Br[C:2]1[CH:9]=[C:8]([C:10]([CH3:13])([CH3:12])[CH3:11])[CH:7]=[C:6]([Br:14])[C:3]=1[C:4]#[N:5].[C:15]([C:17]1[CH:22]=[CH:21][C:20]([NH:23][S:24]([CH3:27])(=[O:26])=[O:25])=[CH:19][CH:18]=1)#[CH:16].CCN(C(C)C)C(C)C>>[Br:14][C:6]1[C:3]([C:4]#[N:5])=[C:2]([C:16]#[C:15][C:17]2[CH:18]=[CH:19][C:20]([NH:23][S:24]([CH3:27])(=[O:25])=[O:26])=[CH:21][CH:22]=2)[CH:9]=[C:8]([C:10]([CH3:13])([CH3:12])[CH3:11])[CH:7]=1step 2—A mixture of 92 (0.750 g, 1.90 mmol), Cu(I) (0.027 g, 0.09 mmol), Pd(II)(PPh3)2Cl2 (0.203 g, 0.19 mmol), 80 (0.748 g, 2.85 mmol) and DIPEA (5 mL mL) under an argon atmosphere was heated overnight at 80° C. The reaction was cooled to RT then concentrated. The crude residue was purified by SiO2 chromatography eluting with 40% EtOAc/hexanes to afford 0.293 g (24%) of N-[4-(3-bromo-5-tert-butyl-2-cyano-phenylethynyl)-phenyl]-methanesulfonamide (94) as a light brown solid.
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