Three-Component Solvent-Free Synthesis of Highly Substituted Bicyclic Pyridines Containing a Ring-Junction Nitrogen. Supporting Information
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- Λυσιστράτος Ανδρεάδης
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1 Three-Component Solvent-Free Synthesis of Highly Substituted Bicyclic Pyridines Containing a Ring-Junction itrogen Shengjiao Yan, Yulan Chen, Lin Liu, engqin He, Jun Lin * Key Laboratory of Medicinal Chemistry for atural Resource (Yunnan University), Ministry of Education, School of Chemical Science and Technology, Yunnan University, Kunming, , P. R. China Supporting Information Table of Contents General Information...3 General Procedure for the Preparation of Bicyclic Pyridines 4 via ne-pot Three-component Reactions...3 Spectroscopic Data of Bicyclic Pyridines General Procedure for the Preparation of Bicyclic Pyridinone (-imine) 6 via ne-pot Three-component Reactions...13 Spectroscopic Data of Bicyclic Pyridinone (-imine) Anti-cancer activities of compounds X-ray Structure and Data of 4m H MR and 13 C MR Spectra for Bicyclic Pyridines 4, Figure 1. Figure 2. Figure 3. Figure 4. Figure 5. Figure 6. Figure 7. Figure 8. Figure 9. Figure 10. Figure 11. Figure 12. Figure 13. Figure H MR (500 MHz, CDCl 3 ) spectra of compound 4a C MR (125 MHz, CDCl 3 ) spectra of compound 4a H MR (500 MHz, CDCl 3 ) spectra of compound 4b C MR (125 MHz, CDCl 3 ) spectra of compound 4b H MR (500 MHz, CDCl 3 ) spectra of compound 4c C MR (125 MHz, CDCl 3 ) spectra of compound 4c H MR (500 MHz, CDCl 3 ) spectra of compound 4d C MR (125 MHz, CDCl 3 ) spectra of compound 4d H MR (500 MHz, CDCl 3 ) spectra of compound 4e C MR (125 MHz, CDCl 3 ) spectra of compound 4e H MR (500 MHz, CDCl 3 ) spectra of compound 4f C MR (125 MHz, CDCl 3 ) spectra of compound 4f H MR (500 MHz, CDCl 3 ) spectra of compound 4g C MR (125 MHz, CDCl 3 ) spectra of compound 4g...39 * Corresponding author. Tel.: ; fax: ; linjun@ynu.edu.cn. These authors contributed equally to this paper S1
2 Figure H MR (500 MHz, CDCl 3 ) spectra of compound 4h...40 Figure C MR (125 MHz, CDCl 3 ) spectra of compound 4h...41 Figure H MR (500 MHz, CDCl 3 ) spectra of compound 4i...42 Figure C MR (125 MHz, CDCl 3 ) spectra of compound 4i...43 Figure H MR (500 MHz, CDCl 3 ) spectra of compound 4j...44 Figure C MR (125 MHz, CDCl 3 ) spectra of compound 4j...45 Figure H MR (500 MHz, CDCl 3 ) spectra of compound 4k...46 Figure C MR (125 MHz, CDCl 3 ) spectra of compound 4k...47 Figure H MR (500 MHz, CDCl 3 ) spectra of compound 4l...48 Figure C MR (125 MHz, CDCl 3 ) spectra of compound 4l...49 Figure H MR (500 MHz, CDCl 3 ) spectra of compound 4m...50 Figure C MR (125 MHz, CDCl 3 ) spectra of compound 4m...51 Figure H MR (500 MHz, CDCl 3 ) spectra of compound 4n...52 Figure C MR (125 MHz, CDCl 3 ) spectra of compound 4n...53 Figure H MR (500 MHz, CDCl 3 ) spectra of compound 4o...54 Figure C MR (125 MHz, CDCl 3 ) spectra of compound 4o...55 Figure H MR (500 MHz, CDCl 3 ) spectra of compound 4p...56 Figure C MR (125 MHz, CDCl 3 ) spectra of compound 4p...57 Figure H MR (500 MHz, CDCl 3 ) spectra of compound 4q...58 Figure C MR (125 MHz, CDCl 3 ) spectra of compound 4q...59 Figure H MR (500 MHz, CDCl 3 ) spectra of compound 4r...60 Figure C MR (125 MHz, CDCl 3 ) spectra of compound 4r...61 Figure H MR (500 MHz, CDCl 3 ) spectra of compound 4s...62 Figure C MR (125 MHz, CDCl 3 ) spectra of compound 4s...63 Figure H MR (500 MHz, CDCl 3 ) spectra of compound 4t...64 Figure C MR (125 MHz, CDCl 3 ) spectra of compound 4t...65 Figure H MR (500 MHz, CDCl 3 ) spectra of compound 4u...66 Figure C MR (125 MHz, CDCl 3 ) spectra of compound 4u...67 Figure H MR (500 MHz, CDCl 3 ) spectra of compound 4v...68 Figure C MR (125 MHz, CDCl 3 ) spectra of compound 4v...69 Figure H MR (500 MHz, CDCl 3 ) spectra of compound 6a...70 Figure C MR (125 MHz, CDCl 3 ) spectra of compound 6a...71 Figure H MR (500 MHz, CH 3 D+DMS-d 6 ) spectra of compound 6b...72 Figure C MR (125 MHz, CH 3 D+DMS-d 6 ) spectra of compound 6b...73 Figure H MR (500 MHz, DMS-d 6 ) spectra of compound 6c...74 Figure C MR (125 MHz, DMS-d 6 ) spectra of compound 6c...75 Figure H MR (500 MHz, DMS-d 6 ) spectra of compound 6d...76 Figure C MR (125 MHz, DMS-d 6 ) spectra of compound 6d...77 Figure H MR (500 MHz, DMS-d 6 ) spectra of compound 6e...78 Figure C MR (125 MHz, DMS-d 6 ) spectra of compound 6e...79 Figure H MR (500 MHz, DMS-d 6 ) spectra of compound 6f...80 Figure C MR (125 MHz, DMS-d 6 ) spectra of compound 6f...81 References and otes...82 S2
