Supporting Information

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1 Supporting Information Diastereoselective Synthesis of Symmetrical and Unsymmetrical Tetrahydropyridines Catalyzed by Bi(III) Immobilized on Triazine Dendrimer Stabilized Magnetic Nanoparticles Beheshteh Asadi, Amir Landarani-Isfahani, Iraj Mohammadpoor-Baltork,*, Shahram Tangestaninejad, Majid Moghadam, Valiollah Mirkhani, and Hadi Amiri Rudbari Catalysis Division, Department of Chemistry, University of Isfahan, Isfahan , Iran. Table of Contents 1 General.S2 2 General procedure for synthesis of symmetrical THP derivatives catalyzed by Fe 3 O Bi(III)...S2 3 General procedure for synthesis of unsymmetrical THP derivatives catalyzed by Fe 3 O Bi(III)...S2 4 Spectroscopic data of the products...s3-s H and 13 CNMR spectra of the products...s13-s31 6 Crystal structure of compound 4b S32 7 Crystal data and structure refinement for compound 4b S33 8 Selected bond lengths (Å) and angles ( ) for compound 4b...S34-S37 9 References S38 S1

2 1. General: The chemicals used in this work were purchased from Fluka and Merck chemical companies. Melting points were determined with a Stuart Scientific SMP2 apparatus. FT-IR spectra were recorded on a Nicolet-Impact 400D spectrophotometer. 1 H and 13 C NMR (400 and 100 MHz) spectra were recorded on a Bruker Avance 400 MHz spectrometer using CDCl 3 as solvent. Elemental analysis was performed on a LECO, CHNS-932 analyzer. 2. General procedure for synthesis of symmetrical THP derivatives catalyzed by Fe 3 O Bi(III): The Fe 3 O catalyst (133 mg, 8 mol% Bi(III)) was added to a mixture of aryl aldehyde (2 mmol), aryl amine (2 mmol), and ethyl acetoacetate (1 mmol), in ethanol (5 ml), and the mixture was stirred at room temperature for the proper time shown in Scheme 2. On completion of the reaction, as evident from the TLC analysis, (eluent: petroleum ether/etoac, 5:1), the catalyst was easily separated using a permanent magnet and washed with EtOH (5 ml). The organic residue was filtered, washed with EtOH for several times and dried under vacuum to give the favored product with excellent yield and purity. All yields are isolated yields. 3. General procedure for synthesis of unsymmetrical THP derivatives catalyzed by Fe 3 O Bi(III): The Fe 3 O catalyst (133 mg, 8 mol% Bi(III)) was added to a mixture of two different aryl aldehydes (2 mmol), aryl amine (2 mmol), and ethyl acetoacetate (1 mmol), in ethanol (5 ml), and the mixture was stirred at room temperature for the proper time shown in Scheme 3. After completion of the reaction, as evident from the TLC analysis, (eluent: petroleum ether/etoac, 5:1), the work-up was done as defined for synthesis of symmetric THP derivatives to give the favored product with excellent yield and purity (Scheme 3, 5a-b). Isolated yields are shown. For synthesis of unsymmetrical THP derivatives (Scheme 4, 7a-b), the Fe 3 O catalyst (133 mg, 8 mol% Bi(III)) was added to a mixture of the related aryl aldehyde (2 mmol), two different aryl amines (2 mmol), and ethyl acetoacetate (1 mmol), in ethanol (5 ml), and the mixture was stirred at room temperature for the proper time shown in Scheme 4 under the same conditions and the pure products were gained in 80-85% isolated yields. S2

3 4. Spectroscopic data of the products: Ethyl 1,2,6-triphenyl-4-(phenylamino)-1,2,5,6-tetrahydropyridine-3-carboxylate (Scheme 2, 4a) Mp o C. (Lit. [1] o C) IR (KBr): ν max = 3244, 3065, 2978, 2871, 1652, 1589, 1498, 1372, 1252, 1172, 1069, 750, 696 cm H NMR (400 MHz, CDCl 3 ): δ = 1.39 (t, J = 7.1 Hz, 3H), 2.69 (dd, 1 J = 15.0 Hz, 2 J = 2.4 Hz, 1H), 2.80 (dd, 1 J = 15.0 Hz, 2 J = 5.7 Hz, 1H), (m, 1H), (m, 1H), (m, 1H), (m, 2H), 6.39 (s, 1H), 6.45 (d, J = 8.2, 2H), 6.53 (t, J = 7.2 Hz, 1H), (m, 5H), (m, 2H), 7.14 (d, J = 7.2, 1H), (m, 5H), 7.21 (d, J = 7.4, 2H), (br s, 1H). Anal. Calcd for C 32 H 30 N 2 O 2 : C, 80.98; H, 6.37; N, Found: C, 81.17; H, 6.30; N, Ethyl 2,6-bis(2-methoxyphenyl)-1-phenyl-4-(phenylamino)-1,2,5,6-tetrahydropyridine-3- carboxylate (Scheme 2, 4b) Mp o C. IR (KBr): ν max = 3225, 3067, 3025, 2976, 2834, 1659, 1591, 1488, 1459, 1240, 1177, 1066, 1027, 749 cm H NMR (400 MHz, CDCl 3 ): δ = 1.46 (t, J = 7.0 Hz, 3H), 2.87 (dd, 1 J = 15.2 Hz, 2 J = 5.6 Hz, 1H), 3.03 (d, J = 15.6 Hz, 1H), 3.62 (s, 3H), 3.86 (s, 3H), (m, 1H), (m, 1H), 5.46 (br s, 1H), 6.30 (d, J = 7.7 Hz, 2H), (m, 3H), (m, 2H), (m, 3H), (m, 1H), (m, 4H), (m, 4H), 9.79 (br s, 1H). 13 C NMR (100 MHz, CDCl 3 ): δ = , , , , , , , , , , , , , , , , , , , , , , 97.59, 58.94, 54.78, 54.33, 52.83, 52.68, 28.81, Anal. Calcd for C 34 H 34 N 2 O 4 : C, 76.38; H, 6.41; N, Found: C, 76.63; H, 6.34; N, Ethyl 1-phenyl-4-(phenylamino)-2,6-di-p-tolyl-1,2,5,6-tetrahydropyridine-3-carboxylate (Scheme 2, 4c) S3

