421 2.490 2.508 2.513 2.532 2.551 2.555 2.574 2.587 2.602 2.610 2.625 2.644 2.653 2.668 4.191 4.206 4.222 4.239 4.255 4.271 7.056 7.078 7.099 7.259 7.298 7.310 7.315 7.320 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 0.0-0.5-1.0 ppm S43

174.17 136.21 124.92 129.05 130.89 76.73 77.05 77.37 55.43 31.22 26.61 19.99 3.83 2.02 1.04 1.02 3.11 7.260 7.332 1.186 1.201 1.698 1.712 1.716 1.722 1.730 1.736 1.740 1.744 1.748 1.754 1.762 1.768 1.771 1.785 1.797 2.312 2.328 2.331 2.336 2.347 2.352 2.354 2.360 2.362 2.368 2.370 2.378 2.384 2.386 2.402 2.472 2.490 2.496 2.515 2.539 2.557 2.582 2.598 2.606 2.622 2.625 2.641 2.649 2.664 4.223 4.239 4.254 4.271 4.287 4.303 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 0.0-0.5-1.0 ppm S44

174.14 136.73 132.00 125.16 118.64 76.75 77.07 77.39 55.34 31.25 26.58 19.97 1.89 1.84 2.04 1.02 3.12 7.276 7.298 7.479 7.501 1.196 1.212 1.650 1.705 1.719 1.722 1.728 1.736 1.742 1.746 1.750 1.754 1.760 1.768 1.774 1.778 1.792 2.317 2.335 2.340 2.351 2.357 2.359 2.365 2.375 2.383 2.388 2.407 2.477 2.495 2.500 2.520 2.538 2.543 2.561 2.588 2.603 2.611 2.627 2.646 2.654 2.670 4.234 4.249 4.265 4.282 4.297 4.313 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 0.0-0.5-1.0 ppm S45

174.23 146.33 146.35 136.25 116.62 119.18 121.74 124.29 124.87 76.71 77.03 77.35 55.49 31.18 26.61 19.99 1.99 2.01 1.02 1.04 0.96 0.99 3.02 7.211 7.233 7.405 7.428 1.200 1.215 1.710 1.724 1.728 1.734 1.742 1.748 1.752 1.756 1.760 1.766 1.774 1.780 1.783 1.798 2.325 2.340 2.343 2.348 2.359 2.364 2.366 2.372 2.374 2.382 2.390 2.396 2.398 2.414 2.483 2.501 2.507 2.526 2.544 2.550 2.568 2.595 2.611 2.618 2.634 2.637 2.653 2.661 2.677 4.243 4.258 4.274 4.291 4.307 4.322 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 0.0-0.5-1.0 ppm S46