3 General Information All compounds were fully characterized by spectroscopic data. The MR spectra were recorded on a Bruker DRX500 ( 1 H: 500 MHz, 13 C: 125 MHz), chemical shifts (δ) are expressed in ppm, and J values are given in Hz, CDCl 3 and DMS-d 6 were used as solvent. IR spectra were recorded on a FT-IR Thermo icolet Avatar 360 using KBr pellet. The reactions were monitored by thin layer chromatography (TLC) using silica gel GF 254. The melting points were determined on XT-4A melting point apparatus and are uncorrected. HRMs were performed on a Agllent LC/Msd TF instrument. All chemicals and solvents were used as received without further purification unless otherwise stated. Column chromatography was performed on silica gel ( mesh). The raw materials 1a~1w were synthesized according to the literature. 1~4 4,4,4-trifluoro-3-oxo-butanoate 3a is lower acute toxicity (LD 50 =1260 mg/kg) in the mice tested according to the literature. 5 Safety phrases of 3a is S61 (Avoid release to the environment) in the safety description; Diethyl malonate 5a is lower acute toxicity (RL-RAT LD 50 =15000 mg/kg, RL-MUS LD 50 =6400mg/kg); Safety phrases of Ethyl 2-cyanoacetate 5b is S in the safety description. n General Procedure for the Preparation of Bicyclic Pyridines 4 via ne-pot Three-component Reactions Z H 1 R HC(Et) 3 2 EtC 3 CF 3 reflux Solvent-free n Z H CEt n = 1, 2, 3; Z = H,, S R = CEt, 2, MeC, ArC 4 R HKAs 1 (2.5mmol), triethoxymethane 2 (3 mmol) and ethyl 4,4,4-trifluoro-3 -oxobutanoate 3 (3mmol) were charged into a 25 ml round-bottom flask and the mixture was refluxed. The resulting solution was stirred for h until the HKAs 1 were completely consumed. The mixture was diluted with EtAc (50 ml x 2) and quenched with water (50 ml). The organic layer was dried by a 2 S 4, concentrated, and purified by flash column chromatography (Petro/AcEt = 6/1) to afford product 4 with 78-94% yield. S3
4 Spectroscopic Data of Bicyclic Pyridines 4 Ethyl 5-hydroxy-8-nitro-5-(trifluoromethyl)-1,2,3,5-tetrahydroimidazo[1,2-a] pyridine-6-carboxylate (4a) H 2 H CEt Yellow solid; Mp C; IR (KBr): 3358, 3086, 1675, 1597, 1460, 1385, 1207, 1078, 763 cm -1 ; 1 H MR (500 MHz, CDCl 3 ): δ = 1.35 (t, J = 7.1 Hz, 3H, CH 3 ), (m, 4H, CH 2 CH 2 ), (m, 2H, CH 2 ), 7.74 (s, 1H, CH), 8.32 (br, 1H, H), 8.36 (br, 1H, H); 13 C HMR (125 MHz, CDCl 3 ): δ = 14.5, 43.9, 44.8, 62.2, 84.5 (d, J = 35.0 Hz), 101.5, 108.9, (d, J = Hz), 135.6, 155.2, 168.2; HRMS (TF ES + ): m/z calcd for C 11 H 13 F [(M+H) + ], ; found, Ethyl 8-acetyl-5-hydroxy-5-(trifluoromethyl)-1,2,3,5-tetrahydroimidazo[1,2-a] pyridine-6-carboxylate (4b) H H Me CEt White solid; Mp C; IR (KBr): 3347, 2990, 1664, 1586, 1497, 1388, 1210, 1114 cm -1 ; 1 H MR (500 MHz, CDCl 3 ): δ = 1.35 (t, J = 7.1 Hz, 3H, CH 3 ), 2.25 (s, 3H, CCH 3 ), (m, 4H, CH 2 CH 2 ), (m, 2H, CH 2 ), 7.81 (s, 1H, CH), 7.95 (br, 1H, H), 9.05 (br, 1H, H); 13 C HMR (125 MHz, CDCl 3 ): δ = 14.7, 25.4, 43.6, 43.6, 61.2, 84.3 (d, J = 32.5 Hz), 92.4, 96.9, (d, J = Hz), 141.9, 159.3, 168.8, 192.6; HRMS (TF ES + ): m/z C 13 H 16 F [(M+H) + ], ; found, Ethyl 8-benzoyl-5-hydroxy-5-(trifluoromethyl)-1,2,3,5-tetrahydroimidazo[1,2-a] pyridine-6-carboxylate (4c) S4
5 H H CEt White solid; Mp C; IR (KBr): 3294, 2987, 1662, 1591, 1499, 1089, 1025, 752, 706 cm -1 ; 1 H MR (500 MHz, CDCl 3 ): δ = 1.21 (t, J = 7.0 Hz, 3H, CH 3 ), (m, 4H, CH 2 CH 2 ), (m, 2H, CH 2 ), (m, 5H, PhH), 7.84 (s, 1H, CH), 7.92 (br, 1H, H), 9.33 (br, 1H, H); 13 C HMR (125 MHz, CDCl 3 ): δ = 14.5, 43.8, 44.2, 61.2, 84.2 (d, J = 33.8 Hz), 91.7, 97.3, (d, J = Hz), 128.6, 128.7, 131.0, 139.7, 143.6, 160.4, 168.8, 191.0; HRMS (TF ES + ): m/z calcd for C 18 H 18 F [(M+H) + ], ; found, Ethyl 5-hydroxy-8-(4-methylbenzoyl)-5-(trifluoromethyl)-1,2,3,5-tetrahydroimidazo[1,2-a]pyridine-6-carboxylate (4d) H H CEt White solid; Mp C; IR (KBr): 3322, 2977, 1656, 1582, 1498, 1401, 1309, 1083, 766 cm -1 ; 1 H MR (500 MHz, CDCl 3 ): δ = 1.25 (t, J = 7.0 Hz, 3H, CH 3 ), 2.44 (s, 3H, ArCH 3 ), (m, 4H, CH 2 CH 2 ), (m, 2H, CH 2 ), 7.27 (t, J = 7.6 Hz, 2H, ArH), 7.47 (d, J = 7.6 Hz, 2H, ArH), 7.90 (s, 1H, CH), 7.97 (br, 1H, H), 9.34 (br, 1H, H); 13 C HMR (125 MHz, CDCl 3 ): δ = 14.6, 21.9, 43.8, 43.8, 61.2, 84.2 (d, J = 33.8 Hz), 91.7, 97.1, (d, J = Hz), 128.9, 129.3, 136.9, 141.4, 143.7, 160.5, 168.9, 191.0; HRMS (TF ES + ): m/z calcd for C 19 H 20 F [(M+H) + ], ; found, Me Ethyl 5-hydroxy-8-(4-methoxybenzoyl)-5-(trifluoromethyl)-1,2,3,5-tetrahydroimidazo[1,2-a]pyridine-6-carboxylate (4e) H Me H CEt White solid; Mp C; IR (KBr): 3288, 2987, 1654, 1594, 1400, 1253, 1170, 1088, 843 cm -1 ; 1 H MR (500 MHz, CDCl 3 ): δ = 1.24 (t, J = 7.1 Hz, 3H, CH 3 ), 3.89 (s, 3H, CH 3 ), (m, 4H, CH 2 CH 2 ), 4.19 (q, J = 7.1 Hz, 2H, CH 2 ), 6.95 (d, J = 8.5 Hz, 2H, ArH), 7.54 (d, J = 8.5 Hz, 2H, ArH), 7.88 (s, 1H, CH), 7.97 (br, S5