4 Mp o C. (Lit. [1] o C) IR (KBr): ν max = 3231, 3095, 3055, 2928, 2884, 1648, 1588, 1497, 1370, 1254, 1068, 1020, 786, 747cm H NMR (400 MHz, CDCl 3 ): δ = 1.50 (t, J = 7.1 Hz, 3H), 2.36 (s, 3H), 2.38 (s, 3H), 2.81 (dd, 1 J = 15.0 Hz, 2 J = 2.4 Hz, 1H), 2.91 (dd, 1 J = 15.0 Hz, 2 J = 5.6 Hz, 1H), (m, 1H), (m, 1H), (m, 1H), (m, 2H), 6.46 (s, 1H), 6.58 (d, J = 8.2 Hz, 2H), 6.64 (t, J = 7.2 Hz, 1H), (m, 11H), 7.27 (d, J = 8.5 Hz, 2H), (br s, 1H). Anal. Calcd for C 34 H 34 N 2 O 2 : C, 81.24; H, 6.82; N, Found: C, 81.41; H, 6.78; N, Ethyl 2,6-bis(4-nitrophenyl)-1-phenyl-4-(phenylamino)-1,2,5,6-tetrahydropyridine-3-carboxylate (Scheme 2, 4d) Mp o C. (Lit. [2] o C) IR (KBr): ν max = 3260, 3062, 2975, 2922, 2854, 1653, 1593, 1420, 1346, 1244, 1172, 1071, 1049, 854, 750 cm H NMR (400 MHz, CDCl 3 ): δ = 1.16 (t, J = 7.1 Hz, 3H), 2.37 (ABq, J = 12.1 Hz, 1H), 2.75 (dd, 1 J = 15.6 Hz, 2 J = 3.3 Hz, 1H), (m, 1H), (m, 1H), 4.60 (dd, 1 J = 12.1 Hz, 2 J = 3.2 Hz, 1H), 5.95 (s, 1H), 6.69 (d, J = 8.0 Hz, 2H), 6.77 (t, J = 7.3 Hz, 1H), 6.92 (d, J = 7.6 Hz, 2H), (m, 3H), 7.25 (t, J = 7.6 Hz, 2H), 7.35 (d, J = 8.7 Hz, 2H), 7.66 (d, J = 8.5 Hz, 2H), 7.80 (d, J = 8.7 Hz, 2H), 8.19 (d, J = 8.8 Hz, 2H), (br s, 1H). Anal. Calcd for C 32 H 28 N 4 O 6 : C, 68.07; H, 5.00; N, Found: C, 68.16; H, 4.95; N, Ethyl (Scheme 2, 4e) 2,6-bis(3-nitrophenyl)-1-phenyl-4-(phenylamino)-1,2,5,6-tetrahydropyridine-3-carboxylate Mp o C. (Lit. [3]) IR (KBr): ν max = 3239, 3068, 2927, 2867, 1655, 1594, 1529, 1499, 1348, 1251, 1175, 1068, 783, 747, 726 cm H NMR (400 MHz, CDCl 3 ): δ = 1.52 (t, J = 7.1 Hz, 3H), 2.88 (d, J = 4.04 Hz, 2H), (m, 1H), (m, 1H), 5.32 (t, J = 3.8 Hz, 1H), (m, 2H), 6.44 (d, J = 8.3 Hz, 2H), 6.49 (s, 1H), 6.69 (t, J = 7.3 Hz, 1H), (m, 5H), (m, 3H), 7.64 (d, J = S4

5 7.6 Hz, 1H), 7.94 (s, 1H), (m, 2H), 8.31 (s, 1H), (br s, 1H). Anal. Calcd for C 32 H 28 N 4 O 6 : C, 68.07; H, 5.00; N, Found: C, 67.89; H, 5.04; N, Ethyl 2,6-bis(4-methoxyphenyl)-1-phenyl-4-(phenylamino)-1,2,5,6-tetrahydropyridine-3- carboxylate (Scheme 2, 4f) Mp o C. (Lit. [2] o C) IR (KBr): ν max = 3241, 3055, 2930, 2834, 1650, 1590, 1503, 1295, 1248, 1172, 1069, 1034, 793, 745 cm H NMR (400 MHz, CDCl 3 ): δ = 1.48 (t, J = 7.0 Hz, 3H), 2.77 (dd, 1 J = 15.0 Hz, 2 J = 2.5 Hz, 1H), 2.87 (dd, 1 J = 15.0 Hz, 2 J = 5.6 Hz, 1H), 3.80 (s, 3H), 3.81 (s, 3H), (m, 1H), (m, 1H), (m, 1H), (m, 3H), 6.55 (d, J = 8.2 Hz, 2H), 6.62 (t, J = 7.2 Hz, 1H), 6.83 (dd, 1 J = 8.7 Hz, 2 J = 2.0 Hz, 4H), (m, 7H), 7.25 (d, J = 8.5 Hz, 2H), (br s, 1H). Anal. Calcd for C 34 H 34 N 2 O 4 : C, 76.38; H, 6.41; N, Found: C, 76.49; H, 6.37; N, Ethyl 2,6-diphenyl-1-(p-tolyl)-4-(p-tolylamino)-1,2,5,6-tetrahydropyridine-3-carboxylate (Scheme 2, 4g) Mp o C. (Lit. [2] o C) IR (KBr): ν max = 3237, 3060, 3028, 2915, 1648, 1613, 1591, 1514, 1448, 1315, 1249, 1073, 873, 771, 700 cm H NMR (400 MHz, CDCl 3 ): δ = 1.38 (t, J = 7.1 Hz, 3H), 2.08 (s, 3H), 2.18 (s, 3H), 2.65 (dd, 1 J = 15.1 Hz, 2 J = 2.4 Hz, 1H), 2.75 (dd, 1 J = 15.1 Hz, 2 J = 5.7 Hz, 1H), (m, 1H), (m, 1H), 5.03 (d, J = 3.6, 1H), 6.07 (d, J = 8.2, 2H), 6.35 (d, J = 8.5, 3H), (m, 4H), (m, 5H), (m, 5H), (br s, 1H). Anal. Calcd for C 34 H 34 N 2 O 2 : C, 81.24; H, 6.82; N, Found: C, 81.00; H, 6.65; N, Ethyl 2,6-bis(4-chlorophenyl)-1-(p-tolyl)-4-(p-tolylamino)-1,2,5,6-tetrahydropyridine-3-carboxylate (Scheme 2, 4h) S5

