Retention time 3

Retention time 3.08 min, >98% purity. (34). 137.29, 137.20, 134.61, 134.41, 129.42 (C 2), 128.85, 128.03, 127.72 (C 2), 119.32, 116.03, 39.38. Retention time 2.95 min, >98% purity. Compounds 5C7 were prepared with a similar procedure as that used for 4. (5). LCCMS (ESI) found (M + H)+ 354.1 (M + H)+; 1H-NMR (400 MHz, CDCl3) 8.72 (d, = 1.9 Hz, 1H), Rabbit polyclonal to Sca1 8.50 (d, = 0.8 Hz, 1H), 7.74 (d, = 0.8 Hz, 1H), 7.69 (dd, = 1.9, 0.8 Hz, 1H), 7.67 (s, 1H), 7.11C7.03 (m, 3H), 6.97 (dd, = 7.9, 1.6 Hz, 2H), 4.70 (s, 2H), 4.00 (s, 3H). 13C-NMR (126 MHz, CDCl3) 146.47, 141.71, 140.45, 137.16, 136.00, 130.55 (C 2), 129.49, 128.56 (C 2), 128.37, 127.73, 126.14, 119.12, 115.27, 60.31, 39.32. Retention time 2.97 min, >98% purity. (6). LCCMS (ESI) found (M + H)+ 290.1 (M + H)+; 1H-NMR (400 MHz, CDCl3) 8.73 (d, = 1.8 Hz, 1H), 8.28 (d, = 0.9 Hz, 1H), 7.81 (s, 1H), 7.72 (s, 1H), PD168393 7.64C7.59 (m, 1H), 7.38C7.30 (m, 3H), 7.25C7.21 (m, 2H), 5.64 (s, 2H), 4.00 (s, 3H). 13C-NMR (126 MHz, CDCl3) 140.67, 140.55, 137.55, 137.52, 137.10, 135.76, 131.18, 128.82 (C 2), 128.54, 127.92, 127.73 (C 2), 121.94, 101.51, 47.90, 39.22. Retention time 3.05 min, 98.25% purity. (7). LCCMS (ESI) found (M + H)+ 304.1 (M + H)+; 1H-NMR (400 MHz, CDCl3) 8.74 (d, = 1.9 Hz, 1H), 8.06 (d, = 1.0 Hz, 1H), 7.96 (s, 1H), 7.88 (s, 1H), 7.75 (s, 1H), 7.32C7.24 (m, 3H), 7.14C7.10 (m, 2H), 4.68 (t, = 7.3 Hz, 2H), 4.01 (s, 3H), 3.35 (t, = 7.3 Hz, 2H). 13C-NMR (126 MHz, CDCl3) 153.72, 147.61, PD168393 145.87, 142.01, 140.34, 139.20, 137.77, 137.60, 136.48, 129.91, 129.02, 120.95, 110.86, 107.81, 105.68, 64.3, 39.36, 34.2. Retention time 3.08 min, >98% purity. (34). A solution of 6-bromo-1(ESI) found (M + H)+ 199.1 (M + H)+; 1H-NMR (400 MHz, DMSO-= 2.8 Hz, 1H), 6.53 (t, = 2.8 Hz, 1H), 3.88 (s, 3H). (8). Sodium hydride (7 mg, 0.28 mmol) was suspended in 3 mL of anhydrous DMF. 6-(1-methyl-1(ESI) found (M + H)+ 339.1 (M + H)+; 1H-NMR (400 MHz, CDCl3) 8.70 (d, = 1.7 Hz, 1H), 8.32 (d, = 1.2 Hz, 1H), 7.91 (s, 1H), 7.89 (t, = 1.7 Hz, 1H), 7.87C7.85 (m, 1H), 7.77 (d, = 3.8 Hz, 2H), 7.63C7.56 (m, 1H), 7.49 (t, = 7.7 Hz, 2H), 6.88 (dd, = 3.8, 0.7 Hz, 1H), 4.02 (s, 3H). 13C-NMR (126 MHz, CDCl3) 147.08, 144.47, 138.00, 136.93, 134.28, 129.53 (C 2), 129.25, 128.86, 127.36, 126.70 (C 2), 124.81, 120.18, 117.08, 110.45, 39.25. Retention time 2.92 min, >98% purity. Compounds 9 were prepared with a similar procedure as that used for 8. (9). LCCMS (ESI) found (M + H)+ 340.0 (M + H)+; 1H-NMR (400 MHz, CDCl3) 8.71 (s, 1H), 8.28C8.19 (m, 2H), 8.09 (s, 1H), 8.03 (s, 1H), 7.94 (d, = 4.1 Hz, 1H), 7.62 (d, = 7.4 Hz, 1H), 7.54 (t, = 7.7 Hz, 2H), 6.80 (d, = 4.1 Hz, 1H), 4.04 (s, 3H). 