6 1H, H), 9.28 (br, 1H, H); 13 C HMR (125 MHz, CDCl 3 ): δ = 14.6, 43.5, 43.8, 55.8, 61.1, 84.2 (d, J = 33.8 Hz), 91.6, 96.8, 113.9, (d, J = Hz), 130.8, 132.2, 143.8, 160.5, 162.1, 168.9, 190.3; HRMS (TF ES + ): m/z calcd for C 19 H 20 F [(M+H) + ], ; found, Diethyl 5-hydroxy-5-(trifluoromethyl)-1,2,3,5-tetrahydroimidazo[1,2-a]pyridine -6,8-dicarboxylate (4f) H H CEt CEt White solid; Mp C; IR (KBr): 3398, 3308, 2988, 1638, 1575, 1411, 1332, 1216, 768 cm -1 ; 1 H MR (500 MHz, CDCl 3 ): δ = (m, 6H, CH 3 ), (m, 4H, CH 2 CH 2 ), (m, 4H, CH 2 ), 7.83 (s, 1H, CH), 7.91 (br, 1H, H), 8.02 (br, 1H, H); 13 C HMR (125 MHz, CDCl 3 ): δ = 14.5, 14.7, 43.5, 44.1, 60.0, 61.0, 80.5, 84.7 (q, J = 33.8 Hz), 96.2, (q, J = Hz), 141.5, 159.4, 166.8, 169.0; HRMS (TF ES + ): m/z calcd for C 14 H 18 F [(M+H) + ], ; found, Ethyl 6-hydroxy-9-nitro-6-(trifluoromethyl)-2,3,4,6-tetrahydro-1H-pyrido [1,2-a]pyrimidine-7-carboxylate (4g) H 2 H CEt Yellow solid; Mp C; IR (KBr): 3182, 2982, 1668, 1607, 1539, 1474, 1370, 1018, 752 cm -1 ; 1 H MR (500 MHz, CDCl 3 ): δ = 1.31 (t, J = 7.2 Hz, 3H, CH 3 ), (m, 1H, CH 2 ), (m, 1H, CH 2 ), (m, 2H, CH 2 ), (m, 1H, CH 2 ), (m, 1H, CH 2 ), (m, 2H, CH 2 ), 8.40 (s, 1H, CH), 8.42 (br, 1H, H), (br, 1H, H); 13 C HMR (125 MHz, CDCl 3 ): δ = 14.5, 19.7, 39.7, 40.5, 62.2, 84.4 (q, J = 33.8 Hz), 100.2, 111.3, (q, J = Hz), 135.9, 151.8, 168.5; HRMS (TF ES + ): m/z calcd for C 12 H 15 F [(M+H) + ], ; found, Ethyl 9-(4-chlorobenzoyl)-6-hydroxy-6-(trifluoromethyl)-2,3,4,6-tetrahydro- 1H-pyrido[1,2-a]pyrimidine-7-carboxylate (4h) S6
7 H Cl H CEt Yellow solid; Mp C; IR (KBr): 3429, 2979, 1657, 1595, 1508, 1239, 1174, 1099, 816 cm -1 ; 1 H MR (500 MHz, CDCl 3 ): δ = 1.21 (t, J = 6.9 Hz, 3H, CH 3 ), (m, 2H, CH 2 ), 3.40 (m, 1H, CH 2 ), 3.54 (d, m, 2H, CH 2 ), 3.94 (m, 1H, CH 2 ), ), 4.17 (q, J = 6.9 Hz, 2H, CH 2 ), 7.4 (d, J = 8.1 Hz, 2H, ArH), 7.43 (d, J = 8.1 Hz, 2H, ArH), 7.70 (s, 1H, CH), 8.63 (br, 1H, H), (br, 1H, H); 13 C HMR (125 MHz, CDCl 3 ): δ = 14.6, 20.1, 39.2, 39.9, 61.2, 84.0 (d, J = 32.5 Hz), 94.1, 95.5, (d, J = Hz), 128.7, 130.5, 136.7, 139.0, 143.7, 156.5, 169.0, 190.2; HRMS (TF ES + ): m/z calcd for C 19 H 19 ClF [(M+H) + ], ; found, Ethyl 9-benzoyl-6-hydroxy-6-(trifluoromethyl)-2,3,4,6-tetrahydro-1H-pyrido [1,2-a]pyrimidine-7-carboxylate (4i) H H CEt Yellow solid; Mp C; IR (KBr): 3427, 2983, 1645, 1598, 1509, 1395, 1241, 1181, 751, 703 cm -1 ; 1 H MR (500 MHz, CDCl 3 ): δ = 1.20 (t, J = 7.0 Hz, 3H, CH 3 ), (m, 2H, CH 2 ), 3.41 (m, 1H, CH 2 ), 3.55 (m, 2H, CH 2 ), (m, 1H, CH 2 ), 4.16 (q, J = 7.0 Hz, 2H, CH 2 ), (m, 5H, PhH), 7.78 (s, 1H, CH), 8.66 (br, 1H, H), (br, 1H, H); 13 C HMR (125 MHz, CDCl 3 ): δ = 14.5, 20.2, 39.2, 39.9, 61.1, 84.1 (d, J = 33.8 Hz), 94.2, 95.0, (d, J = Hz), 128.4, 129.0, 130.6, 140.7, 144.3, 156.6, 169.1, 191.8; HRMS (TF ES + ): m/z calcd for C 19 H 20 F [(M+H) + ], ; found, Ethyl 6-hydroxy-9-(4-methylbenzoyl)-6-(trifluoromethyl)-2,3,4,6-tetrahydro- 1H-pyrido[1,2-a]pyrimidine-7-carboxylate (4j) H Me H CEt Yellow solid; Mp C; IR (KBr): 3374, 2984, 1651, 1601, 1503, 1373, 1236, 1176, 776 cm -1 ; 1 H MR (500 MHz, CDCl 3 ): δ = 1.20 (t, J = 7.1 Hz, 3H, CH 3 ), S7
8 (m, 2H, CH 2 ), 2.42 (s, 3H, ArCH 3 ), (m, 3H, CH 2 CH 2 ), 4.16 (q, J = 7.1 Hz, 2H, CH 2 ), 7.23 (d, J = 7.8 Hz, 2H, ArH), 7.40 (d, J = 7.8 Hz, 2H, ArH), 7.81 (s, 1H, CH), 8.68 (br, 1H, H), (br, 1H, H); 13 C HMR (125 MHz, CDCl 3 ): δ = 14.6, 20.2, 21.9, 39.2, 39.9, 61.1, 84.1 (q, J = 32.5 Hz), 94.2, 94.7, (q, J = Hz), 129.1, 129.2, 137.9, 141.0, 144.5, 156.6, 169.1, 191.7; HRMS (TF ES + ): m/z calcd for C 20 H 22 F [(M+H) + ], ; found, Ethyl 6-hydroxy-9-(4-methoxybenzoyl)-6-(trifluoromethyl)-2,3,4,6-tetrahydro- 1H-pyrido[1,2-a]pyrimidine-7-carboxylate (4k) H Me H CEt Yellow solid; Mp: C; IR (KBr): 3428, 2980, 1645, 1597, 1506, 1372, 1249, 1173, 837 cm -1 ; 1 H MR (500 MHz, CDCl 3 ): δ = 1.20 (m, 3H, CH 3 ), (m, 2H, CH 2 ), (m, 3H, CH 2 CH 2 ), 3.87 (s, 3H, CH 3 ), 3.89 (m, 1H, CH 2 ), 4.15 (m, 2H, CH 2 ), 6.95 (d, J = 6.4 Hz, 2H, ArH), 7.49 (d, J = 6.4 Hz, 2H, ArH), 7.83 (s, 1H, CH), 8.71 (br, 1H, H), (br, 1H, H); 13 C HMR (125 MHz, CDCl 3 ): δ = 14.6, 20.2, 39.2, 39.9, 55.8, 61.0, 84.1 (d, J = 32.5 Hz), 94.1, 94.4, 113.7, (d, J = Hz), 131.1, 133.2, , 156.5, 161.9, 169.1, 191.1; HRMS (TF ES + ): m/z calcd for C 20 H 22 F [(M+H) + ], ; found, Ethyl 10-(4-chlorobenzoyl)-7-hydroxy-7-(trifluoromethyl)-1,2,3,4,5,7,8,9- octahydropyrido[1,2-a][1,3]diazepine-8-carboxylate (4l) H Cl H CEt White solid; Mp C; IR (KBr): 3421, 2946, 1654, 1589, 1367, 1236, 1167, 1097, 807 cm -1 : 1 H MR (500 MHz, CDCl 3 ): δ = 1.21 (t, J = 7.0 Hz, 3H, CH 3 ), (m, 2H, CH 2 ), 2.02 (m, 2H, CH 2 ), 3.49 (m, 2H, CH 2 ), 3.68 (m, 1H, CH 2 ), (m, 2H, CH 2 ), (m, 1H, CH 2 ), (m, 4H, ArH), 7.66 (s, 1H, CH), 9.05 (br, 1H, H), (br, 1H, H); 13 C HMR (125 MHz, CDCl 3 ): δ = 14.6, 25.4, 25.5, 43.5, 45.2, 61.4, 84.3 (d, J = 32.5 Hz), 96.4, 96.7, (d, J = Hz), 128.7, 130.7, 137.0, 139.1, 144.0, 163.1, 169.1, S8
