1.1: Pd2(PPh3)2Cl2; copper(l) iodide / triethylamine / 24 h / 20 °C / |Inert atmosphere 2.1: trichlorophosphate; triethylamine / tetrahydrofuran / 1 h / 0 °C / |Inert atmosphere 3.1: palladium diacetate; di-(1-adamantyl)-n-butylphosphine; caesium carbonate / N,N-dimethyl-formamide / 0.17 h / 100 °C / |Inert atmosphere 3.2: 3 h / 100 °C / |Inert atmosphere View Scheme

1: potassium carbonate / water; N,N-dimethyl-formamide / 20 °C 2: copper diacetate; caesium carbonate / N,N-dimethyl-formamide / 1 h / 125 °C View Scheme

1.1: 81 percent / Et3N; P(o-tol)3 / Pd(OAc)2 / acetonitrile / 2.5 h / Heating 2.1: 85 percent / triphosgene; Et3N / CH2Cl2 / 1 h / 0 - 20 °C 3.1: Bu3SnH; AIBN / acetonitrile / 100 °C 3.2: 56 percent / CuI; (2-bromo-4-methylphenyl)carbamic acid tert-butyl ester / Pd(PPh3)4 / dimethylformamide / 50 °C View Scheme

1: 96 percent / CuI; DMF; Et3N / Pd(PPh3)2Cl2 / 12 h / 20 °C 2: 75 percent / Et3N / CH2Cl2 / -50 - 20 °C 3: 91 percent / LiCl / tetrahydrofuran / 4 h / 20 °C 4: 38 percent / iPr2NH; LiCl; POCl3 / tetrahydrofuran / 3 h / 0 - 20 °C View Scheme

1: With copper(l) iodide; potassium carbonate in dimethyl sulfoxide T=120°C; 0.166667 h; 2: With hydrogenchloride in water; dimethyl sulfoxide T=0°C;

1: With copper(l) iodide; K2S in N,N-dimethyl-formamide T=80°C; 12 h; 2: With hydrogenchloride in N,N-dimethyl-formamide T=20°C;

palladium diacetate; CsO2CCMe3; bis(1,1-diphenylphosphino)methane in N,N-dimethyl-formamide T=110°C; 24 h; Inert atmosphere;

copper(l) iodide; bis-triphenylphosphine-palladium(II) chloride Sonogashira coupling;

1: Pd(OAc)2, (o-tol)3P, Et3N / acetonitrile / 80 °C 2: COCl2, Et3N / CH2Cl2 / 0 °C 3: 1.) n-Bu3SnH, AIBN, 2.) 3 N aq. HCl / 1.) CH3CN, 100 deg C, 1 h View Scheme

1.1: NaH; butyllithium / tetrahydrofuran; hexane / 0.5 h / -78 °C 1.2: 57 percent / tetrahydrofuran; hexane / 3 h / -78 °C 2.1: 51 percent / HCl / ethanol; H2O / 1 h / Heating View Scheme