Supporting Information for Palladium-Catalyzed Oxidative Cyclization of Tertiary Enamines for Synthesis of 1,3,4-Trisubstituted Pyrroles and 1,3-Disubstituted Indoles Xiao-Li Lian, Zhi-Hui Ren, Yao-Yu Wang, and Zheng-Hui Guan* Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, Department of Chemistry & Materials Science, Northwest University, Xi an 710069, P. R. China E-mail: guanzhh@nwu.edu.cn CONTENTS 1. General information-------------------------------------------------------------------------s2 2. General procedure for the preparation of tertiary enamines-----------------------s2 3. The optimization of reaction conditions for Pd-catalyzed oxidative cyclization of enamines for synthesis of 1,3-disubstituted indoles ---------------------------------S2-S3 4. Typical procedure for Pd-catalyzed cyclization of enamines ---------------------- S3 5. Characterization data of products ------------------------------------------------S4 S10 6. Copies of 1 H and 13 C NMR spectra-------------------------------------------------s11-s58 - S 1 -
1. General Information 1 H and 13 C NMR spectra were recorded on Varian instrument (400 MHz) and (100 MHz). The following abbreviations (or combinations thereof) were used to explain multiplicities: s = singlet, d = doublet, t = triplet, q = quartet, m = multiplet, b = broad. Coupling constants, J were reported in Hertz unit (Hz). Thin layer chromatography was carried out using silica gel GF254 and flash column chromatography was performed using silica gel 200-300 mesh. Unless otherwise stated, all reagents and solvents were purchased from commercial suppliers and used without further purification. 2. General procedure for the preparation of N-substituted enamines N-substituted enamines were prepared according to following literatures: (1) Pen, Y.; Liu, H.; Tang, M.; Cai, L.; Pike, V. Chin. J. Chem. 2009, 27, 1339. (2) Byun, E.; Hong, B.; De Castro, K.; Lim, M.; Rhee, H. J. Org. Chem. 2007, 72, 9815. (3) X. Ji, H. Huang, W. Wu, X. Li, H. Jiang, J. Org. Chem. 2013, 78, 11155. 3. The optimization of reaction conditions for Pd-catalyzed oxidative cyclization of enamines for synthesis of 1,3-disubstituted indoles. [a] Entry Catalyst Additive Solvent T ( o C) Yield[%] [b] 1 Pd(OAc) 2 - CH 3 CN 100 5 2 Pd(OAc) 2 K 2 CO 3 CH 3 CN 100 NR 3 Pd(OAc) 2 PivOH CH 3 CN 100 13 4 Pd(TFA) 2 PivOH CH 3 CN 100 18 5 PdCl 2 PivOH CH 3 CN 100 25 6 [c] PdCl 2 PivOH CH 3 CN 100 43 - S 2 -