9 190.6; HRMS (TF ES + ): m/z calcd for C 20 H 21 ClF [(M+H) + ], ; found, Ethyl 10-benzoyl-7-hydroxy-7-(trifluoromethyl)-1,2,3,4,5,7,8,9-octahydropyrido [1,2-a][1,3]diazepine-8-carboxylate (4m) H H CEt White solid; Mp 119 C; IR (KBr): 3433, 2969, 1647, 1578, 1496, 1364, 1096, 759, 699 cm -1 ; 1 H MR (500 MHz, CDCl 3 ): δ = 1.18 (t, J = 7.2 Hz, 3H, CH 3 ), (m, 2H, CH 2 ), (m, 2H, CH 2 ), (m, 2H, CH 2 ), 3.67 (m, 1H, CH 2 ), (m, 2H, CH 2 ), 4.47 (m, 1H, CH 2 ), (m, 5H, PhH), 7.73 (s, 1H, CH), 9.06 (br, 1H, H), (br, 1H, H); 13 C HMR (125 MHz, CDCl 3 ): δ = 14.5, 25.4, 25.5, 43.4, 45.2, 61.2,84.3 (d, J = 32.5 Hz), 96.2, 96.6, (d, J = Hz), 128.4, 129.2, 130.9, 140.6, 144.6, 163.2, 169.3, 192.2; HRMS (TF ES + ): m/z calcd for C 20 H 22 F [(M+H) + ], ; found, Ethyl 7-hydroxy-10-(4-methylbenzoyl)-7-(trifluoromethyl)-1,2,3,4,5,7,8,9- octahydropyrido[1,2-a][1,3]diazepine-8-carboxylate (4n) H Me H CEt White solid; Mp C; IR (KBr): 3427, 2933, 1650, 1589, 1369, 1236, 1169, 1098, 821 cm -1 ; 1 H MR (500 MHz, CDCl 3 ): δ = 1.20 (t, J = 6.9 Hz, 3H, CH 3 ), (m, 2H, CH 2 ), 2.00 (m, 2H, CH 2 ), 2.41 (s, 3H, ArCH 3 ), (m, 2H, CH 2 ), 3.67 (m, 1H, CH 2 ), 4.16 (t, J = 6.9 Hz, 2H, CH 2 ), 4.48 (m, 1H, CH 2 ), 7.22 (d, J = 7.5 Hz, 2H, ArH), 7.40 (d, J = 7.5 Hz, 2H, ArH), 7.76 (s, 1H, CH), 9.09 (br, 1H, H), (br, 1H, H); 13 C HMR (125 MHz, CDCl 3 ): δ = 14.6, 21.9, 25.4, 25.6, 43.5, 45.3, 61.2, 84.4 (q, J = 33.8 Hz), 96.0, 96.6, (q, J = Hz), 129.1, 129.4, 137.9, 141.3, 144.7, 163.3, 169.3, 192.2; HRMS (TF ES + ): m/z calcd for C 21 H 24 F [(M+H) + ], ; found, Ethyl 7-hydroxy-10-(4-methoxybenzoyl)-7-(trifluoromethyl)-1,2,3,4,5,7,8,9- octahydropyrido[1,2-a][1,3]diazepine-8-carboxylate (4o) S9
10 H Me H CEt White solid; Mp C; IR (KBr): 3176, 2945, 1652, 1595, 1494, 1366, 1164, 1031, 836 cm -1 ; 1 H MR (500 MHz, CDCl 3 ): δ = 1.21 (t, J = 7.0 Hz, 3H, CH 3 ), (m, 2H, CH 2 ), 1.99 (m, 2H, CH 2 ), 3.45 (m, 2H, CH 2 ), 3.67 (m, 1H, CH 2 ), 3.86 (s, 3H, CH 3 ), 4.17 (q, J = 7.0 Hz, 2H, CH 2 ), (m, 1H, CH 2 ), 6.93 (d, J = 8.3 Hz, 2H, ArH), 7.49 (d, J = 8.3 Hz, 2H, ArH), 7.77 (s, 1H, CH), 9.11 (br, 1H, H), (br, 1H, H); 13 C HMR (125 MHz, CDCl 3 ): δ = 14.6, 25.4, 25.6, 43.4, 45.3, 55.8, 61.2, 84.4 (d, J = 32.5 Hz), 95.7, 96.6, 113.7, (d, J = Hz), 131.4, 133.2, 144.8, 162.1, 163.2, 169.3, 191.5; HRMS (TF ES + ): m/z calcd for C 21 H 24 F [(M+H) + ], ; found, Ethyl 8-(4-chlorobenzoyl)-5-hydroxy-5-(trifluoromethyl)-3,5-dihydro-2Hoxazolo[3,2-a]pyridine-6-carboxylate (4p) Cl H CEt White solid; Mp: C; IR (KBr): 3178, 2980, 1663, 1600, 1529, 1345, 1262, 1179, 843 cm -1 ; 1 H MR (500 MHz, CDCl 3 ): δ = 1.32 (t, J = 7.2 Hz, 3H, CH 3 ), (m, 2H, CH 2 ), (m, 2H, CH 2 ), (m, 2H, CH 2 ), 7.37 (d, J = 8.3 Hz, 2H, ArH), 7.49 (d, J = 8.3 Hz, 2H, ArH), 7.94 (s, 1H, CH), 8.13 (br, 1H, H); 13 C HMR (125 MHz, CDCl 3 ): δ = 14.6, 43.5, 61.9, 70.3, 85.8 (q, J = 33.8 Hz), 91.2, 99.9, (q, J = Hz), 128.6, 130.2, 137.6, 139.0, 142.7, 163.9, 168.7, 188.0; HRMS (TF ES + ): m/z calcd for C 18 H 16 ClF 3 5 [(M+H) + ], ; found, Ethyl 5-hydroxy-8-(4-methylbenzoyl)-5-(trifluoromethyl)-3,5-dihydro-2Hoxazolo[3,2-a]pyridine-6-carboxylate (4q) Me H CEt S10
11 White solid; Mp C; IR (KBr): 3200, 2982, 1662, 1601, 1524, 1345, 1177, 1012, 838 cm -1 ; 1 H MR (500 MHz, CDCl 3 ): δ = 1.29 (t, J = 7.1 Hz, 3H, CH 3 ), 2.39 (s, 3H, ArCH 3 ), 3.98 (m, 2H, CH 2 ), 4.24 (d, J = 6.5 Hz, 2H, CH 2 ), (m, 2H, CH 2 ), 7.19 (d, J = 7.5 Hz, 2H, ArH), 7.46 (d, J = 7.5 Hz, 2H, ArH), 7.94 (s, 1H, CH), 8.14 (br, 1H, H); 13 C HMR (125 MHz, CDCl 3 ): δ = 14.6, 22.0, 43.5, 61.7, 70.3, 85.9 (q, J = 32.5, Hz), 91.4, 99.2, (q, J = Hz), 129.0, 129.1, 137.7, 142.1, 143.4, 163.8, 168.9, 189.2; HRMS (TF ES + ): m/z calcd for C 19 H 19 F 3 5 [(M+H) + ], ; found, Ethyl 5-hydroxy-8-(4-methoxybenzoyl)-5-(trifluoromethyl)-3,5-dihydro-2Hoxazolo[3,2-a]pyridine-6-carboxylate (4r) Me H CEt White solid; Mp C; IR (KBr): 3184, 3000, 1677, 1596, 1512, 1263, 1167, 1019, 852 cm -1 ; 1 H MR (500 MHz, CDCl 3 ): δ = 1.31 (t, J = 7.2 Hz, 3H, CH 3 ), 3.85 (s, 3H, CH 3 ), (m, 2H, CH 2 ), (m, 2H, CH 2 ), (m, 2H, CH 2 ), 6.90 (d, J = 8.6 Hz, 2H, ArH), 7.57 (d, J = 8.6 Hz, 2H, ArH), 7.95 (s, 1H, CH), 8.14 (br, 1H, H); 13 C HMR (125 MHz, CDCl 3 ): δ = 14.6, 43.5, 55.7, 61.7, 70.2, 85.9 (q, J = 33.8 Hz), 91.3, 99.0, 113.6, (q, J = Hz), 131.1, 132.9, 143.5, 162.6, 163.6, 168.8, 188.3; HRMS (TF ES + ): m/z calcd for C 19 H 19 F 3 6 [(M+H) + ], ; found, Ethyl 8-(4-chlorobenzoyl)-5-hydroxy-5-(trifluoromethiyl)-3,5-dihydro-2Hthiazolo[3,2-a]pyridine-6-carboxylate (4s) S Cl H CEt Yellow solid; Mp C; IR (KBr): 3262, 2983, 1664, 1590, 1453, 1245, 1175, 1099, 845 cm -1 ; 1 H MR (500 MHz, CDCl 3 ): δ = 1.26 (t, J = 7.0 Hz, 3H, CH 3 ), (m, 1H, CH 2 ), (m, 1H, SCH 2 ), (m, 1H, SCH 2 ), 4.24 (q, J = 7.0 Hz, 2H, CH 2 ), (m, 1H, CH 2 ), 7.44 (d, J = 8.1 Hz, 2H, ArH), 7.54 (d, J = 8.1 Hz, 2H, ArH), 7.73 (s, 1H, CH), 8.20 (br, 1H, H); 13 C HMR (125 MHz, CDCl 3 ): δ = 14.5, 29.4, 50.1, 62.0, 86.2 (q, J = 33.8 Hz), 100.2, 103.8, (q, S11