13C-NMR (126 MHz, CDCl3) 142.22, 140.54, 139.05, 138.04, 137.96, 137.77, 134.47, 129.14 (C 2), 129.10, 128.96, 128.24 (C 2), 120.98, 106.58, 39.37. Retention time 2.99 min, >99% purity. (37). To a stirred solution of the 5-bromo-2-methylpyridin-3-amine (36) (200 mg, 1.07 mmol) in anhydrous dichloromethane (15 mL) was added benzenesulfonyl chloride (152.Retention time 2.94 min, 96.21% purity. 4. + H)+ 340.0 (M + H)+; 1H-NMR (400 MHz, CDCl3) 8.84 (d, = 1.7 Hz, 1 H), 8.49 (s, 1 H), 8.38 (s, 1 H), 8.02 (d, = 7.4 Hz, 2 H), 7.94 (s, 1H), 7.86 (s, 1H), 7.62 (t, = 7.4 Hz, 1 H), 7.51 (t, = 7.4 Hz, 2 H), 4.03 (s, 3 H). 13C-NMR (126 MHz, CDCl3) 146.75, 142.02, 141.60, 137.29, 137.20, 134.61, 134.41, 129.42 (C 2), 128.85, 128.03, 127.72 (C 2), 119.32, 116.03, 39.38. Retention time 2.95 min, >98% purity. Compounds 5C7 were prepared with a similar procedure as that used for 4. (5). LCCMS (ESI) found (M + H)+ 354.1 (M + H)+; 1H-NMR (400 MHz, CDCl3) 8.72 (d, = 1.9 Hz, 1H), 8.50 (d, = 0.8 Hz, 1H), 7.74 (d, = 0.8 Hz, 1H), 7.69 (dd, = 1.9, 0.8 Hz, 1H), 7.67 (s, 1H), 7.11C7.03 (m, 3H), 6.97 (dd, = 7.9, 1.6 Hz, 2H), 4.70 (s, 2H), 4.00 (s, 3H). 13C-NMR (126 MHz, CDCl3) 146.47, 141.71, 140.45, 137.16, 136.00, 130.55 (C 2), 129.49, 128.56 (C 2), 128.37, 127.73, 126.14, 119.12, 115.27, 60.31, 39.32. Retention time 2.97 min, >98% purity. (6). LCCMS (ESI) found (M + H)+ 290.1 (M + H)+; 1H-NMR (400 MHz, CDCl3) 8.73 (d, = 1.8 Hz, 1H), 8.28 (d, = 0.9 Hz, 1H), 7.81 (s, 1H), 7.72 (s, 1H), 7.64C7.59 (m, 1H), 7.38C7.30 (m, 3H), 7.25C7.21 (m, 2H), 5.64 (s, 2H), 4.00 (s, 3H). 13C-NMR (126 MHz, CDCl3) 140.67, 140.55, 137.55, 137.52, 137.10, 135.76, 131.18, 128.82 (C 2), 128.54, 127.92, 127.73 (C 2), 121.94, 101.51, 47.90, 39.22. Retention time 3.05 min, 98.25% purity. (7). LCCMS (ESI) found (M + H)+ 304.1 (M + H)+; 1H-NMR (400 MHz, CDCl3) 8.74 (d, = 1.9 Hz, 1H), 8.06 (d, = 1.0 Hz, 1H), 7.96 (s, 1H), 7.88 (s, 1H), 7.75 (s, 1H), 7.32C7.24 (m, 3H), 7.14C7.10 (m, 2H), 4.68 (t, = 7.3 Hz, 2H), 4.01 (s, 3H), 3.35 (t, = 7.3 Hz, 2H). 