7 [c] PdCl 2 TFA CH 3 CN 100 68 8 [c] PdCl 2 TFA DMF 100 33 9 [c] PdCl 2 TFA toluene 100 26 10 [c] PdCl 2 TFA DCE 100 43 11 [c] PdCl 2 TFA CH 3 CN 60 27 [a] Reaction conditions: 3a (0.2 mmol), [Pd] (5 mol%), Cu(OAc) 2 (1.2 equiv), Additive (1.0 equiv) in CH 3 CN (2 ml) at 100 o C, in air. [b] Isolated yield. [c] The reaction was carried out with 2.0 equiv of Cu(OAc) 2. 4. Typical procedure for Pd-catalyzed cyclization of enamines Typical procedure for synthesis of 1,3,4-trisubstituted pyrroles: (E)-ethyl 3-(allyl(phenyl)amino)acrylate 1a (0.2 mmol), Pd(OAc) 2 (5 mol%), Cu(OAc) 2 (0.44 mmol), TFA (0.2 mmol) and CH 3 CN (2 ml) was stirred in a 10 ml round-bottom flask at 60 o C in air. After completion of the reaction (detected by TLC), the reaction mixture was cooled to room temperature, quenched with H 2 O (10 ml) and extracted with EtOAc (3 10 ml) or CH 2 Cl 2 (3 10 ml). Removal of the solvent in vacuo and purification of the residue by flash chromatography (SiO 2, pentane/etoac) provided pyrrole 2a (70%) as a pale yellow solid. Typical procedure for synthesis of 1,3-disubstituted indoles: (E)-butyl 3-(methyl(phenyl)amino)acrylate 3a (0.2 mmol), PdCl 2 (5 mol%), Cu(OAc) 2 (0.40 mmol), TFA (0.2 mmol) and CH 3 CN (2 ml) was stirred in a 10 ml round-bottom flask at 100 o C in air. After completion of the reaction (detected by TLC), the reaction mixture was cooled to room temperature, quenched with H 2 O (10 ml) and extracted with EtOAc (3 10 ml) or CH 2 Cl 2 (3 10 ml). Removal of the solvent in vacuo and purification of the residue by flash chromatography (SiO 2, pentane/etoac) provided indole 4a (68%) as a white solid. - S 3 -
5. Characterization data of products CO 2 Et N 2a 2a: Yield: 70% (32.1 mg), pale yellow solid; 1 H NMR (CDCl 3, 400 MHz): δ = 7.55 (s, 1 H), δ = 7.34-7.30 (m, 2 H), δ = 7.27-7.25 (d, J = 7.6 Hz, 2 H), δ = 7.19-7.16 (m, 1 H), δ = 6.72 (s, 1 H), δ = 4.23-4.17 (m, 2 H), δ = 2.34 (s, 3 H), δ = 1.26 (t, J = 7.2 Hz, 3 H); 13 C NMR (CDCl 3, 100 MHz): δ = 165.2, 139.7, 129.6, 126.3, 124.7, 122.9, 120.4, 118.9, 116.5, 59.4, 14.4, 11.7. HRMS Calcd (ESI) m/z for C 14 H 15 NNaO 2 : [M+Na] + 252.0995, found: 252.0999. 2b: Yield: 62% (30.1 mg), pale yellow liquid; 1 H NMR (CDCl 3, 400 MHz): δ = 7.53 (d, J = 2.4 Hz, 1 H), δ = 7.20-7.14 (m, 4 H), δ = 6.72 (s, 1 H), δ = 4.25-4.19 (m, 2 H), δ = 2.30 (s, 3 H), δ = 2.25 (s, 3 H), δ = 1.28 (t, J = 7.2 Hz, 3 H); 13 C NMR (CDCl 3, 100 MHz): δ = 165.3, 137.5, 136.3, 130.1, 124.8, 122.8, 120.4, 119.0, 116.3, 59.4, 29.7, 20.9, 14.5, 11.8. HRMS Calcd (ESI) m/z for C 15 H 17 NNaO 2 : [M+Na] + 266.1151, found: 266.1158. 