12 J = Hz), 129.0, 130.6, 137.0, 137.9, 140.3, 168.0, 168.7, 188.7; HRMS (TF ES + ): m/z calcd for C 18 H 16 ClF 3 4 S [(M+H) + ], ; found, Ethyl 8-benzoyl-5-hydroxy-5-(trifluoromethyl)-3,5-dihydro-2H-thiazolo[3,2-a] pyridine-6-carb oxylate (4t) S H CEt Yellow solid; Mp C; IR (KBr): 3441, 2987, 1658, 1583, 1498, 1397, 1252, 1182, 729 cm -1 ; 1 H MR (500 MHz, CDCl 3 ): δ = 1.23 (t, J = 7.0 Hz, 3H, CH 3 ), (m, 1H, CH 2 ), (m, 1H, SCH 2 ), (m, 1H, SCH 2 ), 4.22 (q, J = 7.0 Hz, 2H, CH 2 ), 4.33 (m, 1H, CH 2 ), (m, 5H, PhH), 7.79 (s, 1H, CH), 8.19 (br, 1H, H); 13 C HMR (125 MHz, CDCl 3 ): δ = 14.5, 29.3, 50.1, 61.8, 86.2 (d, J = 33.8 Hz), 99.9, 104.1, (d, J = Hz), , 129.1, 131.7, 138.6, 140.8, 167.7, 168.8, 190.1; HRMS (TF ES + ): m/z calcd for C 18 H 17 F 3 4 S [(M+H) + ], ; found, Ethyl 5-hydroxy-8-(4-methylbenzoyl)-5-(trifluoromethyl)-3,5-dihydro-2Hthiazolo[3,2-a]pyridine-6-carboxylate (4u) S Me H CEt Yellow solid; Mp C; IR (KBr): 3273, 2986, 1664, 1581, 1453, 1248, 1176, 1102, 841 cm -1 ; 1 H MR (500 MHz, CDCl 3 ): δ = 1.25 (t, J = 6.7 Hz, 3H, CH 3 ), 2.42 (s, 3H, ArCH 3 ), 3.18 (m, 1H, CH 2 ), (m, 1H, SCH 2 ), (m, 1H, SCH 2 ), 4.22 (q, J = 6.7 Hz, 2H, CH 2 ), (m, 1H, CH 2 ), 7.26 (d, J = 7.5 Hz, 2H, ArH), 7.51 (d, J = 7.4 Hz, 2H, ArH), 7.82 (s, 1H, CH), 8.21 (br, 1H, H); 13 C HMR (125 MHz, CDCl 3 ): δ = 14.5, 21.9, 29.3, 50.0, 61.8, 86.2 (q, J = 33.8 Hz), 99.7, 104.2, (q, J = Hz), 129.3, 129.4, 135.8, 140.9, 142.3, 167.6, 168.9, 189.9; HRMS (TF ES + ): m/z calcd for C 19 H 19 F 3 4 S [(M+H) + ], ; found, Ethyl 5-hydroxy-8-(4-methoxybenzoyl)-5-(trifluoromethyl)-3,5-dihydro-2Hthiazolo[3,2-a]pyridine-6-carboxylate (4v) S12
13 S Me H CEt Yellow solid; Mp C; IR (KBr): 3214, 2993, 1657, 1593, 1452, 1388, 1260, 1020, 847 cm -1 ; 1 H MR (500 MHz, CDCl 3 ): δ = 1.26 (t, J = 7.0 Hz, 3H, CH 3 ), 3.17 (m, 1H, CH 2 ), (m, 1H, SCH 2 ), 3.87 (s, 3H, CH 3 ), (m, 1H, SCH 2 ), 4.23 (q, J = 7.0 Hz, 2H, CH 2 ), (m, 1H, CH 2 ), 6.97 (d, J = 8.6 Hz, 2H, ArH), 7.60 (d, J = 8.6 Hz, 2H, ArH), 7.83 (s, 1H, CH), 8.23 (br, 1H, H); 13 C HMR (125 MHz, CDCl 3 ): δ = 14.5, 29.4, 50.0, 55.8, 61.8, 86.2 (q, J = 33.8 Hz), 99.5, 104.1, 114.0, (q, J = Hz), 131.0, 131.4, 141.0, 162.7, 167.3, 168.9, 189.1; HRMS (TF ES + ): m/z calcd for C 19 H 19 F 3 5 S [(M+H) + ], ; found, General Procedure for the Preparation of Bicyclic Pyridinone (-imine) 6 via ne-pot Three-component Reactions H H R HC(Et) reflux EtC EWG Solvent-free 5a: EWG = CEt 5b: EWG = C X CEt X =, H R = 2, ArC H 6 R HKAs 1 (2.5mmol), triethoxymethane 2 (3 mmol) and diethyl malonate 5a or ethyl 2-cyanoacetate 5b (3mmol) was charged into a 25 ml round-bottom flask and the mixture was refluxed. The resulting solution was stirred for 1 3 h until the HKAs 1 were completely consumed. The mixture was diluted with EtAc (50 ml x 2) and quenched with water (50 ml). The organic layer was dried by a 2 S 4, concentrated, S13
14 and purified by flash column chromatography (Petro/AcEt = 6/1) to afford product 6 with 89-94% yield. Spectroscopic Data of Bicyclic Pyridinone (-imine) 6 Ethyl 1,2,3,5-tetrahydro-8-(4-chlorobenzoyl)-5-oxoimidazo[1,2-a]pyridine-6- carboxylate (6a) H CEt Yellow solid; Mp C; IR (KBr): 3494, 2981, 1727, 1568, 1224, 1171 cm -1 ; 1 H MR (500 MHz, CDCl 3 ): δ = 1.31 (t, J = 6.6 Hz, 3H, CH 3 ), (m, 2H, CH 2 ), (m, 4H, CH 2 and CH 2 ), 7.45 (d, J = 7.2 Hz, 2H, ArH), 7.63 (d, J = 7.2 Hz, 2H, ArH), 8.41 (s, 1H, CH), 8.80 (br, 1H, H); 13 C MR (125 MHz, CDCl 3 ): δ = 14.8, 43.6, 44.0, 61.2, 97.8, 107.4, 129.3, 130.1, 137.0, 138.1, 149.5, 158.3, 158.6, 165.2, 191.7; HRMS (TF ES + ): m/z calcd for C 17 H 15 Cl 2 a 4 [(M+a) + ], ; found, Cl Ethyl (6b) 1,2,3,5-tetrahydro-8-benzoyl-5-oxoimidazo[1,2-a]pyridine-6-carboxylate H CEt Yellow solid; Mp C; IR (KBr): 3302, 2981, 1727, 1568, 1224, 1171, 1105 cm -1 ; 1 H MR (500 MHz, CH 3 D+DMS-d 6 ): δ = 0.74 (t, J = 6.7 Hz, 3H, CH 3 ), (m, 2H, CH 2 ), 3.77 (q, J = 6.7 Hz, 2H, CH 2 ), (m, 2H, CH 2 ), 5.39 (s, 1H, CH), (m, 5H, ArH and CH); 13 C MR (125 MHz, CH 3 D+DMS-d 6 ): δ = 12.3, 41.4, 43.7, 59.2, 85.1, 105.8, 126.2, 127.5, 127.5, 139.7, 153.6, 156.2, 158.2, 166.5, 194.0; HRMS (TF ES + ): m/z calcd for C 17 H 16 2 a 4 [(M+a) + ], ; found, S14