13C-NMR (126 MHz, CDCl3) 153.72, 147.61, 145.87, 142.01, 140.34, 139.20, 137.77, 137.60, 136.48, 129.91, 129.02, 120.95, 110.86, 107.81, 105.68, 64.3, 39.36, 34.2. Retention time 3.08 min, >98% purity. (34). A solution of 6-bromo-1(ESI) found (M + H)+ 199.1 (M + H)+; 1H-NMR (400 MHz, DMSO-= 2.8 Hz, 1H), 6.53 (t, = 2.8 Hz, 1H), 3.88 (s, 3H). (8). Sodium hydride (7 mg, 0.28 mmol) was suspended in 3 mL of anhydrous DMF. 6-(1-methyl-1(ESI) found (M + H)+ 339.1 (M + H)+; 1H-NMR (400 MHz, CDCl3) 8.70 (d, = 1.7 Hz, 1H), 8.32 (d, = 1.2 Hz, 1H), 7.91 (s, 1H), 7.89 (t, = 1.7 Hz, 1H), 7.87C7.85 (m, 1H), 7.77 (d, = 3.8 Hz, 2H), 7.63C7.56 (m, 1H), 7.49 (t, = 7.7 Hz, 2H), 6.88 (dd, = 3.8, 0.7 Hz, 1H), 4.02 (s, 3H). 13C-NMR (126 MHz, CDCl3) 147.08, 144.47, 138.00, 136.93, 134.28, 129.53 (C 2), 129.25, 128.86, 127.36, 126.70 (C 2), 124.81, 120.18, 117.08, 110.45, 39.25. Retention time 2.92 min, >98% purity. Compounds 9 were prepared with a similar procedure as that used for 8. (9). LCCMS (ESI) found (M + H)+ 340.0 (M + H)+; 1H-NMR (400 MHz, CDCl3) 8.71 (s, 1H), 8.28C8.19 (m, 2H), 8.09 (s, 1H), 8.03 (s, 1H), 7.94 (d, = 4.1 Hz, 1H), 7.62 (d, = 7.4 Hz, 1H), 7.54 (t, = 7.7 Hz, 2H), 6.80 (d, = 4.1 Hz, 1H), 4.04 (s, 3H). 13C-NMR (126 MHz, CDCl3) 142.22, 140.54, 139.05, 138.04, 137.96, 137.77, 134.47, 129.14 (C 2), 129.10, 128.96, 128.24 (C 2), 120.98, 106.58, 39.37. Retention time 2.99 min, >99% purity. (37). To a stirred solution of the 5-bromo-2-methylpyridin-3-amine (36) (200 mg, 1.07 mmol) in anhydrous dichloromethane (15 mL) was added benzenesulfonyl chloride (152 L, 1.12 mmol). After 1 h, The mixture was then partially concentrated in vacuo, diluted with EtOAc (40 mL) and saturated NaHCO3 solution (20 mL) and partitioned. The aqueous layer was extracted with EtOAc (2 20 mL). The combined organic layers were dried (Na2SO4), filtered and concentrated to afford 37 (300 mg, 85% yield); LCCMS (ESI) found (M + H)+ 328.1 (M + H)+;.Reagents and conditions: (a) Pd(dppf)Cl2, K2CO3, Dioxane:H2O (= 4:1), 80 C, 3 h, 89% yield (34), 82% yield (35); (b) NaH, DMF, benzenesulfonyl chloride, r.t., 2 h, 82% yield (8), 79% yield (9). Open in a separate window Scheme 3 The synthesis route of compound 10. 4.03 (s, 3 H). 13C-NMR (126 MHz, CDCl3) 146.75, 142.02, 141.60, 137.29, 137.20, 134.61, 134.41, 129.42 (C 2), 128.85, 128.03, 127.72 (C 2), 119.32, 116.03, 39.38. Retention time 2.95 min, >98% purity. Compounds 5C7 were prepared with a similar procedure as that used for 4. (5). LCCMS (ESI) found (M + H)+ 354.1 (M + H)+; 1H-NMR (400 MHz, CDCl3) 8.72 (d, = 1.9 Hz, 1H), 8.50 (d, = 0.8 Hz, 1H), 7.74 (d, = 0.8 Hz, 1H), 7.69 (dd, = 1.9, 0.8 Hz, 1H), 7.67 (s, 1H), 7.11C7.03 (m, 3H), 6.97 (dd, = 7.9, 1.6 Hz, 2H), 4.70 (s, 2H), 4.00 (s, 3H). 