6 Mp o C. (Lit. [4] o C) IR (KBr): ν max = 3246, 3093, 3063, 3030, 2979, 2918, 1653, 1612, 1593, 1514, 1253, 1072, 803 cm H NMR (400 MHz, CDCl 3 ): δ = 1.36 (t, J = 7.1 Hz, 3H), 2.09 (s, 3H), 2.21 (s, 3H), 2.63 (dd, 1 J = 15.2 Hz, 2 J = 2.8 Hz, 1H), 2.70 (dd, 1 J = 15.2 Hz, 2 J = 5.4 Hz, 1H), (m, 1H), (m, 1H), (m, 1H), 6.20 (d, J = 8.2 Hz, 2H), 6.24 (s, 1H), 6.28 (d, J = 8.7 Hz, 2H), 6.81 (d, J = 8.4 Hz, 2H), 6.87 (d, J = 8.1 Hz, 2H), 6.98 (d, J = 8.4 Hz, 2H), (m, 6H), (br s, 1H). Anal. Calcd for C 34 H 32 Cl 2 N 2 O 2 : C, 71.45; H, 5.64; N, Found: C, 71.58; H, 5.59; N, Ethyl 2,6-bis(3-bromophenyl)-1-(p-tolyl)-4-(p-tolylamino)-1,2,5,6-tetrahydropyridine-3-carboxylate (Scheme 2, 4i) Mp o C. IR (KBr): ν max = 3223, 3064, 2987, 2857, 1647, 1595, 1569, 1513, 1467, 1252, 1065, 898, 797, 779 cm H NMR (400 MHz, CDCl 3 ): δ = 1.48 (t, J = 7.1 Hz, 3H), 2.19 (s, 3H), 2.31 (s, 3H), 2.72 (dd, 1 J = 15.3 Hz, 2 J = 2.6 Hz, 1H), 2.80 (dd, 1 J = 15.2 Hz, 2 J = 5.5 Hz,1H), (m, 1H), (m, 1H), 5.08 (br s, 1H), 6.26 (d, J = 8.1 Hz, 2H), 6.34 (s, 1H), 6.38 (d, J = 8.6 Hz, 2H), 6.91 (d, J = 8.6 Hz, 2H), 6.99 (d, J = 8.1 Hz, 2H), (m, 5H), 7.35 (d, J = 7.8 Hz,1H), (m, 1H), 7.56 (s, 1H), (br s, 1H). 13 C NMR (100 MHz, CDCl 3 ): δ = , , , , , , , , , , , , , , , , , , , , , , 96.37, 59.25, 56.97, 54.60, 32.99, 20.45, 19.65, Anal. Calcd for C 34 H 32 Br 2 N 2 O 2 : C, 61.83; H, 4.88; N, Found: C, 62.00; H, 4.83; N, Ethyl 1,2,6-tri-p-tolyl-4-(p-tolylamino)-1,2,5,6-tetrahydropyridine-3-carboxylate (Scheme 2, 4j) Mp o C. (Lit. [2] o C) IR (KBr): ν max = 3236, 3092, 3025, 2979, 2918, 2858, 1647, 1617, 1594, 1514, 1253, 1072, 801 cm H NMR (400 MHz, CDCl 3 ): δ = 1.47 (t, J = 7.1 Hz, 3H), 2.18 (s, 3H), 2.29 (s, 3H), 2.34 (s, 3H), 2.36 (s, 3H), 2.75 (dd, 1 J = 15.0 Hz, 2 J = 2.4 Hz, 1H), 2.84 (dd, 1 J = 15.0 Hz, 2 J = 5.6 Hz, 1H), (m, 1H), (m, 1H), (m, 1H), 6.20 (d, J = 8.2 Hz, 2H), 6.39 (s, 1H), 6.46 (d, J = 8.6 Hz, 2H), 6.90 (t, J = 7.7 Hz, 4H), (m, 6H), 7.24 (d, J = 8.0 Hz, S6

7 2H), (br s, 1H). Anal. Calcd for C 36 H 38 N 2 O 2 : C, 81.47; H, 7.22; N, Found: C, 81.56; H, 7.17; N, Ethyl 1-(4-bromophenyl)-4-((4-bromophenyl)amino)-2,6-diphenyl-1,2,5,6-tetrahydropyridine-3- carboxylate (Scheme 2, 4k) Mp o C. (Lit. [2] o C) IR (KBr): ν max = 3239, 3088, 2974, 2929, 1645, 1602, 1582, 1492, 1318, 1253, 1068, 799, 775, 719 cm H NMR (400 MHz, CDCl 3 ): δ = 1.50 (t, J = 7.1 Hz, 3H), 2.73 (dd, 1 J = 15.1 Hz, 2 J = 2.3 Hz, 1H), 2.88 (dd, 1 J = 15.1 Hz, 2 J = 5.8 Hz, 1H), (m, 1H), (m, 1H), (m, 1H), 6.13 (d, J = 8.6 Hz, 2H), (m, 3H), (m, 4H), 7.22 (d, J = 8.6 Hz, 2H), (m, 6H), (br s, 1H). Anal. Calcd for C 32 H 28 Br 2 N 2 O 2 : C, 60.78; H, 4.46; N, Found: C, 60.92; H, 4.43; N, Ethyl 1-(4-bromophenyl)-4-((4-bromophenyl)amino)-2,6-bis(4-methoxyphenyl)-1,2,5,6- tetrahydropyridine-3-carboxylate (Scheme 2, 4l) Mp o C. (Lit. [2] o C) IR (KBr): ν max = 3230, 3064, 2993, 2826, 1644, 1602, 1583, 1506, 1248, 1070, 1030, 795 cm H NMR (400 MHz, CDCl 3 ): δ = 1.48 (t, J = 7.1 Hz, 3H), 2.71 (dd, 1 J = 15.1 Hz, 2 J = 2.4 Hz, 1H), 2.85 (dd, 1 J = 15.1 Hz, 2 J = 5.6 Hz, 1H), 3.80 (s, 3H), 3.81 (s, 3H), (m, 1H), (m, 1H), (m, 1H), 6.22 (d, J = 8.6 Hz, 2H), 6.31 (s, 1H), 6.41 (d, J = 9.1 Hz, 2H), (m, 4H), 7.06 (d, J = 8.6 Hz, 2H), 7.15 (d, J = 9.1 Hz, 2H), 7.20 (d, J = 8.6 Hz, 2H), 7.25 (d, J = 8.6 Hz, 2H), (br s, 1H). Anal. Calcd for C 34 H 32 Br 2 N 2 O 4 : C, 58.97; H, 4.66; N, Found: C, 59.11; H, 4.63; N, Ethyl 1-(4-chlorophenyl)-4-((4-chlorophenyl)amino)-2,6-di-p-tolyl-1,2,5,6-tetrahydropyridine-3- carboxylate (Scheme 2, 4m) S7

8 Mp o C. (Lit. [2] o C) IR (KBr): ν max = 3231, 3088, 2979, 2857, 1647, 1603, 1496, 1320, 1251, 1071, 797 cm H NMR (400 MHz, CDCl 3 ): δ = 1.38 (t, J = 7.1 Hz, 3H), 2.24 (s, 3H), 2.27 (s, 3H), 2.61 (dd, 1 J = 15.1 Hz, 2 J = 2.3 Hz, 1H), 2.77 (dd, 1 J = 15.1 Hz, 2 J = 5.8 Hz, 1H), (m, 1H), (m, 1H), (m, 1H), 6.11 (d, J = 8.6 Hz, 2H), 6.25 (s, 1H), 6.35 (d, J = 9.2 Hz, 2H), (m, 10H), 7.09 (d, J = 8.0 Hz, 2H), (br s, 1H). Anal. Calcd for C 34 H 32 Cl 2 N 2 O 2 : C, 71.45; H, 5.64; N, Found: C, 71.31; H, 5.68; N, Ethyl 1-(4-chlorophenyl)-4-((4-chlorophenyl)amino-2,6-diphenyl-1,2,5,6-tetrahydropyridine-3- carboxylate (Scheme 2, 4n) Mp o C. (Lit. [2] o C) IR (KBr): ν max = 3241, 3092, 3025, 2974, 1644, 1602, 1495, 1320, 1254, 1070, 1028, 802, 775, 728 cm H NMR (400 MHz, CDCl 3 ): δ = 1.50 (t, J = 7.1 Hz, 3H), 2.72 (dd, 1 J = 15.1 Hz, 2 J = 2.3 Hz, 1H), 2.88 (dd, 1 J = 15.1 Hz, 2 J = 5.8 Hz, 1H), (m, 1H), (m, 1H), (m, 1H), 6.20 (d, J = 8.6 Hz, 2H), 6.41 (s, 1H), 6.45 (d, J = 9.1 Hz, 2H), 7.02 (d, J = 9.1 Hz, 2H), (m, 2H), (m, 1H), (m, 7H), (br s, 1H). Anal. Calcd for C 32 H 28 Cl 2 N 2 O 2 : C, 70.72; H, 5.19; N, Found: C, 70.87; H, 5.17; N, Ethyl 1,2,6-tris(4-chlorophenyl)-4-((4-chlorophenyl)amino)-1,2,5,6-tetrahydropyridine-3- carboxylate (Scheme 2, 4o) Mp o C. (Lit. [5] o C) IR (KBr): ν max = 3235, 3064, 2980, 1652, 1600, 1492, 1254, 1091, 1071, 808 cm H NMR (400 MHz, CDCl 3 ): δ = 1.47 (t, J = 7.1 Hz, 3H), 2.70 (dd, 1 J = 15.2 Hz, 2 J = 2.5 Hz, 1H), 2.83 (dd, 1 J = 15.2 Hz, 2 J = 5.6 Hz, 1H), (m, 1H), (m, 1H), (m, S8

