triethylamine; palladium diacetate; tris-(o-tolyl)phosphine in acetonitrile T=75°C; P=2585.81 Torr; 16 h; Product distribution / selectivity;

bis (triortho-tolylphosphine)palladium(II) chloride in ethylene glycol diethyl ether T=115°C; 48 h;

hydrogen fluoride in tetrahydrofuran; water; acetonitrile T=65°C; 8 h; Product distribution / selectivity;

1: With potassium carbonate in 1,4-dioxane T=90°C; 1 h; 2: With hydrogenchloride in 1,4-dioxane; water Product distribution / selectivity;

trans-dichlorobis(tri-o-tolyl-phosphine)palladium(II)

potassium carbonate

1: bromine; NaOAc; AcOH / 2.5 h / 20 - 70 °C 2: 96 percent / H2 / tetrahydrofuran / 2.5 h / 1292.87 Torr 3: 46.5 g / pyridine / CH2Cl2 / 0 °C 4: 81 percent / p-toluenesulfonic acid monohydrate; p-xylene / 3 h / Heating 5: 93 percent / BBr3 / CH2Cl2 / -78 - 20 °C 6: 72 percent / dichlorobis(tri-o-tolylphosphine)palladium (II) / 1,2-diethoxy-ethane / 48 h / 115 °C View Scheme

1: thionyl chloride; DMF / 1 h / Heating 2: 46.5 g / pyridine / CH2Cl2 / 0 °C 3: 81 percent / p-toluenesulfonic acid monohydrate; p-xylene / 3 h / Heating 4: 93 percent / BBr3 / CH2Cl2 / -78 - 20 °C 5: 72 percent / dichlorobis(tri-o-tolylphosphine)palladium (II) / 1,2-diethoxy-ethane / 48 h / 115 °C View Scheme

1: 46.5 g / pyridine / CH2Cl2 / 0 °C 2: 81 percent / p-toluenesulfonic acid monohydrate; p-xylene / 3 h / Heating 3: 93 percent / BBr3 / CH2Cl2 / -78 - 20 °C 4: 72 percent / dichlorobis(tri-o-tolylphosphine)palladium (II) / 1,2-diethoxy-ethane / 48 h / 115 °C View Scheme

1: 96 percent / H2 / tetrahydrofuran / 2.5 h / 1292.87 Torr 2: 46.5 g / pyridine / CH2Cl2 / 0 °C 3: 81 percent / p-toluenesulfonic acid monohydrate; p-xylene / 3 h / Heating 4: 93 percent / BBr3 / CH2Cl2 / -78 - 20 °C 5: 72 percent / dichlorobis(tri-o-tolylphosphine)palladium (II) / 1,2-diethoxy-ethane / 48 h / 115 °C View Scheme