2c: Yield: 62% (30.1 mg), pale yellow liquid; 1 H NMR (CDCl 3, 400 MHz): δ = 7.54 (s, 1 H), δ = 7.23-7.17 (m, 1 H), δ = 7.10-7.07 (d, J = 11.6 Hz, 2 H), δ = 7.01-7.00 (d, J = 7.2 Hz, 1 H), δ = 6.73 (s, 1 H), δ = 4.24-4.19 (m, 2 H), δ = 2.31 (s, 3 H), 2.25 (s, 3 H), δ = 1.27 (t, J = 6.8 Hz, 3 H); 13 C NMR (CDCl 3, 100 MHz): δ = 165.2, 139.7, 139.7, 129.4, 127.1, 124.7, 122.8, 121.1, 118.9, 117.5, 116.4, 59.4, 21.4, 14.5, 11.8. HRMS Calcd (ESI) m/z for C 15 H 17 NNaO 2 : [M+Na] + 266.1151, found: 266.1156. CO 2 Et N 2d 2d: Yield: 52% (26.7 mg), yellow solid; 1 H NMR (CDCl 3, 400 MHz): δ = 7.53 (d, J = 2.4 Hz, 1 H), δ = 7.08 (s, 2 H), δ = 7.03-7.01 (m, 1 H), δ = 6.71 (s, 1 H), δ = 4.25-4.19 (m, 2 H), δ = 2.25 (s, 3 - S 4 -
H), δ = 2.23 (s, 3 H), δ = 2.20 (s, 3 H), δ = 1.28 (t, J = 7.2 Hz, 3 H); 13 C NMR (CDCl 3, 100 MHz): δ = 165.3, 138.0, 137.7, 134.9, 130.5, 124.8, 122.7, 121.8, 119.1, 117.8, 116.1, 59.4, 19.9, 19.2, 14.5, 11.8. HRMS Calcd (ESI) m/z for C 16 H 19 NNaO 2 : [M+Na] + 280.1308, found: 280.1314. CO 2 Et N 2e 2e: Yield: 40% (19.4 mg), colourless liquid; 1 H NMR (CDCl 3, 400 MHz): δ = 7.34 (d, J = 2.4 Hz, 1 H), 7.30-7.29 (d, J = 3.6 Hz, 2H), 7.27-7.19( m, 3H), δ = 4.31-4.26 (m, 2 H), δ = 2.33 (s, 3 H), δ = 2.21 (s, 3 H), δ = 1.34 (t, J = 8.0 Hz, 3 H); 13 C NMR (CDCl 3, 100 MHz): δ = 165.4, 139.6, 133.6, 131.1, 128.1, 127.7, 126.7, 126.4, 121.8, 121.6, 59.4, 17.8, 14.5, 11.7. HRMS Calcd (ESI) m/z for C 15 H 17 NNaO 2 : [M+Na] + 266.1151, found: 266.1157. 2f: Yield: 55% (28.5 mg), pale yellow liquid; 1 H NMR (CDCl 3, 400 MHz): δ = 7.47 (d, J = 2.0 Hz, 1 H), δ = 7.19 (d, J = 3.6 Hz, 2 H), δ = 6.86 (d, J = 8.8 Hz, 2 H), δ = 6.66 (s, 1 H), δ = 4.24-4.19 (m, 2 H), δ = 3.75 (s, 3 H), δ = 2.25 (s, 3 H), δ = 1.27 (t, J = 7.2 Hz, 3 H); 13 C NMR (CDCl 3, 100 MHz): δ = 165.3, 158.1, 133.4, 125.0, 122.1, 119.4, 116.0, 114.7, 59.4, 55.5, 29.7, 14.5, 11.7. HRMS Calcd (ESI) m/z for C 15 H 17 NNaO 3 : [M+Na] + 282.1101, found: 282.1108. 2g: Yield: 60% (49.4 mg), yellow solid; 1 H NMR (CDCl 3, 400 MHz): δ = 7.48 (d, J = 1.6 Hz, 1 H), δ = 7.26-7.23 (m, 2 H), δ = 7.04-7.02 (m, 2 H), δ = 6.67 (s, 1 H), δ = 4.24-4.19 (m, 2 H), δ = 2.24 (s, 3 H), δ = 1.27 (t, J = 6.8 Hz, 3 H); 13 C NMR (CDCl 3, 100 MHz): δ = 165.1, 161.0 (d, J CF = 244.8Hz), 136.2, 125.0, 123.1, 122.3 (d, J CF = 8.3 Hz), 119.2, 116.7, 116.4 (d, J CF = 22.9 Hz), 59.5, 14.5, 11.7. HRMS Calcd (ESI) m/z for C 14 H 14 FNNaO 2 : [M+Na] + 270.0901, found: 270.0893. CO 2 Et N 2h Cl - S 5 -
