KHF2; hydrogen fluoride in various solvent(s) T=160°C; 1 h;

1: SO2Cl2 / CH2Cl2; dimethylformamide / 3.5 h / -40 - 20 °C 2: 21.0 g / CH2Cl2; dimethylformamide / 15 h / 20 °C 3: 64 percent / aq. HF; KHF2 / various solvent(s) / 1 h / 160 °C View Scheme

1: 1.) HCl gas, AcCl, 2.) H2O / 1.) CH2Cl2, 0 deg C, 12 h, 2.) MeCN, 0 deg C, 30 min 2: 1.) SO2Cl2 / 1.) CH2Cl2, DMF, room temperature, 3 h, 2.) room temperature, 20 h 3: 1.) Et3N*3HF, 2.) Et3N / 1.) EtOAc, 80 deg C, 3 h, 2.) 80 deg C, 1 h View Scheme

1: 98 percent / pyridine / 3 h / Ambient temperature 2: 1percent HCl / methanol / 30 h / Ambient temperature 3: pyridine / 3 h / Ambient temperature 4: AcOH, conc. H2SO4 / Ambient temperature 5: 1.) HCl(g), AcCl, 2.) H2O / 1.) CH2Cl2, 0 deg C, 2.) CH3CN 6: 1.) SO2Cl2 / 1.) CH2Cl2, DMF, from -40 deg C to RT, 3.5 h, 2.) CH2Cl2, DMF, RT, 15 h 7: 65 percent / KHF2, 48percent aq. HF / various solvent(s) / 1 h / 160 °C View Scheme

1: 79 percent / NaBH4, H2O / ethanol / 4 h / Ambient temperature 2: 98 percent / pyridine / 3 h / Ambient temperature 3: 1percent HCl / methanol / 30 h / Ambient temperature 4: pyridine / 3 h / Ambient temperature 5: AcOH, conc. H2SO4 / Ambient temperature 6: 1.) HCl(g), AcCl, 2.) H2O / 1.) CH2Cl2, 0 deg C, 2.) CH3CN 7: 1.) SO2Cl2 / 1.) CH2Cl2, DMF, from -40 deg C to RT, 3.5 h, 2.) CH2Cl2, DMF, RT, 15 h 8: 65 percent / KHF2, 48percent aq. HF / various solvent(s) / 1 h / 160 °C View Scheme

1: 96 percent / pyridinium dichromate, Ac2O / CH2Cl2 / 1.5 h / Heating 2: 79 percent / NaBH4, H2O / ethanol / 4 h / Ambient temperature 3: 98 percent / pyridine / 3 h / Ambient temperature 4: 1percent HCl / methanol / 30 h / Ambient temperature 5: pyridine / 3 h / Ambient temperature 6: AcOH, conc. H2SO4 / Ambient temperature 7: 1.) HCl(g), AcCl, 2.) H2O / 1.) CH2Cl2, 0 deg C, 2.) CH3CN 8: 1.) SO2Cl2 / 1.) CH2Cl2, DMF, from -40 deg C to RT, 3.5 h, 2.) CH2Cl2, DMF, RT, 15 h 9: 65 percent / KHF2, 48percent aq. HF / various solvent(s) / 1 h / 160 °C View Scheme

1: 1percent HCl / methanol / 30 h / Ambient temperature 2: pyridine / 3 h / Ambient temperature 3: AcOH, conc. H2SO4 / Ambient temperature 4: 1.) HCl(g), AcCl, 2.) H2O / 1.) CH2Cl2, 0 deg C, 2.) CH3CN 5: 1.) SO2Cl2 / 1.) CH2Cl2, DMF, from -40 deg C to RT, 3.5 h, 2.) CH2Cl2, DMF, RT, 15 h 6: 65 percent / KHF2, 48percent aq. HF / various solvent(s) / 1 h / 160 °C View Scheme

1: 98 percent / pyridine / 3 h / Ambient temperature 2: 1percent HCl / methanol / 30 h / Ambient temperature 3: pyridine / 3 h / Ambient temperature 4: AcOH, conc. H2SO4 / Ambient temperature 5: 1.) HCl(g), AcCl, 2.) H2O / 1.) CH2Cl2, 0 deg C, 2.) CH3CN 6: 1.) SO2Cl2 / 1.) CH2Cl2, DMF, from -40 deg C to RT, 3.5 h, 2.) CH2Cl2, DMF, RT, 15 h 7: 65 percent / KHF2, 48percent aq. HF / various solvent(s) / 1 h / 160 °C View Scheme

1: 82 percent / pyridine / CH2Cl2 / 1 h / 0 °C 2: 96 percent / pyridinium dichromate, Ac2O / CH2Cl2 / 1.5 h / Heating 3: 79 percent / NaBH4, H2O / ethanol / 4 h / Ambient temperature 4: 98 percent / pyridine / 3 h / Ambient temperature 5: 1percent HCl / methanol / 30 h / Ambient temperature 6: pyridine / 3 h / Ambient temperature 7: AcOH, conc. H2SO4 / Ambient temperature 8: 1.) HCl(g), AcCl, 2.) H2O / 1.) CH2Cl2, 0 deg C, 2.) CH3CN 9: 1.) SO2Cl2 / 1.) CH2Cl2, DMF, from -40 deg C to RT, 3.5 h, 2.) CH2Cl2, DMF, RT, 15 h 10: 65 percent / KHF2, 48percent aq. HF / various solvent(s) / 1 h / 160 °C View Scheme

1: NaBH4 / methanol / 3 h / -20 °C 2: CF3CO2H / Heating 3: HCl / 2 h / Ambient temperature 4: pyridine / 1.) room temperature, 8 h, 2.) 45 deg C, 1.5 h 5: AcOH, H2SO4 / 0 °C 6: 1.) HCl gas, AcCl, 2.) H2O / 1.) CH2Cl2, 0 deg C, 12 h, 2.) MeCN, 0 deg C, 30 min 7: 1.) SO2Cl2 / 1.) CH2Cl2, DMF, room temperature, 3 h, 2.) room temperature, 20 h 8: 1.) Et3N*3HF, 2.) Et3N / 1.) EtOAc, 80 deg C, 3 h, 2.) 80 deg C, 1 h View Scheme