13C-NMR (126 MHz, CDCl3) 146.47, 141.71, 140.45, 137.16, 136.00, 130.55 (C 2), 129.49, 128.56 (C 2), 128.37, 127.73, 126.14, 119.12, 115.27, 60.31, 39.32. Retention time 2.97 min, >98% purity. (6). LCCMS (ESI) found (M + H)+ 290.1 (M + H)+; 1H-NMR (400 MHz, CDCl3) 8.73 (d, = 1.8 Hz, 1H), 8.28 (d, = 0.9 Hz, 1H), 7.81 (s, 1H), 7.72 (s, 1H), 7.64C7.59 (m, 1H), 7.38C7.30 (m, 3H), 7.25C7.21 (m, 2H), 5.64 (s, 2H), 4.00 (s, 3H). 13C-NMR (126 MHz, CDCl3) 140.67, 140.55, 137.55, 137.52, 137.10, 135.76, 131.18, 128.82 (C 2), 128.54, 127.92, 127.73 (C 2), 121.94, 101.51, 47.90, 39.22. Retention time 3.05 min, 98.25% purity. (7). LCCMS (ESI) found (M + H)+ 304.1 (M + H)+; 1H-NMR (400 MHz, CDCl3) 8.74 (d, = 1.9 Hz, 1H), 8.06 (d, = 1.0 Hz, 1H), 7.96 (s, 1H), 7.88 (s, 1H), 7.75 (s, 1H), 7.32C7.24 (m, 3H), 7.14C7.10 (m, 2H), 4.68 (t, = 7.3 Hz, 2H), 4.01 (s, 3H), 3.35 (t, = 7.3 Hz, 2H). 13C-NMR (126 MHz, CDCl3) 153.72, 147.61, 145.87, 142.01, 140.34, 139.20, 137.77, 137.60, 136.48, 129.91, 129.02, 120.95, 110.86, 107.81, 105.68, 64.3, 39.36, 34.2. Retention time 3.08 min, >98% purity. (34). A solution of 6-bromo-1(ESI) found (M + H)+ 199.1 (M + H)+; 1H-NMR (400 MHz, DMSO-= 2.8 Hz, 1H), 6.53 (t, = 2.8 Hz, 1H), 3.88 (s, 3H). (8). Sodium hydride (7 mg, 0.28 mmol) was suspended in 3 mL of anhydrous DMF. 6-(1-methyl-1(ESI) found (M + H)+ 339.1 (M + H)+; 1H-NMR (400 MHz, CDCl3) 8.70 (d, = 1.7 Hz, 1H), 8.32 (d, = 1.2 Hz, 1H), 7.91 (s, 1H), 7.89 (t, = 1.7 Hz, 1H), 7.87C7.85 (m, 1H), 7.77 (d, = 3.8 Hz, 2H), 7.63C7.56 (m, 1H), 7.49 (t, = 7.7 Hz, 2H), 6.88 (dd, = 3.8, 0.7 Hz, 1H), 4.02 (s, 3H). 13C-NMR (126 MHz, CDCl3) 147.08, 144.47, 138.00, 136.93, 134.28, 129.53 (C 2), 129.25, 128.86, 127.36, 126.70 (C 2), 124.81, 120.18, 117.08, 110.45, 39.25. Retention time 2.92 min, >98% purity. Compounds 9 were prepared with a similar procedure as that used for 8. (9). LCCMS (ESI) found (M + H)+ 340.0 (M + H)+; 1H-NMR (400 MHz, CDCl3) 8.71 (s, 1H), 8.28C8.19 (m, 2H), 8.09 (s, 1H), 8.03 (s, 1H), 7.94 (d, = 4.1 Hz, 1H), 7.62 (d, = 7.4 Hz, 1H), 7.54 (t, = 7.7 Hz, 2H), 6.80 (d, = 4.1 Hz, 1H), 4.04 (s, 3H). 13C-NMR (126 MHz, CDCl3) 142.22, 140.54, 139.05, 138.04, 137.96, 137.77, 134.47, 129.14 (C 2), 129.10, 128.96, 128.24 (C 2), 120.98, 106.58, 39.37. Retention time 2.99 min, >99% purity. (37). To a stirred solution of the 5-bromo-2-methylpyridin-3-amine (36) (200 mg, 1.07 mmol) in anhydrous dichloromethane (15 mL) was added benzenesulfonyl chloride (152 L, 1.12 mmol). After 1 h, The mixture was then partially concentrated in vacuo, diluted with EtOAc (40 mL) and saturated NaHCO3 solution (20 mL) and partitioned. The aqueous layer was extracted with