9 1H), 6.30 (s, 1H), 6.34 (d, J = 8.6 Hz, 2H), 6.38 (d, J = 9.2 Hz, 2H), (m, 4H), 7.15 (d, J = 8.6 Hz, 2H), (m, 5H), 7.29 (s, 1H), (br s, 1H). Anal. Calcd for C 32 H 26 Cl 4 N 2 O 2 : C, 62.76; H, 4.28; N, Found: C, 62.93; H, 4.23; N, Ethyl 1-(4-bromophenyl)-4-((4-bromophenyl)amino)-2,6-di(naphthalen-2-yl)-1,2,5,6- tetrahydropyridine-3-carboxylate (Scheme 2, 4p) Mp o C. (Lit. [6] o C) IR (KBr): ν max = 3230, 3057, 2972, 2854, 1646, 1600, 1586, 1490, 1317, 1250, 1064, 817, 796 cm H NMR (400 MHz, CDCl 3 ): δ = 1.56 (t, J = 7.1 Hz, 3H), 2.87 (d, J = 13.4 Hz, 1H), 3.05 (dd, 1 J = 15.2 Hz, 2 J = 5.6 Hz,1H), (m, 1H), (m, 1H), (m, 1H), 6.03 (d, J = 8.4 Hz, 2H), 6.48 (d, J = 8.9 Hz, 2H), 6.60 (s, 1H), 7.07 (d, J = 8.4 Hz, 2H), 7.12 (d, J = 8.9 Hz, 2H), (m, 7H), (m, 7H), (br s, 1H). Anal. Calcd for C 40 H 32 Br 2 N 2 O 2 : C, 65.59; H, 4.40; N, Found: C, 65.73; H, 4.37; N, Ethyl 2,6-di(naphthalen-2-yl)-1-phenyl-4-(phenylamino)-1,2,5,6-tetrahydropyridine-3-carboxylate (Scheme 2, 4q) Mp o C. IR (KBr): ν max = 3225, 3052, 3025, 2972, 2903, 1655, 1590, 1500, 1323, 1242, 1068, 896, 795, 747 cm H NMR (400 MHz, CDCl 3 ): δ = 1.55 (t, J = 7.0 Hz, 3H), 2.92 (dd, 1 J = 15.2 Hz, 2 J = 2.2 Hz, 1H), 3.07 (dd, 1 J = 15.1 Hz, 2 J = 5.7 Hz,1H), (m, 1H), (m, 1H), (m, 1H), 6.17 (d, J = 7.5 Hz, 2H), (m, 2H), 6.68 (s, 1H), (m, 5H), 7.32 (dd, 1 J = 8.5 Hz, 2 J = 1.5 Hz, 1H), (m, 4H), (m, 10H), (br s, 1H). 13 C NMR (100 MHz, CDCl 3 ): δ = , , , , , , , , , , , , , , , , , , , , , , , , , , , 97.57, 59.30, 57.90, 55.18, 33.27, Anal. Calcd for C 40 H 34 N 2 O 2 : C, 83.59; H, 5.96; N, Found: C, 83.70; H, 5.92; N, Ethyl 2,6-di(naphthalen-2-yl)-1-(p-tolyl)-4-(p-tolylamino)-1,2,5,6-tetrahydropyridine-3-carboxylate (Scheme 2, 4r) S9

10 Mp o C. IR (KBr): ν max = 3234, 3054, 3025, 2976, 2860, 1646, 1616, 1586, 1513, 1384, 1250, 1064, 818, 796, 750 cm H NMR (400 MHz, CDCl 3 ): δ = 1.54 (t, J = 7.1 Hz, 3H), 2.15 (s, 3H), 2.22 (s, 3H), 2.88 (dd, 1 J = 15.2 Hz, 2 J = 2.5 Hz, 1H), 3.02 (dd, 1 J = 15.1 Hz, 2 J = 5.6 Hz,1H), (m, 1H), (m, 1H), (m, 1H), 6.06 (d, J = 8.2 Hz, 2H), 6.52 (d, J = 8.7 Hz, 2H), 6.63 (s, 1H), 6.75 (d, J = 8.0 Hz, 2H), 6.86 (d, J = 8.4 Hz, 2H), 7.32 (dd, 1 J = 8.4 Hz, 2 J = 1.6 Hz, 1H), (m, 4H), (m, 2H), (m, 7H), (br s, 1H). 13 C NMR (100 MHz, CDCl 3 ): δ = , , , , , , , , , , , , , , , , , , , , , , , , , , , , , 97.09, 59.17, 57.88, 55.35, 33.22, 20.36, 19.66, Anal. Calcd for C 42 H 38 N 2 O 2 : C, 83.69; H, 6.35; N, Found: C, 83.88; H, 6.28; N, Ethyl 1-(4-chlorophenyl)-4-((4-chlorophenyl)amino)-2,6-di(naphthalen-2-yl)-1,2,5,6- tetrahydropyridine-3-carboxylate (Scheme 2, 4s) Mp o C. IR (KBr): ν max = 3234, 3058, 2980, 2852, 1647, 1597, 1495, 1320, 1252, 1066, 819, 798, 748 cm H NMR (400 MHz, CDCl 3 ): δ = 1.56 (t, J = 7.0 Hz, 3H), 2.86 (d, J = 15.2 Hz, 1H), 3.05 (dd, 1 J = 15.2 Hz, 2 J = 5.6 Hz,1H), (m, 1H), (m, 1H), (m, 1H), 6.09 (d, J = 8.4 Hz, 2H), 6.53 (d, J = 8.9 Hz, 2H), 6.60 (s, 1H), 6.92 (d, J = 8.4 Hz, 2H), 6.99 (d, J = 8.9 Hz, 2H), (m, 7H), (m, 7H), (br s, 1H). 13 C NMR (100 MHz, CDCl 3 ): δ = , , , , , , , , , , , , , , , , , , , , , , , , , , , , , 98.67, 59.99, 58.45, 55.87, 33.62, Anal. Calcd for C 40 H 32 Cl 2 N 2 O 2 : C, 74.65; H, 5.01; N, Found: C, 74.51; H, 5.05; N, Ethyl 1-(4-chlorophenyl)-4-((4-chlorophenyl)amino)-6-(naphthalen-2-yl)-2-phenyl-1,2,5,6- tetrahydropyridine-3-carboxylate (Scheme 3, 5a) S10