15 Ethyl 1,2,3,5-tetrahydro-8-(4-methylbenzoyl)-5-oxoimidazo[1,2-a]pyridine-6- carboxylate (6c) H CEt Yellow solid; Mp C; IR (KBr): 3266, 2978, 1694, 1632, 1571, 1275, 1120 cm -1 ; 1 H MR (500 MHz, DMS-d 6 ): δ = 0.86 (t, J = 6.9 Hz, 3H, CH 3 ), 2.32 (s, 3H, ArCH 3 ), (m, 2H, CH 2 ), 3.83 (q, J = 6.9 Hz, 2H, CH 2 ), (m, 2H, CH 2 ), 5.29 (s, 1H, CH), 7.15 (d, J = 7.3 Hz, 2H, ArH), 7.20 (d, J = 7.3 Hz, 2H, ArH), 7.88 (br, 1H, H); 13 C MR (125 MHz, DMS-d 6 ): δ = 14.0, 21.1, 42.3, 44.5, 59.9, 84.3, 107.4, 127.1, 129.2, 137.4, 138.1, 154.3, 155.2, 158.1, 167.2; HRMS (TF CH 3 ES - ): m/z calcd for C 18 H [(M-H) + ], ; found, Ethyl (6d) 1,2,3,5-tetrahydro-5-imino-8-nitroimidazo[1,2-a]pyridine-6-carboxylate H 2 H CEt Yellow solid; Mp C; IR (KBr): 3493, 2984, 1688, 1535, 1376, 600 cm -1 ; 1 H MR (500 MHz, DMS-d 6 ): δ = (m, 3H, CH 3 ), (m, 4H, CH 2 CH 2 ), (m, 2H, CH 2 ), 8.41 (s, 1H, CH), 8.81 (br, 1H, H), (br, 1H, H); 13 C MR (125 MHz, DMS-d 6 ): δ = 14.5, 45.2, 47.1, 60.7, 98.9, 114.2, 137.7, 150.8, 153,4, 165.1; HRMS (TF ES + ): m/z calcd for C 10 H [(M+H) + ], ; found, Ethyl 1,2,3,5-tetrahydro-5-imino-8-(4-chlorobenzoyl)imidazo[1,2-a]pyridine-6- carboxylate (6e) H H CEt Yellow solid; Mp C; IR (KBr): 3494, 2982, 1669, 1569, 1374, 1224, 717 cm -1 ; 1 H MR (500 MHz, DMS-d 6 ): δ = 1.22 (m, 3H, CH 3 ), 3.96 (m, 2H, CH 2 ), (m, 4H, CH 2 and CH 2 ), 7.61 (m, 4H, ArH), 7.96 (s, 1H, Cl S15
16 CH), 8.08 (br, 1H, H), 9.69 (br, 1H, H); 13 C MR (125 MHz, DMS-d 6 ): δ = 14.9, 43.7, 43.8, 59.5, 98.6, 117.3, 118.4, 129.0, 130.4, 136.4, 137.2, 150.5, 157.2, 167.0, 189.6; HRMS (TF ES + ): m/z calcd for C 17 H 17 Cl 3 3 [(M+H) + ], ; found, Ethyl 1,2,3,5-tetrahydro-5-imino-8-benzoylimidazo[1,2-a]pyridine-6- carboxylate (6f) H H CEt Yellow solid; Mp: C; IR (KBr): 3494, 2985, 1652, 1536, 1374, 1231, 759 cm -1 ; 1 H MR (500 MHz, DMS-d 6 ): δ = 1.24 (m, 3H, CH 3 ), (m, 2H, CH 2 ), (m, 4H, CH 2 and CH 2 ), 7.59 (m, 5H, PhH), 7.89 (s, 1H, CH), 9.12 (br, 1H, H), 9.60 (br, 1H, H); 13 C MR (125 MHz, DMS-d 6 ): δ = 14.9, 43.7, 43.8, 59.5, 98.7, 117.3, 118.4, 128.4, 128.9, 131.5, 138.6, 150.4, 157.3, 167.0, 190.8; HRMS (TF ES + ): m/z calcd for C 17 H [(M+H) + ], ; found, S16
17 Anti-cancer activities of compounds 4 The cytotoxic potential of the newly synthesized bicyclic pyridines 4 were evaluated in vitro against a series of human tumor cell lines according to the procedure described in the literature. 6 The tumor cell lines were myeloid leukaemia (HL-60 and K562). Cisplatin (DDP) was servered as the reference drug. (IC 50 value, defined as the concentrations corresponding to 50% growth inhibition). The tested compounds showed moderate to excellent cellular cytotoxicity in the in vitro antitumor screening expressed by the IC 50 values (Table S1). Table S1. Cytotoxic activities of bicyclic pyridines 4 in vitro a (IC 50, g/ml b ) Compd. K562 HL60 DDP a >200 >200 4b c d e >200 >200 4f 70 >200 4g >200 >200 4h >200 >200 4i >200 >200 4j >200 >200 4k l m n o p 12.1 >200 4q >200 >200 4r s t u S17
18 4v a Cytotoxicity as IC 50 for each cell line, is the concentration of compound which reduced by 50% the optical density of treated cells with respect to untreated cells using the MTT assay. b Data represent the mean values of three independent determinations. X-ray Structure and Data 7 of 4m Figure S1 X-Ray crystal structure of 4m Table S2 Crystal data and structure refinement for c Identification code c Empirical formula C 20 H 22 F Formula weight Temperature 298(2) K Wavelength Å Crystal system, space group Hexagonal, R-3 Unit cell dimensions a = (3) A alpha = 90 deg. b = (3) A beta = 90 deg. c = (15) A gamma = 120 deg. Volume (19) A^3 Z, Calculated density 18, Mg/m^3 Absorption coefficient mm^-1 S18
19 F(000) 3924 Crystal size 0.24x 0.14 x 0.10 mm Theta range for data collection 2.00 to deg. Limiting indices -29<=h<=47, -47<=k<=41, -11<=l<=9 Reflection collected/unique 19538/4676[R(int) = ] Completeness to theta = % Absorption correction Semi-empirical from equivalents Max. and min. transmission and Refinement method Full-matrix least-squares on F^2 Data/restraints/parameters 4676/ 186/ 271 Goodness-of-fit on F^ Final R indices [I>2sigma(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Extinction coefficient (15) Semi-empirical from equivalents and e.a^-3 Table S3 Bond lengths [A] and angles [deg] for c C(1)-(1) 1.247(3) C(1)-C(8) 1.437(3) C(1)-C(2) 1.504(3) C(2)-C(7) 1.389(3) C(2)-C(3) 1.390(3) C(3)-C(4) 1.380(4) C(3)-H(3) C(4)-C(5) 1.375(4) C(4)-H(4) C(5)-C(6) 1.383(4) C(5)-H(5) C(6)-C(7) 1.382(4) C(6)-H(6) C(7)-H(7) C(8)-C(9) 1.414(3) C(8)-C(19) 1.433(3) C(9)-C(18) 1.357(3) C(9)-H(9) C(10)-(3) 1.221(3) S19