EtOAc (2 20 mL). The combined organic layers were dried (Na2SO4), filtered and concentrated to afford 37 (300 mg, 85% yield); LCCMS (ESI) found (M + H)+ 328.1 (M + H)+; 1H-NMR (400 MHz, CDCl3) 8.37 (d, = 2.1 Hz, 1H), 7.92 (d, = 2.1 Hz, 1H), 7.82C7.76 (m, 2H), 7.67C7.61 (m, 1H), 7.56C7.49 (m, 2H), 2.17 (s, 3H). (10). A solution of (ESI) found (M + H)+ 329.1 (M +.13C-NMR (126 MHz, CDCl3) 169.38, 148.24, 142.03, 140.64, 140.34, 140.19, 139.73, 139.00, 133.57, 130.68, 129.81, 129.04, 126.08, 124.04, 123.66, 107.39, 21.67. DMF. 6-(1-methyl-1(ESI) found (M + H)+ 340.0 (M + H)+; 1H-NMR (400 MHz, CDCl3) 8.84 (d, = 1.7 Hz, 1 H), 8.49 (s, 1 H), 8.38 (s, 1 H), 8.02 (d, = 7.4 Hz, 2 H), 7.94 (s, 1H), 7.86 (s, 1H), 7.62 (t, = 7.4 Hz, 1 H), 7.51 (t, = 7.4 Hz, 2 H), 4.03 (s, 3 H). 13C-NMR (126 MHz, CDCl3) 146.75, 142.02, 141.60, 137.29, 137.20, 134.61, 134.41, 129.42 (C 2), 128.85, 128.03, 127.72 (C 2), 119.32, 116.03, 39.38. Retention time 2.95 min, >98% purity. Compounds 5C7 were prepared with a similar procedure as that used for 4. (5). LCCMS (ESI) found (M + H)+ 354.1 (M + H)+; 1H-NMR (400 MHz, CDCl3) 8.72 (d, = 1.9 Hz, 1H), 8.50 (d, = 0.8 Hz, 1H), 7.74 (d, = 0.8 Hz, 1H), 7.69 (dd, = 1.9, 0.8 Hz, 1H), 7.67 (s, 1H), 7.11C7.03 (m, 3H), 6.97 (dd, = 7.9, 1.6 Hz, 2H), 4.70 (s, 2H), 4.00 (s, 3H). 13C-NMR (126 MHz, CDCl3) 146.47, 141.71, 140.45, 137.16, 136.00, 130.55 (C 2), 129.49, 128.56 PD168393 (C 2), 128.37, 127.73, 126.14, 119.12, 115.27, 60.31, 39.32. Retention time 2.97 min, >98% purity. (6). LCCMS (ESI) found (M + H)+ 290.1 (M + H)+; 1H-NMR (400 MHz, CDCl3) 8.73 (d, = 1.8 Hz, 1H), 8.28 (d, = 0.9 Hz, 1H), 7.81 (s, 1H), 7.72 (s, 1H), 7.64C7.59 (m, 1H), 7.38C7.30 (m, 3H), 7.25C7.21 (m, 2H), 5.64 (s, 2H), 4.00 (s, 3H). 13C-NMR (126 MHz, CDCl3) 140.67, 140.55, 137.55, 137.52, 137.10, 135.76, 131.18, 128.82 (C 2), 128.54, 127.92, 127.73 (C 2), 121.94, 101.51, 47.90, 39.22. Retention time 3.05 min, 98.25% purity. (7). LCCMS (ESI) found (M + H)+ 304.1 (M + H)+; 1H-NMR (400 MHz, CDCl3) 8.74 (d, = 1.9 Hz, 1H), 8.06 (d, = 1.0 Hz, 1H), 7.96 (s, 1H), 7.88 (s, 1H), 7.75 (s, 1H), 7.32C7.24 (m, 3H), 7.14C7.10 (m, 2H), 4.68 (t, = 7.3 Hz, 2H), 4.01 (s, 3H), 3.35 (t, = 7.3 Hz, 2H). 