[CH3:1][Si:2]([CH3:27])([CH3:26])[CH2:3][CH2:4][O:5][C:6](=[O:25])[NH:7][C:8]1[CH:13]=[C:12]([CH3:14])[C:11](B2OC(C)(C)C(C)(C)O2)=[C:10]([NH2:24])[CH:9]=1.[C:28]([O:32][C:33](=[O:54])[NH:34][C:35]([C:37]1[S:38][C:39]([S:52][CH3:53])=[C:40]([S:42]([C:45]2[CH:50]=[CH:49][CH:48]=[C:47](Br)[CH:46]=2)(=[O:44])=[O:43])[CH:41]=1)=[NH:36])([CH3:31])([CH3:30])[CH3:29].C([O-])([O-])=O.[Na+].[Na+].C(O)C>C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.O.CCOC(C)=O.C1(C)C=CC=CC=1>[CH3:27][Si:2]([CH3:1])([CH3:26])[CH2:3][CH2:4][O:5][C:6](=[O:25])[NH:7][C:8]1[CH:9]=[C:10]([NH2:24])[C:11]([C:49]2[CH:48]=[CH:47][CH:46]=[C:45]([S:42]([C:40]3[CH:41]=[C:37]([C:35]([NH:34][C:33]([O:32][C:28]([CH3:29])([CH3:30])[CH3:31])=[O:54])=[NH:36])[S:38][C:39]=3[S:52][CH3:53])(=[O:43])=[O:44])[CH:50]=2)=[C:12]([CH3:14])[CH:13]=1A flask with a stirbar was charged with [3-amino-5-methyl-4-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-phenyl]-carbamic acid 2-trimethylsilanyl-ethyl ester ((Example 294: step e) 2.34 g, 5.96 mmol), {[4-(3-bromo-benzenesulfonyl)-5-methylsulfanyl-thiophen-2-yl]-imino-methyl}-carbamic acid tert-butyl ester ((Example 27: step c) 2.93 g, 5.96 mmol), aqueous Na2CO3 (2M, 11.9 mL, 23.8 mmol), ethanol (12 mL) and toluene (24 mL). The solution was sparged with argon for 10 min and Pd(PPh3)4 (689 mg, 0.6 mmol) was added. The biphasic solution was vigorously stirred under inert atmosphere at 80° C. for 16 h, then was cooled to rt. EtOAc (80 mL) and water (20 mL) were added and the layers were separated. The organic layer was washed with saturated NaHCO3 (2×20 mL), brine (20 mL) and was dried over sodium sulfate. Removal of the solvents in vacuo followed by column chromatography (85:15 DCM/EtOAc) of the residue yielded the title compound (2.24 g, 55%) as a light brown solid. 1H-NMR (CDCl3): δ 7.98 (ddd, 1H, J=1.3, 1.9, 7.8 Hz), 7.89 (m, 2H), 7.61 (t, 1H, J=7.7 Hz), 7.5 (dt, 1H, J=1.3, 7.7 Hz), 6.88 (s, 1H), 6.55 (d, 1H, J=1.7 Hz), 6.47 (s, 1H), 4.26 (m, 2H), 3.42 (s, 2H), 2.56 (s, 3H), 1.9 (s, 3H), 1.52 (s, 9H), 1.06 (m, 2H), 0.08 (s, 9H).
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