20 C(10)-(4) 1.334(3) C(10)-C(18) 1.455(3) C(11)-(4) 1.454(3) C(11)-C(12) 1.497(4) C(11)-H(11A) C(11)-H(11B) C(12)-H(12A) C(12)-H(12B) C(12)-H(12C) C(13)-F(2) 1.328(3) C(13)-F(3) 1.332(3) C(13)-F(1) 1.344(3) C(13)-C(20) 1.538(4) C(14)-(1) 1.470(3) C(14)-C(15) 1.514(4) C(14)-H(14A) C(14)-H(14B) C(15)-C(16) 1.514(4) C(15)-H(15A) C(15)-H(15B) C(16)-C(17) 1.497(4) C(16)-H(16A) C(16)-H(16B) C(17)-(2) 1.466(3) C(17)-H(17A) C(17)-H(17B) C(18)-C(20) 1.508(3) C(19)-(2) 1.329(3) C(19)-(1) 1.366(3) C(20)-(2) 1.400(3) C(20)-(1) 1.478(3) (2)-H(2) (2)-H(2A) (2W)-H(11D) (2W)-H(11E) (1W)-H(11D) (1W)-H(10A) (1W)-H(10B) (1)-C(1)-C(8) 124.1(2) (1)-C(1)-C(2) 117.7(2) S20
21 C(8)-C(1)-C(2) 118.2(2) C(7)-C(2)-C(3) 118.6(2) C(7)-C(2)-C(1) 121.7(2) C(3)-C(2)-C(1) 119.7(2) C(4)-C(3)-C(2) 120.1(3) C(4)-C(3)-H(3) C(2)-C(3)-H(3) C(5)-C(4)-C(3) 121.0(3) C(5)-C(4)-H(4) C(3)-C(4)-H(4) C(4)-C(5)-C(6) 119.5(3) C(4)-C(5)-H(5) C(6)-C(5)-H(5) C(7)-C(6)-C(5) 119.7(3) C(7)-C(6)-H(6) C(5)-C(6)-H(6) C(6)-C(7)-C(2) 121.1(2) C(6)-C(7)-H(7) C(2)-C(7)-H(7) C(9)-C(8)-C(19) 116.6(2) C(9)-C(8)-C(1) 121.5(2) C(19)-C(8)-C(1) 121.5(2) C(18)-C(9)-C(8) 123.5(2) C(18)-C(9)-H(9) C(8)-C(9)-H(9) (3)-C(10)-(4) 122.3(2) (3)-C(10)-C(18) 124.6(2) (4)-C(10)-C(18) 113.1(2) (4)-C(11)-C(12) 110.8(2) (4)-C(11)-H(11A) C(12)-C(11)-H(11A) (4)-C(11)-H(11B) C(12)-C(11)-H(11B) H(11A)-C(11)-H(11B) F(2)-C(13)-F(3) 106.9(2) F(2)-C(13)-F(1) 106.2(2) F(3)-C(13)-F(1) 106.4(2) F(2)-C(13)-C(20) 113.1(2) F(3)-C(13)-C(20) 113.1(2) F(1)-C(13)-C(20) 110.8(2) S21
22 (1)-C(14)-C(15) 113.7(2) (1)-C(14)-H(14A) C(15)-C(14)-H(14A) (1)-C(14)-H(14B) C(15)-C(14)-H(14B) H(14A)-C(14)-H(14B) C(16)-C(15)-C(14) 110.1(2) C(16)-C(15)-H(15A) C(14)-C(15)-H(15A) C(16)-C(15)-H(15B) C(14)-C(15)-H(15B) H(15A)-C(15)-H(15B) C(17)-C(16)-C(15) 113.7(2) C(17)-C(16)-H(16A) C(15)-C(16)-H(16A) C(17)-C(16)-H(16B) C(15)-C(16)-H(16B) H(16A)-C(16)-H(16B) (2)-C(17)-C(16) 114.1(2) (2)-C(17)-H(17A) C(16)-C(17)-H(17A) (2)-C(17)-H(17B) C(16)-C(17)-H(17B) H(17A)-C(17)-H(17B) C(9)-C(18)-C(10) 122.5(2) C(9)-C(18)-C(20) 117.7(2) C(10)-C(18)-C(20) 119.8(2) (2)-C(19)-(1) 120.3(2) (2)-C(19)-C(8) 120.0(2) (1)-C(19)-C(8) 119.6(2) (2)-C(20)-(1) (18) (2)-C(20)-C(18) (19) (1)-C(20)-C(18) (19) (2)-C(20)-C(13) 105.9(2) (1)-C(20)-C(13) (18) C(18)-C(20)-C(13) 110.8(2) C(19)-(1)-C(14) 118.9(2) C(19)-(1)-C(20) (18) C(14)-(1)-C(20) (19) C(19)-(2)-C(17) 130.2(2) S22
23 C(19)-(2)-H(2) C(17)-(2)-H(2) C(10)-(4)-C(11) (18) H(11D)-(2W)-H(11E) H(11D)-(1W)-H(10A) H(11D)-(1W)-H(10B) H(10A)-(1W)-H(10B) Symmetry transformations used to generate equivalent atoms: Table S4 Torsion angles [deg] for c (1)-C(1)-C(2)-C(7) 130.3(3) C(8)-C(1)-C(2)-C(7) -49.9(3) (1)-C(1)-C(2)-C(3) -47.3(3) C(8)-C(1)-C(2)-C(3) 132.5(2) C(7)-C(2)-C(3)-C(4) 1.7(4) C(1)-C(2)-C(3)-C(4) 179.4(2) C(2)-C(3)-C(4)-C(5) -1.9(4) C(3)-C(4)-C(5)-C(6) 0.3(5) C(4)-C(5)-C(6)-C(7) 1.4(4) C(5)-C(6)-C(7)-C(2) -1.6(4) C(3)-C(2)-C(7)-C(6) 0.0(4) C(1)-C(2)-C(7)-C(6) (2) (1)-C(1)-C(8)-C(9) 163.4(2) C(2)-C(1)-C(8)-C(9) -16.4(3) (1)-C(1)-C(8)-C(19) -9.1(4) C(2)-C(1)-C(8)-C(19) 171.1(2) C(19)-C(8)-C(9)-C(18) -15.3(3) C(1)-C(8)-C(9)-C(18) 171.9(2) (1)-C(14)-C(15)-C(16) 47.8(3) C(14)-C(15)-C(16)-C(17) 39.3(3) C(15)-C(16)-C(17)-(2) -76.7(3) C(8)-C(9)-C(18)-C(10) 171.6(2) C(8)-C(9)-C(18)-C(20) -6.4(3) (3)-C(10)-C(18)-C(9) (2) (4)-C(10)-C(18)-C(9) 2.0(3) (3)-C(10)-C(18)-C(20) 0.4(4) (4)-C(10)-C(18)-C(20) 180.0(2) C(9)-C(8)-C(19)-(2) (2) C(1)-C(8)-C(19)-(2) 4.5(3) C(9)-C(8)-C(19)-(1) 8.1(3) C(1)-C(8)-C(19)-(1) (2) S23
24 C(9)-C(18)-C(20)-(2) 153.5(2) C(10)-C(18)-C(20)-(2) -24.6(3) C(9)-C(18)-C(20)-(1) 32.1(3) C(10)-C(18)-C(20)-(1) (2) C(9)-C(18)-C(20)-C(13) -87.0(3) C(10)-C(18)-C(20)-C(13) 95.0(3) F(2)-C(13)-C(20)-(2) (19) F(3)-C(13)-C(20)-(2) -53.7(3) F(1)-C(13)-C(20)-(2) 65.6(3) F(2)-C(13)-C(20)-(1) -60.3(3) F(3)-C(13)-C(20)-(1) 61.3(3) F(1)-C(13)-C(20)-(1) (19) F(2)-C(13)-C(20)-C(18) 60.2(3) F(3)-C(13)-C(20)-C(18) (2) F(1)-C(13)-C(20)-C(18) -58.9(3) (2)-C(19)-(1)-C(14) 22.3(3) C(8)-C(19)-(1)-C(14) (2) (2)-C(19)-(1)-C(20) (2) C(8)-C(19)-(1)-C(20) 20.7(3) C(15)-C(14)-(1)-C(19) -85.0(3) C(15)-C(14)-(1)-C(20) 100.3(3) (2)-C(20)-(1)-C(19) (2) C(18)-C(20)-(1)-C(19) -39.8(3) C(13)-C(20)-(1)-C(19) 81.1(2) (2)-C(20)-(1)-C(14) 9.7(3) C(18)-C(20)-(1)-C(14) 134.9(2) C(13)-C(20)-(1)-C(14) (2) (1)-C(19)-(2)-C(17) 20.3(4) C(8)-C(19)-(2)-C(17) (2) C(16)-C(17)-(2)-C(19) 20.5(4) (3)-C(10)-(4)-C(11) 12.8(3) C(18)-C(10)-(4)-C(11) (2) C(12)-C(11)-(4)-C(10) 79.6(3) Table S5 Hydrogen bonds for c [A and deg.]. D-H...A d(d-h) d(h...a) d(d...a) <(DHA) S24
25 C(14)-H(14A)...(2) (3) C(9)-H(9)...(4) (3) (2)-H(2A)...(3) (2) (2)-H(2)...(1) (3) H MR and 13 C MR Spectra for Bicyclic Pyridines 4, 6 S25
26 H 2 CEt H Figure 1. 1 H MR (500 MHz, CDCl 3 ) spectra of compound 4a S26
27 H 2 CEt H Figure C MR (125 MHz, CDCl 3 ) spectra of compound 4a S27
28 H Me H CEt Figure 3. 1 H MR (500 MHz, CDCl 3 ) spectra of compound 4b S28
29 H Me H CEt Figure C MR (125 MHz, CDCl 3 ) spectra of compound 4b S29
30 H H CEt Figure 5. 1 H MR (500 MHz, CDCl 3 ) spectra of compound 4c S30