11 Mp o C. IR (KBr): ν max = 3234, 3053, 2983, 2854, 1652, 1601, 1493, 1321, 1251, 1067, 802, 754 cm H NMR (400 MHz, CDCl 3 ): δ = 1.51 (t, J = 7.2 Hz, 3H), 2.95 (dd, 1 J = 15.2 Hz, 2 J = 5.6 Hz, 1H), 3.04 (dd, 1 J = 15.2 Hz, 2 J = 5.6 Hz,1H), (m, 2H), (m, 1H), 6.09 (d, J = 8.5 Hz, 2H), (m, 2H), 6.60 (s, 1H), 6.91 (d, J = 8.5 Hz, 2H), (m, 2H), (m, 3H), (m, 3H), (m, 1H), (m, 5H), (br s, 1H). 13 C NMR (100 MHz, CDCl 3 ): δ = , , , , , , , , , , , , , , , , , , , , , , , 98.35, 59.45, 57.89, 55.00, 33.01, Anal. Calcd for C 36 H 30 Cl 2 N 2 O 2 : C, 72.85; H, 5.09; N, Found: C, 73.11; H, 5.05; N, Ethyl 6-(naphthalen-2-yl)-2-phenyl-1-(p-tolyl)-4-(p-tolylamino)-1,2,5,6-tetrahydropyridine-3- carboxylate (Scheme 3, 5b) Mp o C. IR (KBr): ν max = 3236, 3053, 2978, 2857, 1652, 1596, 1513, 1381, 1249, 1066, 820, 800, 751 cm H NMR (400 MHz, CDCl 3 ): δ = 1.53 (t, J = 7.1 Hz, 3H), 2.15 (s, 3H), 2.22 (s, 3H), 2.89 (dd, 1 J = 11.1 Hz, 2 J = 2.7 Hz, 1H), 3.02 (dd, 1 J = 15.2 Hz, 2 J = 5.6 Hz,1H), (m, 2H), 5.28 (br s, 1H), 6.06 (d, J = 8.1 Hz, 2H), (m, 2H), 6.62 (s, 1H), 6.75 (d, J = 8.1 Hz, 2H), (m, 2H), (m, 1H), (m, 2H), 7.38 (d, J = 7.4 Hz, 1H), (m, 2H), (m, 1H), (m, 5H), (br s, 1H). 13 C NMR (100 MHz, CDCl 3 ): δ = , , , , , , , , , , , , , , , , , , , , , , , 97.32, 59.08, 57.81, 54.94, 33.09, 20.32, 19.61, Anal. Calcd for C 38 H 36 N 2 O 2 : C, 82.58; H, 6.57; N, Found: C, 82.49; H, 6.54; N, Ethyl 1-(4-chlorophenyl)-2,6-di(naphthalen-2-yl)-4-(p-tolylamino)-1,2,5,6-tetrahydropyridine-3- carboxylate (Scheme 4, 7a) S11

12 Mp o C. IR (KBr): ν max = 3233, 3054, 2976, 2916, 2880, 1647, 1591, 1512, 1494, 1384, 1314, 1250, 1064, 796, 749 cm H NMR (400 MHz, CDCl 3 ): δ = 1.54 (t, J = 7.1 Hz, 3H), 2.15 (s, 3H), (m, 1H), (m, 1H), (m, 1H), (m, 1H), (m, 1H), 6.53 (d, J = 8.0 Hz, 2H), 6.62 (d, J = 9.2 Hz, 2H), (m, 2H), (m, 3H), (m, 1H), (m, 4H), (m, 9H), (br s, 1H). 13 C NMR (100 MHz, CDCl 3 ): δ = , , , , , , , , , , , , , , , , , , , , , , , 97.56, 59.64, 58.35, 55.82, 33.70, 20.83, Anal. Calcd for C 41 H 35 ClN 2 O 2 : C, 79.02; H, 5.66; N, Found: C, 78.93; H, 5.63; N, Ethyl (Scheme 4, 7b) 1-(4-chlorophenyl)-2,6-diphenyl-4-(p-tolylamino)-1,2,5,6-tetrahydropyridine-3-carboxylate Mp o C. IR (KBr): ν max = 3237, 3085, 2982, 2912, 2864, 1647, 1594, 1510, 1495, 1372, 1316, 1250, 1180, 1074, 946, 799, 773, 700 cm H NMR (400 MHz, CDCl 3 ): δ = 1.38 (t, J = 7.0 Hz, 3H), 2.18 (s, 3H), (m, 1H), (m, 1H), (m, 1H), (m, 1H), (m, 1H), (m, 2H), (m, 3H), (m, 3H), (m, 1H), (m, 4H), (m, 6H), (br s, 1H). 13 C NMR (100 MHz, CDCl 3 ): δ = , , , , , , , , , , , , , , , , , , 97.66, 59.56, 58.23, 55.15, 33.55, 20.90, Anal. Calcd for C 33 H 31 ClN 2 O 2 : C, 75.78; H, 5.97; N, Found: C, 75.64; H, 6.01; N, N-benzylidene-4-chloroaniline (Scheme 3, 6a) Mp o C. (Lit. [7]) IR (KBr): ν max = 3059, 2920, 2872, 1623, 1575, 1483, 1449, 1189, 1089, 881, 822, 755 cm H NMR (400 MHz, CDCl 3 ): δ = (m, 2H), (m, 2H), (m, 3H), (m, 2H), 8.45 (s, 1H). Anal. Calcd for C 13 H 10 ClN: C, 72.39; H, 4.67; N, Found: C, 72.63; H, 4.60; N, Ethyl 3-(p-tolylamino)but-2-enoate (Scheme 4, 8a) S12

13 Oil. (Lit. [8]) IR (KBr): ν max = 3258, 3032, 2979, 2928, 1653, 1610, 1517, 1269, 1167, 1059, 1020, 786 cm H NMR (400 MHz, CDCl 3 ): δ = 1.30 (t, J = 7.1 Hz, 3H), 1.96 (s, 3H), 2.34 (s, 3H), 4.16 (q, J = 7.1 Hz, 2H), 4.68 (s, 1H), 6.99 (d, J = 8.2 Hz, 2H), 7.13 (d, J = 8.2 Hz, 2H), (br s, 1H). Anal. Calcd for C 13 H 17 NO 2 : C, 71.21; H, 7.81; N, Found: C, 71.62; H, 7.77; N, H NMR and 13 C NMR spectra of the products Ethyl 1,2,6-triphenyl-4-(phenylamino)-1,2,5,6-tetrahydropyridine-3-carboxylate (Scheme 2, 4a); 1 H NMR (400 MHz, CDCl 3 ) S13

14 Ethyl 2,6-bis(2-methoxyphenyl)-1-phenyl-4-(phenylamino)-1,2,5,6-tetrahydropyridine-3- carboxylate (Scheme 2, 4b); 1 H NMR (400 MHz, CDCl 3 ) S14

