1.1: palladium 10 on activated carbon; hydrogen / ethyl acetate; ethanol / 3 h / 20 °C / 51683.5 Torr 2.1: N-bromosuccinmide / N,N-dimethyl-formamide / 0.5 h / 0 - 20 °C 3.1: sulfuric acid / water; acetonitrile / 0.17 h / 0 °C 3.2: 1.5 h / 0 - 5 °C 3.3: 0.25 h / 0 °C 4.1: potassium hydroxide / methanol; dichloromethane / 1 h / 20 °C / |Inert atmosphere 5.1: potassium carbonate / acetone / 16 h / |Reflux View Scheme

potassium carbonate in ethanol; water T=50°C; Suzuki-Miyaura Coupling; 24 h;

1: palladium 10 on activated carbon; hydrogen / ethyl acetate; ethanol / 3 h / 20 °C / 51683.5 Torr 2: N-bromosuccinmide / N,N-dimethyl-formamide / 0.5 h / 0 - 20 °C View Scheme

1.1: H2 / 10 percent Pd/C / methanol / 1 h / 20 °C 2.1: 0.33 h / 70 °C 3.1: HNO3 / 0.5 h / 0 °C 4.1: HCl / methanol / 2 h / 70 °C 5.1: NaNO2; aq. HCl / ethyl acetate / -15 °C 5.2: KI / ethyl acetate / 0.25 h / -15 °C 6.1: 83 percent / BnEt3NCl / Pd(OAc)2 / dimethylformamide / 2 h / 50 °C 7.1: NaBH4 / methanol / 0.5 h / -15 °C 8.1: pyridine / 0.25 h / 20 °C 9.1: Zn; AcOH / CH2Cl2 / 0.5 h / 20 °C 10.1: Ac2O / CH2Cl2 / 0.5 h / 0 °C 11.1: 89 percent / POCl3; pyridine / CH2Cl2 / 0.67 h / 0 °C 12.1: n-Bu3SnH; AIBN / acetonitrile / 0.5 h / 80 °C 12.2: I2 / acetonitrile / 0.33 h / 20 °C 13.1: Et3N; DMAP / acetonitrile / 1 h / 20 °C 14.1: Ph3As; CuI / BnPd(PPh3)2Cl / hexamethylphosphoric acid triamide; dimethylformamide / 3.5 h / 85 °C 15.1: Na2CO3; H2O / methanol / 2 h / 20 °C 16.1: 89 percent / diethyl azodicarboxylate; PPh3 / benzene; toluene / 0.5 h / 20 °C 17.1: TFA / CH2Cl2 / 0.25 h / 20 °C 18.1: pyrrolidine / methanol; acetonitrile / 0.08 h / 20 °C 19.1: pyrrolidine / methanol; acetonitrile / 4 h / Heating 20.1: 88 percent / PPh3 / CCl4; acetonitrile / 0.5 h / 70 °C 21.1: KOH / methanol / 0.75 h / 80 °C View Scheme

water; hydroxide in 1,4-dioxane T=25°C; Rate constant;

ethanol; sodium hydride in N,N,N',N',N'',N''-hexamethylphosphoric triamide Yields of byproduct given;

palladium diacetate; triphenylphosphine on polystyrene in tetrahydrofuran T=120°C; 2 h;

1.1: H2 / 10 percent Pd/C / methanol / 1 h / 20 °C 2.1: 0.33 h / 70 °C 3.1: HNO3 / 0.5 h / 0 °C 4.1: HCl / methanol / 2 h / 70 °C 5.1: NaNO2; aq. HCl / ethyl acetate / -15 °C 5.2: KI / ethyl acetate / 0.25 h / -15 °C 6.1: 83 percent / BnEt3NCl / Pd(OAc)2 / dimethylformamide / 2 h / 50 °C 7.1: NaBH4 / methanol / 0.5 h / -15 °C 8.1: pyridine / 0.25 h / 20 °C 9.1: Zn; AcOH / CH2Cl2 / 0.5 h / 20 °C 10.1: Ac2O / CH2Cl2 / 0.5 h / 0 °C 11.1: 89 percent / POCl3; pyridine / CH2Cl2 / 0.67 h / 0 °C 12.1: n-Bu3SnH; AIBN / acetonitrile / 0.5 h / 80 °C 12.2: I2 / acetonitrile / 0.33 h / 20 °C 13.1: Et3N; DMAP / acetonitrile / 1 h / 20 °C 14.1: Ph3As; CuI / BnPd(PPh3)2Cl / hexamethylphosphoric acid triamide; dimethylformamide / 3.5 h / 85 °C 15.1: Na2CO3; H2O / methanol / 2 h / 20 °C 16.1: 89 percent / diethyl azodicarboxylate; PPh3 / benzene; toluene / 0.5 h / 20 °C 17.1: TFA / CH2Cl2 / 0.25 h / 20 °C 18.1: pyrrolidine / methanol; acetonitrile / 0.08 h / 20 °C 19.1: pyrrolidine / methanol; acetonitrile / 4 h / Heating 20.1: 88 percent / PPh3 / CCl4; acetonitrile / 0.5 h / 70 °C 21.1: KOH / methanol / 0.75 h / 80 °C 22.1: t-BuOK / tetrahydrofuran; 2-methyl-propan-2-ol / 1.5 h / 0 °C 23.1: 88 percent / (PhSeO)2O / benzene / 0.5 h / 80 °C 24.1: MCPBA; NaHCO3; H2O / methanol; CH2Cl2 / 0.08 h / 0 °C 25.1: NaBH3CN; aq. HCl / methanol; CH2Cl2 / 0.58 h / 0 - 20 °C / pH 3.0 25.2: NaHSO3; Na2CO3 / aq. methanol; CH2Cl2 / 0.5 h / 20 °C / pH 9 - 10 26.1: 91 percent / AcONa / 4 h / 20 °C View Scheme

hydrogen; Ra-Ni in ethanol; ethyl acetate T=23°C; P=72400.7 Torr; 24 h;

sodium hydride 1) HMPA, 20 min, 2) HMPA, RT, 2 h; Yield given. Multistep reaction;