2h: Yield: 67% (35.2 mg), yellow solid; 1 H NMR (CDCl 3, 400 MHz): δ = 7.56 (s, 1 H), δ = 7.36 (d, J = 8.0 Hz, 2 H), δ = 7.27 (d, J = 8.0 Hz, 2 H), δ = 6.75 (s, 1 H), δ = 4.29-4.24 (m, 2 H), δ = 2.29 (s, 3 H), δ = 1.32 (t, J = 7.2 Hz, 3 H); 13 C NMR (CDCl 3, 100 MHz): δ = 165.0, 138.3, 131.9, 129.7, 124.6, 123.4, 121.6, 118.8, 117.0, 59.5, 14.5, 11.7. HRMS Calcd (ESI) m/z for C 14 H 14 ClNNaO 2 : [M+Na] + 286.0605, found: 286.0601. 2i: Yield: 61% (32.1 mg), pale yellow liquid; 1 H NMR (CDCl 3, 400 MHz): δ = 7.54 (s, 1 H), δ = 7.30-7.25 (m, 2 H), δ = 7.18 (s, 2 H), δ = δ = 6.73 (s, 1 H), δ = 4.24-4.19 (m, 2 H), δ = 2.24 (s, 3 H), δ = 1.28 (t, J = 7.2 Hz, 3 H); 13 C NMR (CDCl 3, 100 MHz): δ = 165.0, 140.7, 135.3, 130.7, 126.4, 123.5, 120.6, 118.7, 118.4, 117.2, 59.6, 14.5, 11.7. HRMS Calcd (ESI) m/z for C 14 H 14 ClNNaO 2 : [M+Na] + 286.0605, found: 286.0612. 2j: Yield: 56% (34.4 mg), pale yellow solid; 1 H NMR (CDCl 3, 400 MHz): δ = 7.52 (s, 1 H), δ = 7.49 (d, J = 8.4 Hz, 2 H), δ = 7.17 (d, J = 8.8 Hz, 2 H), δ = 6.71 (s, 1 H), δ = 4.25-4.19 (m, 2 H), δ = 2.24 (s, 3 H), δ = 1.28 (t, J = 7.2 Hz, 3 H); 13 C NMR (CDCl 3, 100 MHz): δ = 165.0, 138.8, 132.7, 124.5, 123.4, 121.8, 119.6, 118.7, 117.1, 59.7, 14.5, 11.7. HRMS Calcd (ESI) m/z for C 14 H 14 BrNNaO 2 : [M+Na] + 330.0100, found: 330.0108. 2k: Yield: 45% (25.1 mg), pale yellow solid 1 H NMR (CDCl 3, 400 MHz): δ = 7.82 (d, J = 8.8 Hz, 1 H), δ = 7.78-7.74 (m, 2 H), δ = 7.69-7.68 (m, 2 H), 7.46-7.40 (m, 3 H), δ = 6.87 (s, 1 H), δ = 4.27-4.21 (m, 2 H), δ = 2.29 (s, 3 H), δ = 1.30 (t, J = 7.2 Hz, 3 H); 13 C NMR (CDCl 3, 100 MHz): δ = 165.2, 137.1, 133.6, 131.7, 129.8, 127.8, 126.0, 124.9, 123.2, 119.6, 119.1, 117.7, 116.8, 59.5, 14.5, 11.8. HRMS Calcd (ESI) m/z for C 18 H 17 NNaO 2 : [M+Na] + 302.1151, found: 302.1144. - S 6 -
CO 2 Me N CO 2 Me 2l 2l: Yield: 65% (32.5 mg), pale yellow solid; 1 H NMR (CDCl 3, 400 MHz): δ = 7.34 (d, J = 7.6 Hz, 2 H), δ = 7.20 (d, J = 6.8 Hz, 2 H), δ = 6.58 (s, 1 H), δ = 3.78 (s, 3 H), δ = 3.63 (s, 3 H), δ =2.16 (s, 3 H); 13 C NMR (CDCl 3, 100 MHz): δ = 165.4, 161.9, 139.3, 129.0, 128.1, 126.0, 125.2, 124.4, 120.9, 119.4, 52.2, 51.6, 11.0. HRMS Calcd (ESI) m/z for C 15 H 15 NNaO 4 : [M+Na] + 273.1009, found: 273.1000. 2m: Yield: 62% (30.1 mg), yellow solid; 1 H NMR (CDCl 3, 400 MHz): δ = 7.58 (s, 1 H), δ = 7.34-7.32 (m, 4 H), δ = 7.22-7.21 (d, J = 6.4 Hz, 2 H), δ = 6.76 (s, 1 H), δ = 4.25-4.21 (m, 2 H), δ = 2.74-2.72 (m, 3 H), δ = 1.28 (t, J = 6.8 Hz, 3 H), δ = 1.20-1.16 (t, J = 7.2 Hz, 3 H); 13 C NMR (CDCl 3, 100 MHz): δ = 165.0, 139.9, 130.0, 129.6, 125.0, 120.5, 117.8, 116.0, 59.4, 19.6, 14.5, 14.4. HRMS Calcd (ESI) m/z for C 15 H 17 NNaO 2 : [M+Na] + 266.1165, found: 266.1157. 