Cl[C:2]1[N:7]=[C:6]([O:8][C@@H:9]([C@H:11]2[CH2:15][NH:14][C:13](=[O:16])[CH2:12]2)[CH3:10])[C:5]2[N:17]([CH3:20])[CH:18]=[N:19][C:4]=2[CH:3]=1.O[C@@H]([C@H]1CN([C@@H]([C:31]2[CH:36]=[CH:35][C:34](OC)=[CH:33][CH:32]=2)C)C(=O)C1)C.B(O)O.C(=O)([O-])[O-].[Cs+].[Cs+].CO[CH2:51][CH2:52]OC>O>[CH3:20][N:17]1[C:5]2[C:6]([O:8][C@@H:9]([C@H:11]3[CH2:15][NH:14][C:13](=[O:16])[CH2:12]3)[CH3:10])=[N:7][C:2]([C:31]3[CH:32]=[CH:33][C:34]([N:7]4[CH2:52][CH2:51][NH:17][CH2:5][CH2:6]4)=[CH:35][CH:36]=3)=[CH:3][C:4]=2[N:19]=[CH:18]1To an appropriate sized container charged with a magnetic stir bar, aryl halide 2.06, 2.58 or 2.62 (1 equiv), boronic acid or ester (1.2 equiv), cesium carbonate (3 equiv), and PEPPSI-IPr catalyst (0.1 equiv) were added and reagents were taken up in 2:1 DME:water. After evacuating and backfilling with argon, mixture was heated at 100° C. for one hour. After cooling to room temperature, mixture is poured into water and extracted with ethyl acetate. Combined organics were dried, filtered, and concentrated under reduced pressure and resulting residues were purified by silica gel column chromatography or reverse phase HPLC to yield Examples 3B.01-3B.31.
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