15 Ethyl 2,6-bis(2-methoxyphenyl)-1-phenyl-4-(phenylamino)-1,2,5,6-tetrahydropyridine-3- carboxylate (Scheme 2, 4b); 13 C NMR (100 MHz, CDCl 3 ) Ethyl 1-phenyl-4-(phenylamino)-2,6-di-p-tolyl-1,2,5,6-tetrahydropyridine-3-carboxylate (Scheme 2, 4c); 1 H NMR (400 MHz, CDCl 3 ) S15

16 Ethyl 2,6-bis(4-nitrophenyl)-1-phenyl-4-(phenylamino)-1,2,5,6-tetrahydropyridine-3-carboxylate (Scheme 2, 4d); 1 H NMR (400 MHz, CDCl 3 ) Ethyl 2,6-bis(3-nitrophenyl)-1-phenyl-4-(phenylamino)-1,2,5,6-tetrahydropyridine-3-carboxylate (Scheme 2, 4e); 1 H NMR (400 MHz, CDCl 3 ) S16

17 Ethyl 2,6-bis(4-methoxyphenyl)-1-phenyl-4-(phenylamino)-1,2,5,6-tetrahydropyridine-3- carboxylate (Scheme 2, 4f); 1 H NMR (400 MHz, CDCl 3 ) Ethyl 2,6-diphenyl-1-(p-tolyl)-4-(p-tolylamino)-1,2,5,6-tetrahydropyridine-3-carboxylate (Scheme 2, 4g); 1 H NMR (400 MHz, CDCl 3 ) Ethyl 2,6-bis(4-chlorophenyl)-1-(p-tolyl)-4-(p-tolylamino)-1,2,5,6-tetrahydropyridine-3-carboxylate (Scheme 2, 4h); 1 H NMR (400 MHz, CDCl 3 ) S17

18 Ethyl 2,6-bis(3-bromophenyl)-1-(p-tolyl)-4-(p-tolylamino)-1,2,5,6-tetrahydropyridine-3-carboxylate (Scheme 2, 4i); 1 H NMR (400 MHz, CDCl 3 ) Ethyl 2,6-bis(3-bromophenyl)-1-(p-tolyl)-4-(p-tolylamino)-1,2,5,6-tetrahydropyridine-3-carboxylate (Scheme 2, 4i); 13 C NMR (100 MHz, CDCl 3 ) S18

19 Ethyl 1,2,6-tri-p-tolyl-4-(p-tolylamino)-1,2,5,6-tetrahydropyridine-3-carboxylate (Scheme 2, 4j); 1 H NMR (400 MHz, CDCl 3 ) Ethyl 1-(4-bromophenyl)-4-((4-bromophenyl)amino)-2,6-diphenyl-1,2,5,6-tetrahydropyridine-3- carboxylate (Scheme 2, 4k); 1 H NMR (400 MHz, CDCl 3 ) S19

20 Ethyl 1-(4-bromophenyl)-4-((4-bromophenyl)amino)-2,6-bis(4-methoxyphenyl)-1,2,5,6- tetrahydropyridine-3-carboxylate (Scheme 2, 4l); 1 H NMR (400 MHz, CDCl 3 ) Ethyl 1-(4-chlorophenyl)-4-((4-chlorophenyl)amino)-2,6-di-p-tolyl-1,2,5,6-tetrahydropyridine-3- carboxylate (Scheme 2, 4m); 1 H NMR (400 MHz, CDCl 3 ) S20

21 Ethyl 1-(4-chlorophenyl)-4-((4-chlorophenyl)amino-2,6-diphenyl-1,2,5,6- tetrahydropyridine-3- carboxylate (Scheme 2, 4n); 1 H NMR (400 MHz, CDCl 3 ) Ethyl 1,2,6-tris(4-chlorophenyl)-4-((4-chlorophenyl)amino)-1,2,5,6-tetrahydropyridine-3- carboxylate (Scheme 2, 4o); 1 H NMR (400 MHz, CDCl 3 ) S21

22 Ethyl 1-(4-bromophenyl)-4-((4-bromophenyl)amino)-2,6-di(naphthalen-2-yl)-1,2,5,6- tetrahydropyridine-3-carboxylate (Scheme 2, 4p); 1 H NMR (400 MHz, CDCl 3 ) S22

23 Ethyl 2,6-di(naphthalen-2-yl)-1-phenyl-4-(phenylamino)-1,2,5,6-tetrahydropyridine-3-carboxylate (Scheme 2, 4q); 1 H NMR (400 MHz, CDCl 3 ) Ethyl 2,6-di(naphthalen-2-yl)-1-phenyl-4-(phenylamino)-1,2,5,6-tetrahydropyridine-3-carboxylate (Scheme 2, 4q); 13 C NMR (100 MHz, CDCl 3 ) S23

24 Ethyl 2,6-di(naphthalen-2-yl)-1-(p-tolyl)-4-(p-tolylamino)-1,2,5,6-tetrahydropyridine-3-carboxylate (Scheme 2, 4r); 1 H NMR (400 MHz, CDCl 3 ) Ethyl 2,6-di(naphthalen-2-yl)-1-(p-tolyl)-4-(p-tolylamino)-1,2,5,6-tetrahydropyridine-3-carboxylate (Scheme 2, 4r); 13 C NMR (100 MHz, CDCl 3 ) S24

25 Ethyl 1-(4-chlorophenyl)-4-((4-chlorophenyl)amino)-2,6-di(naphthalen-2-yl)-1,2,5,6- tetrahydropyridine-3-carboxylate (Scheme 2, 4s); 1 H NMR (400 MHz, CDCl 3 ) Ethyl 1-(4-chlorophenyl)-4-((4-chlorophenyl)amino)-2,6-di(naphthalen-2-yl)-1,2,5,6- tetrahydropyridine-3-carboxylate (Scheme 2, 4s); 13 C NMR (100 MHz, CDCl 3 ) S25

26 Ethyl 1-(4-chlorophenyl)-4-((4-chlorophenyl)amino)-6-(naphthalen-2-yl)-2-phenyl-1,2,5,6- tetrahydropyridine-3-carboxylate (Scheme 3, 5a); 1 H NMR (400 MHz, CDCl 3 ) Ethyl 1-(4-chlorophenyl)-4-((4-chlorophenyl)amino)-6-(naphthalen-2-yl)-2-phenyl-1,2,5,6- tetrahydropyridine-3-carboxylate (Scheme 3, 5a); 13 C NMR (100 MHz, CDCl 3 ) S26

27 Ethyl 6-(naphthalen-2-yl)-2-phenyl-1-(p-tolyl)-4-(p-tolylamino)-1,2,5,6-tetrahydropyridine-3- carboxylate (Scheme 3, 5b); 1 H NMR (400 MHz, CDCl 3 ) Ethyl 6-(naphthalen-2-yl)-2-phenyl-1-(p-tolyl)-4-(p-tolylamino)-1,2,5,6-tetrahydropyridine-3- carboxylate (Scheme 3, 5b); 13 C NMR (100 MHz, CDCl 3 ) S27