2n: Yield: 55% (28.3 mg), pale yellow solid; 1 H NMR (CDCl 3, 400 MHz): δ = 7.58 (s, 1 H), δ = 7.34-7.31 (m, 4 H), δ = 7.21-7.19 (d, J = 10.8 Hz, 1 H), δ = 6.77 (s, 1 H), δ = 4.25-4.20 (m, 2 H), δ =3.40-3.33 (m, 1 H), δ = 1.28 (t, J = 6.8 Hz, 3 H), δ = 1.20 (d, J = 6.8 Hz, 6 H); 13 C NMR (CDCl 3, 100 MHz): δ = 164.9, 139.9, 135.4,129.6, 126.4,125.2, 120.6, 116.5, 115.4, 59.4, 25.5, 23.6, 14.5. HRMS Calcd (ESI) m/z for C 16 H 19 NNaO 2 : [M+Na] + 280.1313, found: 280.1315. 4a: Yield: 68% (31.4 mg), white solid; 1 H NMR (CDCl 3, 400 MHz): δ = 8.17 (t, J = 4.8 Hz,1 H), 7.77 (s, 1H), 7.34-7.25 (m, 3 H), 4.33 (t, J = 6.4 Hz, 2 H), 3.81 (s, 3 H), 1.78 (t, J = 6.8 Hz, 2 H), 1.52-1.48 (m, 2 H), 0.99 (t, J = 7.2 Hz, 3H) ; 13 C NMR (CDCl 3, 100 MHz): δ =165.2, 137.1, 135.1, 126.5, 122.6, 121.7, 121.6, 109.7, 107.1, 63.5, 33.4, 31.0, 19.4, 13.8. HRMS Calcd (ESI) m/z for - S 7 -
C 14 H 17 NNaO 2 : [M+Na] + 254.1151, found: 254.1161. CO 2 Me N 4b 4b: Yield: 55% (20.8 mg), white solid; 1 H NMR (CDCl 3, 400 MHz): δ = 8.18-8.16 (m, 1 H), 7.78 (s, 1 H), 7.36-7.26 (m, 3 H), 3.91 (s, 3 H), 3.82 (s, 3 H); 13 C NMR (CDCl 3, 100 MHz): δ =165.4, 137.1, 135.1, 126.5, 122.7, 121.8, 121.5, 109.7, 106.7, 50.9, 33.4. HRMS Calcd (ESI) m/z for C 11 H 11 NNaO 2 : [M+Na] + 212.0682, found: 212.0691. CO 2 Et N 4c 4c: Yield: 55% (22.3 mg), white solid; 1 H NMR (CDCl 3, 400 MHz): δ = 8.18 (d, J = 6.8 Hz, 1 H), 7.77 (s, 1 H), 7.33-7.25 (m, 3 H), 4.37(d, J = 6.8 Hz, 2 H), 3.80 (s, 3 H), 1.43-1.40 (m, 3 H); 13 C NMR (CDCl 3, 100 MHz): δ =165.1, 137.1, 135.1, 126.5, 122.6, 121.7, 121.6, 109.7, 107.0, 59.6, 33.3, 29.7, 14.5. HRMS Calcd (ESI) m/z for C 12 H 13 NNaO 2 : [M+Na] + 226.0838, found: 226.0845. 4d: Yield: 61% (28.2 mg), pale yellow solid; 1 H NMR (CDCl 3, 400 MHz): δ = 8.15 (d, J = 6.0 Hz, 1 H), 7.70 (s, 1 H), 7.30-7.25 (m, 3 H), 3.78 (s, 3 H), 1.63(s, 9 H); 13 C NMR (CDCl 3, 100 MHz): δ =164.6, 137.1, 135.0, 126.5, 122.5, 121.6, 109.6, 108.6, 79.7, 33.3, 28.5. HRMS Calcd (ESI) m/z for C 14 H 17 NNaO 2 : [M+Na] + 254.1151, found: 254.1156. 4e: Yield: 50% (25.1 mg), white solid; 1 H NMR (CDCl 3, 400 MHz): δ = 8.25-8.23 (m, 1 H), 7.93 (s, 1 H), 7.44-7.29 (m, 5 H), 7.24 (d, J = 8.0 Hz, 2 H), 3.84 (s, 3 H); 13 C NMR (CDCl 3, 100 MHz): δ =164.6, 137.1, 135.0, 126.5, 122.5, 121.6, 109.6, 108.6, 79.7, 33.3, 28.5. HRMS Calcd (ESI) m/z for C 16 H 13 NNaO 2 : [M+Na] + 274.0838, found: 274.0848. - S 8 -