13C-NMR (126 MHz, CDCl3) 153.72, 147.61, 145.87, 142.01, 140.34, 139.20, 137.77, 137.60, 136.48, 129.91, 129.02, 120.95, 110.86, 107.81, 105.68, 64.3, 39.36, 34.2. Retention time 3.08 min, >98% purity. (34). A solution of 6-bromo-1(ESI) found (M + H)+ 199.1 (M + H)+; 1H-NMR (400 MHz, DMSO-= 2.8 Hz, 1H), 6.53 (t, = 2.8 Hz, 1H), 3.88 (s, 3H). (8). Sodium hydride (7 mg, 0.28 mmol) was suspended in 3 mL of anhydrous DMF. 6-(1-methyl-1(ESI) found (M + H)+ 339.1 (M + H)+; 1H-NMR (400 MHz, CDCl3) 8.70 (d, = 1.7 Hz, 1H), 8.32 (d, = 1.2 Hz, 1H), 7.91 (s, 1H), 7.89 (t, = 1.7 Hz, 1H), 7.87C7.85 (m, 1H), 7.77 (d, = 3.8 Hz, 2H), 7.63C7.56 (m, 1H), 7.49 (t, = 7.7 Hz, 2H), 6.88 (dd, = 3.8, 0.7 PD168393 Hz, 1H), 4.02 (s, 3H). 13C-NMR (126 MHz, CDCl3) 147.08, 144.47, 138.00, 136.93, 134.28, 129.53 (C 2), 129.25, 128.86, 127.36, 126.70 (C 2), 124.81, 120.18, 117.08, 110.45, 39.25. Retention time 2.92 min, >98% purity. Compounds 9 were prepared with a similar procedure as that used for 8. (9). LCCMS (ESI) found (M + H)+ 340.0 (M + H)+; 1H-NMR (400 MHz, CDCl3) 8.71 (s, 1H), 8.28C8.19 (m, 2H), 8.09 (s, 1H), 8.03 (s, 1H), 7.94 (d, = 4.1 Hz, 1H), 7.62 (d, = 7.4 Hz, 1H), 7.54 (t, = 7.7 Hz, 2H), 6.80 (d, = 4.1 Hz, 1H), 4.04 (s, 3H). 13C-NMR (126 MHz, CDCl3) 142.22, 140.54, 139.05, 138.04, 137.96, 137.77, 134.47, 129.14 (C 2), 129.10, 128.96, 128.24 (C 2), 120.98, 106.58, 39.37. Retention time 2.99 min, >99% purity. (37). To a stirred solution of the 5-bromo-2-methylpyridin-3-amine (36) (200 mg, 1.07 mmol) in anhydrous dichloromethane (15 mL) was added benzenesulfonyl chloride (152 L, 1.12 mmol). After 1 h, The mixture was then partially concentrated in vacuo, diluted with EtOAc (40 mL) and saturated NaHCO3 solution (20 mL) and partitioned. The aqueous layer was extracted with EtOAc (2 20 mL). The combined organic layers were dried (Na2SO4), filtered and concentrated to afford 37 (300 mg, 85% yield); LCCMS (ESI) found (M + H)+ 328.1 (M + H)+; 1H-NMR (400 MHz, CDCl3) 8.37 (d, = 2.1 Hz, 1H), 7.92 (d, = 2.1 Hz, 1H), 7.82C7.76 (m, 2H), 7.67C7.61.A solution of 6-bromo-1(ESI) found (M + H)+ 200.0 (M + H)+; 1H-NMR (400 MHz, DMSO-(4). 7.51 (t, = 7.4 Hz, 2 H), 4.03 (s, 3 H). 13C-NMR (126 MHz, CDCl3) 146.75, 142.02, 141.60, 137.29, 137.20, 134.61, 134.41, 129.42 (C 2), 128.85, 128.03, 127.72 (C 2), 119.32, 116.03, 39.38. Retention time 2.95 min, >98% purity. Compounds 5C7 were prepared with a similar procedure as that used for 4. (5). LCCMS (ESI) found (M + H)+ 354.1 (M + H)+; 1H-NMR (400 MHz, CDCl3) 8.72 (d, = 1.9 Hz, 1H), 8.50 (d, = 0.8 Hz, 1H), 7.74 (d, = 0.8 Hz, 1H), 7.69 (dd, = 1.9, 0.8 Hz, 1H), 7.67 (s, 1H), 7.11C7.03 (m, 3H), 6.97 (dd, = 7.9, 1.6 Hz, 2H), 4.70 (s, 2H), 4.00 (s, 3H). 