28 Ethyl 1-(4-chlorophenyl)-2,6-di(naphthalen-2-yl)-4-(p-tolylamino)-1,2,5,6-tetrahydropyridine-3- carboxylate (Scheme 4, 7a); 1 H NMR (400 MHz, CDCl 3 ) Ethyl 1-(4-chlorophenyl)-2,6-di(naphthalen-2-yl)-4-(p-tolylamino)-1,2,5,6-tetrahydropyridine-3- carboxylate (Scheme 4, 7a); 13 C NMR (100 MHz, CDCl 3 ) S28

29 Ethyl 1-(4-chlorophenyl)-2,6-diphenyl-4-(p-tolylamino)-1,2,5,6-tetrahydropyridine-3-carboxylate (Scheme 4, 7b); 1 H NMR (400 MHz, CDCl 3 ) Ethyl 1-(4-chlorophenyl)-2,6-diphenyl-4-(p-tolylamino)-1,2,5,6-tetrahydropyridine-3-carboxylate (Scheme 4, 7b); 13 C NMR (100 MHz, CDCl 3 ) S29

30 N-benzylidene-4-chloroaniline (Scheme 3, 6a); 1 H NMR (400 MHz, CDCl 3 ) S30

31 Ethyl 3-(p-tolylamino)but-2-enoate (Scheme 4, 8a); 1 H NMR (400 MHz, CDCl 3 ) S31

32 Figure 1. ORTEP representation of 4b. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. There are two independent molecules in asymmetric unit cell. One molecule is omitted for clarity. S32

33 Table 1. Crystal data and structure refinement for 4b Empirical formula C 34 H 34 N 2 O 4 Formula weight Temperature 298(2) K Wavelength Å Crystal system Monoclinic Space group P2(1)/c Unit cell dimensions a = (3) Å b = (6) Å c = (3) Å β= 90.29(3) º Volume 5692(2) Å 3 Z 8 Density (calculated) Mg/m 3 Absorption coefficient mm -1 F(000) 2272 Theta range for data collection 2.54 to Index ranges -17 h k l 14 Reflections collected Independent reflections 9791 [R (int) = ] Data Completeness 97.6% Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 9791 / 1 / 729 Goodness-of-fit on F Final R indices [I>2σ (I)] R 1 = wr 2 = R indices (all data) R 1 = wr 2 = Largest diff. peak and hole and e.å -3 S33

34 Table 2. Selected bond lengths (Å) and angles ( ) for 4b N(4)-C(53) 1.395(5) C(46)-C(51) 1.377(6) N(4)-C(43) 1.467(5) C(46)-C(47) 1.386(6) N(4)-C(44) 1.474(5) C(46)-C(44) 1.525(5) O(5)-C(51) 1.373(6) O(8)-C(64) 1.390(6) O(5)-C(52) 1.403(6) O(8)-C(65) 1.435(7) N(2)-C(19) 1.405(5) C(12)-C(13) 1.362(6) N(2)-C(10) 1.458(5) C(12)-C(17) 1.411(6) N(2)-C(9) 1.484(5) C(12)-C(10) 1.537(5) O(1)-C(17) 1.369(6) O(6)-C(66) 1.229(6) O(1)-C(18) 1.412(6) C(44)-C(45) 1.531(6) O(3)-C(32) 1.346(6) C(7)-C(11) 1.521(6) O(3)-C(33) 1.452(6) C(10)-C(11) 1.536(5) O(4)-C(30) 1.367(6) N(3)-C(40) 1.421(6) O(4)-C(31) 1.441(5) N(3)-H(3) 0.86(2) O(7)-C(66) 1.343(6) C(9)-C(25) 1.558(6) O(7)-C(67) 1.483(7) C(19)-C(24) 1.392(6) N(1)-C(7) 1.371(6) C(19)-C(20) 1.405(6) N(1)-C(6) 1.418(6) C(47)-C(48) 1.403(6) N(1)-H(1) 0.85(5) C(53)-C(54) 1.394(6) C(41)-C(42) 1.353(6) C(53)-C(58) 1.411(6) C(41)-N(3) 1.377(6) C(25)-C(26) 1.369(6) C(41)-C(45) 1.502(6) C(25)-C(30) 1.400(6) O(2)-C(32) 1.219(5) C(40)-C(35) 1.371(7) C(8)-C(7) 1.354(6) C(40)-C(39) 1.387(6) C(8)-C(32) 1.452(6) C(56)-C(57) 1.373(8) C(8)-C(9) 1.517(6) C(56)-C(55) 1.384(7) S34

35 C(55)-C(54) 1.390(7) C(33)-C(34) 1.478(9) C(30)-C(29) 1.416(7) C(5)-C(4) 1.350(8) C(57)-C(58) 1.368(6) C(37)-C(38) 1.351(9) C(20)-C(21) 1.367(7) C(28)-C(27) 1.333(7) C(26)-C(27) 1.406(7) C(21)-C(22) 1.403(9) C(6)-C(1) 1.380(7) C(60)-C(61) 1.384(6) C(6)-C(5) 1.398(6) C(1)-C(2) 1.381(8) C(42)-C(66) 1.441(6) C(4)-C(3) 1.361(8) C(42)-C(43) 1.513(6) C(62)-C(61) 1.343(9) C(51)-C(50) 1.417(6) C(67)-C(68) 1.442(11) C(16)-C(17) 1.382(6) C(3)-C(2) 1.328(7) C(16)-C(15) 1.395(8) C(53)-N(4)-C(43) 120.7(3) C(23)-C(22) 1.346(8) C(53)-N(4)-C(44) 119.2(3) C(23)-C(24) 1.388(6) C(43)-N(4)-C(44) 118.4(3) C(14)-C(15) 1.367(8) C(51)-O(5)-C(52) 119.4(4) C(14)-C(13) 1.400(6) C(19)-N(2)-C(10) 120.1(3) C(29)-C(28) 1.389(8) C(19)-N(2)-C(9) 120.0(3) C(59)-C(64) 1.366(7) C(10)-N(2)-C(9) 118.3(3) C(59)-C(60) 1.399(6) C(17)-O(1)-C(18) 116.6(4) C(59)-C(43) 1.552(6) C(32)-O(3)-C(33) 115.3(4) C(49)-C(48) 1.351(8) C(30)-O(4)-C(31) 117.5(4) C(49)-C(50) 1.377(7) C(66)-O(7)-C(67) 118.2(5) C(39)-C(38) 1.389(8) C(7)-N(1)-C(6) 124.7(4) C(35)-C(36) 1.370(8) C(42)-C(41)-N(3) 124.8(4) C(63)-C(62) 1.385(8) C(42)-C(41)-C(45) 116.1(4) C(63)-C(64) 1.407(7) N(3)-C(41)-C(45) 119.1(4) C(36)-C(37) 1.407(9) C(7)-C(8)-C(32) 121.0(4) S35