4f: Yield:60% (29.4 mg), pale yellow solid; 1 H NMR (CDCl 3, 400 MHz): δ = 8.03 (d, J = 8.0 Hz, 1 H), 7.70 (s, 1 H), 7.11 (d, J =9.2 Hz, 2 H), 4.32 (t, J = 6.4 Hz, 2 H), 3.77 (s, 3 H), 2.50 (s, 3 H), 1.77 (t, J = 7.2 Hz,2 H), 1.51-1.48 (m, 2 H), 0.99 (t, J = 7.6 Hz, 3 H) ; 13 C NMR (CDCl 3, 100 MHz): δ =165.3, 137.5, 134.6, 132.6, 124.3, 123.5, 121.2, 109.7, 107.0, 63.4, 33.2, 31.0, 21.8, 19.4, 13.8. HRMS Calcd (ESI) m/z for C 15 H 19 NNaO 2 : [M+Na] + 268.1308, found: 268.1323. 4g: Yield: 52% (27.0 mg), pale yellow solid; 1 H NMR (CDCl 3, 400 MHz): δ = 7.92 (s, 1 H), 7.65 (s, 1 H), 7.09 (s, 1 H), 4.32 (t, J = 6.8 Hz, 2 H), 3.75 (s, 3 H), 2.39 (s, 6 H), 1.77 (t, J = 7.2 Hz, 2 H), 1.52-1.48 (m, 2 H), 0.99 (t, J = 7.2 Hz, 3H) ; 13 C NMR (CDCl 3, 100 MHz): δ =165.3, 136.0, 134.3, 131.8, 130.6, 124.8, 121.6, 110.0, 106.4, 63.3, 33.3, 31.0, 20.6, 20.2, 19.4, 13.8. HRMS Calcd (ESI) m/z for C 16 H 21 NNaO 2 : [M+Na] + 282.1465, found: 282.1471. 4h: Yield: 65% (31.9 mg), pale yellow solid; 1 H NMR (CDCl 3, 400 MHz): δ = 8.18-8.16 (m, 1 H), 7.85 (s, 1 H), 7.37-7.35 (m, 1 H), 7.28-7.25 (m, 2 H), 4.35-4.32 (m, 2 H), 4.21-4.16 (m, 2 H), 1.78 (t, J = 7.6 Hz, 2 H), 1.50 (t, J = 7.6 Hz, 5 H), 0.99 (t, J = 7.2 Hz, 3 H); 13 C NMR (CDCl 3, 100 MHz): δ =165.3, 136.2, 133.4, 126.7, 121.7, 121.7, 109.8, 107.2, 63.5, 41.5, 31.0, 19.4, 15.1, 13.8. HRMS Calcd (ESI) m/z for C 15 H 19 NNaO 2 : [M+Na] + 268.1308, found: 268.1321. 4i: Yield: 51% (26.2 mg), pale yellow solid; 1 H NMR (CDCl 3, 400 MHz): δ = 7.89 (d, J = 8.0 Hz, 1 H), 7.79 (s, 1 H), 7.18 (t, J = 7.2 Hz, 1 H), 7.00-6.98 (m, 1 H), 4.34-4.31 (m, 2 H), 4.19 (s, 2 H), 3.00 (s, 2 H), 2.25 (s, 2 H), 1.80-1.76 (m, 2 H), 1.51 (d, J = 7.2 Hz, 2 H), 0.99 (t, J = 7.2 Hz, 3 H); 13 C NMR (CDCl 3, 100 MHz): δ =165.6, 134.4, 132.3, 124.4, 122.2, 122.2, 119.8, 119.0, 107.3, - S 9 -
63.5, 44.7, 31.0, 24.3, 22.7, 19.4, 13.8. HRMS Calcd (ESI) m/z for C 16 H 19 NNaO 2 : [M+Na] + 280.1308, found: 280.1311. 4j: Yield: 15% (8.0 mg), pale yellow liquid; 1 H NMR (CDCl 3, 400 MHz): δ = 8.26 (d, J = 7.2 Hz, 1 H), 8.04 (s, 1 H), 7.54-7.50 (m, 5 H), 7.33-7.26 (m, 3 H), 4.43-4.41 (m, 2 H), 1.44 (t, J = 7.2 Hz, 3 H); 13 C NMR (CDCl 3, 100 MHz): δ =165.1, 138.5, 136.6, 134.1, 129.8, 127.8, 126.9, 124.8, 123.4, 122.4, 121.9, 111.0, 109.4, 59.9, 14.6. HRMS Calcd (ESI) m/z for C 17 H 15 NNaO 2 : [M+Na] + 288.1000, found: 288.0994. - S 10 -
6. Copies of 1 H and 13 C NMR Spectra CO 2 Et N 2a - S 11 -
CO 2 Et N 2a - S 12 -
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CO 2 Et N 2d - S 17 -
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CO 2 Et N 2h Cl - S 25 -
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CO 2 Me N CO 2 Me 2l - S 33 -
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CO 2 Me N 4b - S 41 -
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