pyridine Title compound not separated from byproducts;

N,N,N',N',N'',N''-hexamethylphosphoric triamide; dilithium tetrachlorocuprate in tetrahydrofuran T=-70 - 0°C;

toluene-4-sulfonic acid in methanol; water T=60°C; 2 h; Yield given;

1: 85 percent / Me3SiBr, ZnBr2 / CH2Cl2 / 0.5 h / -20 °C 2: 1.) EtMgBr, 2.) Li2CuCl4 / 1.) THF, 40-50 deg C, 2.) THF, HMPA, from -70 deg C to 0 deg C, 1 h View Scheme

1: 90 percent / TsOH*H2O / benzene / 0.25 h / Heating 2: 84 percent / CaCl3*7H2O, NaBH4 / methanol / 0.25 h / -50 °C 3: 85 percent / Me3SiBr, ZnBr2 / CH2Cl2 / 0.5 h / -20 °C 4: 1.) EtMgBr, 2.) Li2CuCl4 / 1.) THF, 40-50 deg C, 2.) THF, HMPA, from -70 deg C to 0 deg C, 1 h View Scheme

1: 1.) MeLi / 1.) hexane, Et2O, a) -78 deg C, 2 h, b) -20 deg C, 15 min, 2.) hexane, Et2O, a) -78 deg C, 0.5 h, b) 25 deg C, 2 h 2: 79 percent / diisobutylaluminum hydride / diethyl ether / 3.33 h / 25 - 40 °C 3: 1.) Br2, 2.) tetrabutylammonium fluoride trihydrate / 1.) CH2Cl2, -78 deg C, 2.) THF, CH2Cl2, -20 deg C 4: 87 percent / EtONa, BHA, Pd(PPh3)4 / toluene; ethanol / 0.75 h / 65 °C 5: pyridinium tosylate, BHA, / ethanol / 3 h / 45 °C View Scheme

1: 79 percent / diisobutylaluminum hydride / diethyl ether / 3.33 h / 25 - 40 °C 2: 1.) Br2, 2.) tetrabutylammonium fluoride trihydrate / 1.) CH2Cl2, -78 deg C, 2.) THF, CH2Cl2, -20 deg C 3: 87 percent / EtONa, BHA, Pd(PPh3)4 / toluene; ethanol / 0.75 h / 65 °C 4: pyridinium tosylate, BHA, / ethanol / 3 h / 45 °C View Scheme

1: 87 percent / EtONa, BHA, Pd(PPh3)4 / toluene; ethanol / 0.75 h / 65 °C 2: pyridinium tosylate, BHA, / ethanol / 3 h / 45 °C View Scheme

1: 1.) Br2, 2.) tetrabutylammonium fluoride trihydrate / 1.) CH2Cl2, -78 deg C, 2.) THF, CH2Cl2, -20 deg C 2: 87 percent / EtONa, BHA, Pd(PPh3)4 / toluene; ethanol / 0.75 h / 65 °C 3: pyridinium tosylate, BHA, / ethanol / 3 h / 45 °C View Scheme

1: Li2CuCl4 / tetrahydrofuran / 2 h / 0 °C 2: p-toluol sulfonic acid / methanol; H2O / 2 h / 60 °C View Scheme