31 H H CEt Figure C MR (125 MHz, CDCl 3 ) spectra of compound 4c S31
32 H Me CEt H Figure 7. 1 H MR (500 MHz, CDCl 3 ) spectra of compound 4d S32
33 H Me CEt H Figure C MR (125 MHz, CDCl 3 ) spectra of compound 4d S33
34 H Me H CEt Figure 9. 1 H MR (500 MHz, CDCl 3 ) spectra of compound 4e S34
35 H Me H CEt Figure C MR (125 MHz, CDCl 3 ) spectra of compound 4e S35
36 H CEt CEt H Figure H MR (500 MHz, CDCl 3 ) spectra of compound 4f S36
37 H CEt CEt H Figure C MR (125 MHz, CDCl 3 ) spectra of compound 4f S37
38 H 2 H CEt Figure H MR (500 MHz, CDCl 3 ) spectra of compound 4g S38
39 H 2 H CEt Figure C MR (125 MHz, CDCl 3 ) spectra of compound 4g S39
40 H Cl H CEt Figure H MR (500 MHz, CDCl 3 ) spectra of compound 4h S40
41 H Cl H CEt Figure C MR (125 MHz, CDCl 3 ) spectra of compound 4h S41
42 H H CEt Figure H MR (500 MHz, CDCl 3 ) spectra of compound 4i S42
43 H H CEt Figure C MR (125 MHz, CDCl 3 ) spectra of compound 4i S43
44 H Me H CEt Figure H MR (500 MHz, CDCl 3 ) spectra of compound 4j S44
45 H Me H CEt Figure C MR (125 MHz, CDCl 3 ) spectra of compound 4j S45
46 H Me H CEt Figure H MR (500 MHz, CDCl 3 ) spectra of compound 4k S46
47 H Me H CEt Figure C MR (125 MHz, CDCl 3 ) spectra of compound 4k S47
48 H Cl H CEt Figure H MR (500 MHz, CDCl 3 ) spectra of compound 4l S48
49 H Cl H CEt Figure C MR (125 MHz, CDCl 3 ) spectra of compound 4l S49
50 H H CEt Figure H MR (500 MHz, CDCl 3 ) spectra of compound 4m S50
51 H H CEt Figure C MR (125 MHz, CDCl 3 ) spectra of compound 4m S51
52 H Me H CEt Figure H MR (500 MHz, CDCl 3 ) spectra of compound 4n S52
53 H Me H CEt Figure C MR (125 MHz, CDCl 3 ) spectra of compound 4n S53
54 H Me H CEt Figure H MR (500 MHz, CDCl 3 ) spectra of compound 4o S54
55 H Me H CEt Figure C MR (125 MHz, CDCl 3 ) spectra of compound 4o S55
56 Cl H CEt Figure H MR (500 MHz, CDCl 3 ) spectra of compound 4p S56
57 Cl H CEt Figure C MR (125 MHz, CDCl 3 ) spectra of compound 4p S57
58 Me H CEt Figure H MR (500 MHz, CDCl 3 ) spectra of compound 4q S58
59 Me H CEt Figure C MR (125 MHz, CDCl 3 ) spectra of compound 4q S59
60 Me H CEt Figure H MR (500 MHz, CDCl 3 ) spectra of compound 4r S60
61 Me H CEt Figure C MR (125 MHz, CDCl 3 ) spectra of compound 4r S61
62 S Cl H CEt Figure H MR (500 MHz, CDCl 3 ) spectra of compound 4s S62
63 S Cl H CEt Figure C MR (125 MHz, CDCl 3 ) spectra of compound 4s S63
64 S CEt H Figure H MR (500 MHz, CDCl 3 ) spectra of compound 4t S64
65 S CEt H Figure C MR (125 MHz, CDCl 3 ) spectra of compound 4t S65
66 S Me CEt H Figure H MR (500 MHz, CDCl 3 ) spectra of compound 4u S66
67 S Me CEt H Figure C MR (125 MHz, CDCl 3 ) spectra of compound 4u S67
68 S Me H CEt Figure H MR (500 MHz, CDCl 3 ) spectra of compound 4v S68
69 S Me H CEt Figure C MR (125 MHz, CDCl 3 ) spectra of compound 4v S69
70 H CEt Cl Figure H MR (500 MHz, CDCl 3 ) spectra of compound 6a S70
71 H CEt Cl Figure C MR (125 MHz, CDCl 3 ) spectra of compound 6a S71
72 H CEt Figure H MR (500 MHz, CH 3 D+DMS-d 6 ) spectra of compound 6b S72
73 H CEt Figure C MR (125 MHz, CH 3 D+DMS-d 6 ) spectra of compound 6b S73
74 H CEt CH 3 Figure H MR (500 MHz, DMS-d 6 ) spectra of compound 6c S74
75 H CEt CH 3 Figure C MR (125 MHz, DMS-d 6 ) spectra of compound 6c S75
76 H 2 H CEt Figure H MR (500 MHz, DMS-d 6 ) spectra of compound 6d S76
77 H 2 H CEt Figure C MR (125 MHz, DMS-d 6 ) spectra of compound 6d S77
78 H H CEt Cl Figure H MR (500 MHz, DMS-d 6 ) spectra of compound 6e S78
79 H H CEt Cl Figure C MR (125 MHz, DMS-d 6 ) spectra of compound 6e S79
80 H H CEt Figure H MR (500 MHz, DMS-d 6 ) spectra of compound 6f S80
81 H H CEt Figure C MR (125 MHz, DMS-d 6 ) spectra of compound 6f S81
82 References and otes 1. (a) Reddy, A. V..; Maiti, S..; Singh, I. P.; Micetich, G. Synth. Commun. 1989, 19, (b) Foks, H.; Pancechowska-Ksepko, D.; Janowiec, M.; Zwolska, Z.; Augustynowicz-Kopec, E. Phosphorus, Sulfur Silicon Relat. Elem. 2005, 180, Zhao, M.-X.; Wang, M.-X.; Huang, Z.-T. Tetrahedron 2002, 58, (a) Huang, Z.-T.; Wang, M.-X. Synthesis 1992, 12, (b) Li, Z.-J.; Charles, D. Synth. Commun. 2001, 31, (a) Huang, Z.-T.; Zhang, P.-C. Chem. Ber. 1989, 122, (b)huang, Z.-T.; Shi, X. Synthesis 1990, 2, Wang, F.-M.; Li H.; Cheng D.; Feng,.; Zhang, S.-L. Port health control (in Chinese) 2004, 4, (a) Kim, D. K.; Ryu, D. H.; Lee, J. Y.; Lee,.; Kim, Y. W.; Kim, J. S.; Chang, K.; Im, G. J.; Kim, T. K.; Choi, W. S. J. Med. Chem., 2001, 44, (b) Carmichael, J.; DeGraff, W. D.; Gazdar, A. F.; Minna, J. D.; Mitchell, J. B. Cancer Res. 1987, 47, (c) Mossman, T. J. Immunol. Methods 1983, 65, CCDC contain the supplementary crystallographic data for compound 4m. These data can be obtained free of charge from The Cambridge Crystallographic Data Center via S82
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