36 C(7)-C(8)-C(9) 118.0(4) C(24)-C(19)-N(2) 121.5(4) C(32)-C(8)-C(9) 120.7(4) C(20)-C(19)-N(2) 120.8(4) C(51)-C(46)-C(47) 118.7(4) C(46)-C(47)-C(48) 120.0(5) C(51)-C(46)-C(44) 119.1(4) C(54)-C(53)-N(4) 121.9(4) C(47)-C(46)-C(44) 122.1(4) C(54)-C(53)-C(58) 116.5(4) C(64)-O(8)-C(65) 117.2(5) N(4)-C(53)-C(58) 121.5(4) C(13)-C(12)-C(17) 118.4(4) C(26)-C(25)-C(30) 117.7(4) C(13)-C(12)-C(10) 122.7(4) C(26)-C(25)-C(9) 122.6(4) C(17)-C(12)-C(10) 118.9(4) C(30)-C(25)-C(9) 119.6(4) N(4)-C(44)-C(46) 112.7(3) C(35)-C(40)-C(39) 118.7(5) N(4)-C(44)-C(45) 110.2(3) C(35)-C(40)-N(3) 120.8(4) C(46)-C(44)-C(45) 110.7(3) C(39)-C(40)-N(3) 120.5(5) C(41)-C(45)-C(44) 110.4(4) C(57)-C(56)-C(55) 118.1(5) C(8)-C(7)-N(1) 124.2(4) C(56)-C(55)-C(54) 120.9(5) C(8)-C(7)-C(11) 115.9(4) O(4)-C(30)-C(25) 115.3(4) N(1)-C(7)-C(11) 119.9(4) O(4)-C(30)-C(29) 125.0(5) N(2)-C(10)-C(12) 112.0(3) C(25)-C(30)-C(29) 119.8(5) N(2)-C(10)-C(11) 111.2(3) C(58)-C(57)-C(56) 121.9(5) C(12)-C(10)-C(11) 110.6(3) C(21)-C(20)-C(19) 120.7(5) N(2)-C(10)-H(10) C(25)-C(26)-C(27) 122.9(5) C(12)-C(10)-H(10) C(1)-C(6)-C(5) 117.1(5) C(11)-C(10)-H(10) C(1)-C(6)-N(1) 121.4(4) C(41)-N(3)-C(40) 125.2(4) C(5)-C(6)-N(1) 121.5(4) N(2)-C(9)-C(8) 110.2(3) C(41)-C(42)-C(66) 120.6(4) N(2)-C(9)-C(25) 110.6(3) C(41)-C(42)-C(43) 117.6(4) C(8)-C(9)-C(25) 114.5(3) C(66)-C(42)-C(43) 121.4(5) C(24)-C(19)-C(20) 117.8(4) O(2)-C(32)-O(3) 121.5(5) S36

37 O(2)-C(32)-C(8) 123.9(5) O(6)-C(66)-C(42) 125.1(6) O(3)-C(32)-C(8) 114.6(4) O(7)-C(66)-C(42) 114.3(5) O(5)-C(51)-C(46) 115.8(4) C(57)-C(58)-C(53) 121.3(5) O(5)-C(51)-C(50) 123.7(5) N(4)-C(43)-C(42) 110.3(3) C(46)-C(51)-C(50) 120.5(5) N(4)-C(43)-C(59) 112.0(3) C(17)-C(16)-C(15) 119.7(5) C(42)-C(43)-C(59) 114.0(4) C(7)-C(11)-C(10) 109.4(3) C(38)-C(37)-C(36) 118.5(6) C(22)-C(23)-C(24) 119.2(6) C(49)-C(50)-C(51) 119.7(5) C(15)-C(14)-C(13) 119.1(5) C(59)-C(64)-O(8) 114.8(4) C(12)-C(13)-C(14) 121.9(5) C(59)-C(64)-C(63) 122.5(5) O(1)-C(17)-C(16) 124.8(5) O(8)-C(64)-C(63) 122.6(5) O(1)-C(17)-C(12) 114.8(4) C(27)-C(28)-C(29) 121.7(5) C(16)-C(17)-C(12) 120.4(5) C(55)-C(54)-C(53) 121.3(5) C(23)-C(24)-C(19) 121.6(5) C(20)-C(21)-C(22) 119.5(5) C(28)-C(29)-C(30) 119.2(5) C(23)-C(22)-C(21) 121.2(5) C(64)-C(59)-C(60) 117.5(4) C(14)-C(15)-C(16) 120.5(5) C(64)-C(59)-C(43) 121.4(4) C(61)-C(60)-C(59) 120.7(5) C(60)-C(59)-C(43) 121.1(4) C(6)-C(1)-C(2) 119.8(5) C(48)-C(49)-C(50) 119.7(5) C(5)-C(4)-C(3) 120.4(5) C(40)-C(39)-C(38) 119.6(6) C(61)-C(62)-C(63) 121.6(5) C(36)-C(35)-C(40) 121.6(5) C(28)-C(27)-C(26) 118.7(6) C(49)-C(48)-C(47) 121.3(5) C(37)-C(38)-C(39) 121.8(6) C(62)-C(63)-C(64) 117.3(5) C(68)-C(67)-O(7) 107.6(7) C(35)-C(36)-C(37) 119.7(6) C(2)-C(3)-C(4) 119.7(6) O(3)-C(33)-C(34) 106.7(5) C(3)-C(2)-C(1) 121.7(6) C(4)-C(5)-C(6) 121.3(5) C(62)-C(61)-C(60) 120.4(6) O(6)-C(66)-O(7) 120.5(5) S37

38 1. Khan, A. T.; Parvin, T.; Choudhury, L. H. Effects of Substituents in the β-position of 1,3-Dicarbonyl Compounds in Bromodimethylsulfonium Bromide-Catalyzed Multicomponent Reactions: A Facile Access to Functionalized Piperidines. J. Org. Chem. 2008, 73, Abbasi, M. Design, Preparation and Characterization of A New Ionic Liquid, 1,3-Disulfonic Acid Benzimidazolium Chloride, as an Efficient and Recyclable Catalyst for the Synthesis of Tetrahydropyridine under Solventfree Conditions. RSC Adv. 2015, 5, Safaei-Ghomi, J.; Ziarati, A.. An efficient FeCl 3 /SiO 2 NPs as a Reusable Heterogeneous Catalyzed Five-Component Reactions of Tetrahydropyridines under Mild Conditions. J. Iran Chem. Soc. 2013, 10, Brahmachari, G.; Das, S. Bismuth Nitrate-Catalyzed Multicomponent Reaction for Efficient and One-Pot Synthesis of Densely Functionalized Piperidine Scaffolds at Room Temperature.Tetrahedron Lett. 2012, 53, Javidan, A.; Ziarati, A.; Safaei-Ghomi, J. Simultaneous Sonication Assistance for the Synthesis of Tetrahydropyridines and its Efficient Catalyst ZrP 2 O 7 Nanoparticles. Ultrason Sonochem. 2014, 21, Aeluri, R.; Alla, M.; Bommena, V. R.; Murthy, R.; Jain, N. Synthesis and Antiproliferative Activity of Polysubstituted Tetrahydropyridine and Piperidin-4-one-3-carboxylate Derivatives. Asian J. Org. Chem. 2012, 1, Xu, J.; Zhuang, R.; Bao, L.; Tang, G.; Zhao, Y. KOH-Mediated Transition-Metal-Free Synthesis of Imines from Alcohols and Amines. Green Chem. 2012, 14, Rout, L.; Kumar, A.; Dhaka, R. S.; Dash, P. Bimetallic Ag-Cu Alloy Nanoparticles as Highly Active Catalyst for Enamination of 1, 3 dicarbonyl Compounds. RSC Adv. 2016, 6, S38