13C-NMR (126 MHz, CDCl3) 146.47, 141.71, 140.45, 137.16, 136.00, 130.55 (C 2), 129.49, 128.56 (C 2), 128.37, 127.73, 126.14, 119.12, 115.27, 60.31, 39.32. Retention time 2.97 min, >98% purity. (6). LCCMS (ESI) found (M + H)+ 290.1 (M + H)+; 1H-NMR (400 MHz, CDCl3) 8.73 (d, = 1.8 Hz, 1H), 8.28 (d, = 0.9 Hz, 1H), 7.81 (s, 1H), 7.72 (s, 1H), 7.64C7.59 (m, 1H), 7.38C7.30 (m, 3H), 7.25C7.21 (m, 2H), 5.64 (s, 2H), 4.00 (s, 3H). 13C-NMR (126 MHz, CDCl3) 140.67, 140.55, 137.55, 137.52, 137.10, 135.76, 131.18, 128.82 (C 2), 128.54, 127.92, 127.73 (C 2), 121.94, 101.51, 47.90, 39.22. Retention time 3.05 min, 98.25% purity. (7). LCCMS (ESI) found (M + H)+ 304.1 (M + H)+; 1H-NMR (400 MHz, CDCl3) 8.74 (d, = 1.9 Hz, 1H), 8.06 (d, = 1.0 Hz, 1H), 7.96 (s, 1H), 7.88 (s, 1H), 7.75 (s, 1H), 7.32C7.24 (m, 3H), 7.14C7.10 (m, 2H), 4.68 (t, = 7.3 Hz, 2H), 4.01 (s, 3H), 3.35 (t, = 7.3 Hz, 2H). 13C-NMR (126 MHz, CDCl3) 153.72, 147.61, 145.87, 142.01, 140.34, 139.20, 137.77, 137.60, 136.48, 129.91, 129.02, 120.95, 110.86, 107.81, 105.68, 64.3, 39.36, 34.2. Retention time 3.08 min, >98% purity. (34). A solution of 6-bromo-1(ESI) found (M + H)+ 199.1 (M + H)+; 1H-NMR (400 MHz, DMSO-= 2.8 Hz, 1H), 6.53 (t, = 2.8 Hz, 1H), 3.88 (s, 3H). (8). Sodium hydride (7 mg, 0.28 mmol) was suspended in 3 mL of anhydrous DMF. 6-(1-methyl-1(ESI) found (M + H)+ 339.1 (M + H)+; 1H-NMR (400 MHz, CDCl3) 8.70 (d, = 1.7 Hz, 1H), 8.32 (d, = 1.2 Hz, 1H), 7.91 (s, 1H), 7.89 PD168393 (t, = 1.7 Hz, 1H), 7.87C7.85 (m, 1H), 7.77 (d, = 3.8 Hz, 2H), 7.63C7.56 (m, 1H), 7.49 (t, = 7.7 Hz, 2H), 6.88 (dd, = 3.8, 0.7 Hz, 1H), 4.02 (s, 3H). 13C-NMR (126 MHz, CDCl3) 147.08, 144.47, 138.00, 136.93, 134.28, 129.53 (C 2), 129.25, 128.86, 127.36, 126.70 (C 2), 124.81, 120.18, 117.08, 110.45, 39.25. Retention time 2.92 min, >98% purity. Compounds 9 were prepared with a similar procedure as that used for 8. (9). LCCMS (ESI) found (M + H)+ 340.0 (M + H)+; 1H-NMR (400 MHz, CDCl3) 8.71 (s, 1H), 8.28C8.19 (m, 2H), 8.09 (s, 1H), 8.03 (s, 1H), 7.94 (d, = 4.1 Hz, 1H), 7.62 (d, = 7.4 Hz, 1H), 7.54 (t, = 7.7 Hz, 2H), 6.80 (d, = 4.1 Hz, 1H), 4.04 (s, 3H). 13C-NMR (126 MHz, CDCl3) 142.22, 140.54, 139.05, 138.04, 137.96, 137.77, 134.47, 129.14 (C 2), 129.10, 128.96, 128.24 (C 2), 120.98, 106.58, 39.37. Retention time 2.99 min, >99% purity. (37). To a stirred solution of the 5-bromo-2-methylpyridin-3-amine (36) (200 mg, 1.07 mmol) in anhydrous dichloromethane (15 mL) was added benzenesulfonyl chloride (152 L, 1.12 mmol). After 1 h, The mixture was then partially concentrated in vacuo, diluted with EtOAc (40 mL) and saturated NaHCO3 solution (20 mL) and partitioned. The aqueous layer was extracted with EtOAc (2 20 mL). The.