ammonia; water

human carboxylesterase 1b, recombinant in aq. phosphate buffer T=37°C; pH=7.4; 1 h; Enzymatic reaction;

sodium nitrite in acetic anhydride; acetic acid 1.) 0 deg C, 16 h, 2.) room temperature, 8 h;

1: 93 percent / H2 / Pd/C / methanol / 6.5 h / 3102.9 Torr / Ambient temperature 2: 1.) (COCl)2, DMF, 2.) N-hydroxy-2-thiopyridone / 1.) CH2ClCH2Cl, room temperature, 12 h, 2.) CH2ClCH2Cl, room temperature, 1.5 h, 3.) CH2Cl2, irradiation, 0 deg C, 2 h 3: toluene / 24 h / Heating 4: 2.) Et3N / 1.) MeOH, reflux, 2 h, 2.) MeOH, room temperature, 15 h 5: 91 percent / NaIO4 / tetrahydrofuran; H2O / 2 h / Ambient temperature 6: 78 percent / Na2CO3*H2O / tetrahydrofuran; H2O / 16 h 7: 96 percent / aq. NaOH / ethanol / 1.) 0 deg C, 1 h, 2.) room temperature, 1.5 h 8: 80 percent / 0.67 h / 105 - 110 °C 9: 94 percent / Na2CO3, aq. H2O2 / H2O / 24 h / Ambient temperature 10: 96 percent / DMAP / CH2Cl2 / 12 h / Ambient temperature 11: 90 percent / TFA / CH2Cl2 / 1 h / Ambient temperature 12: 75 percent / NaBH3CN / acetonitrile / 1 h / Ambient temperature 13: 93 percent / NaNO2 / acetic acid; acetic anhydride / 1.) 0 deg C, 16 h, 2.) room temperature, 8 h View Scheme

1: 93 percent / Et3N / methanol / 14 h / Ambient temperature 2: 85 percent / KHMDS / tetrahydrofuran / 6 h / -78 °C 3: 87 percent / NaI / pyridine / 7.5 h 4: 88 percent / methanol / 2 h / Ambient temperature 5: 70 percent / NaH / toluene / 1.) room temperature, 30 min, 2.) reflux, 5 h 6: 78 percent / Na2CO3*H2O / tetrahydrofuran; H2O / 16 h 7: 96 percent / aq. NaOH / ethanol / 1.) 0 deg C, 1 h, 2.) room temperature, 1.5 h 8: 80 percent / 0.67 h / 105 - 110 °C 9: 94 percent / Na2CO3, aq. H2O2 / H2O / 24 h / Ambient temperature 10: 96 percent / DMAP / CH2Cl2 / 12 h / Ambient temperature 11: 90 percent / TFA / CH2Cl2 / 1 h / Ambient temperature 12: 75 percent / NaBH3CN / acetonitrile / 1 h / Ambient temperature 13: 93 percent / NaNO2 / acetic acid; acetic anhydride / 1.) 0 deg C, 16 h, 2.) room temperature, 8 h View Scheme

1: 95 percent / AcCl / 14 h / Heating 2: 93 percent / Et3N / methanol / 14 h / Ambient temperature 3: 85 percent / KHMDS / tetrahydrofuran / 6 h / -78 °C 4: 87 percent / NaI / pyridine / 7.5 h 5: 88 percent / methanol / 2 h / Ambient temperature 6: 70 percent / NaH / toluene / 1.) room temperature, 30 min, 2.) reflux, 5 h 7: 78 percent / Na2CO3*H2O / tetrahydrofuran; H2O / 16 h 8: 96 percent / aq. NaOH / ethanol / 1.) 0 deg C, 1 h, 2.) room temperature, 1.5 h 9: 80 percent / 0.67 h / 105 - 110 °C 10: 94 percent / Na2CO3, aq. H2O2 / H2O / 24 h / Ambient temperature 11: 96 percent / DMAP / CH2Cl2 / 12 h / Ambient temperature 12: 90 percent / TFA / CH2Cl2 / 1 h / Ambient temperature 13: 75 percent / NaBH3CN / acetonitrile / 1 h / Ambient temperature 14: 93 percent / NaNO2 / acetic acid; acetic anhydride / 1.) 0 deg C, 16 h, 2.) room temperature, 8 h View Scheme

1: 87 percent / ammonium formate / Pd/C / methanol / 12 h / Heating 2: 95 percent / AcCl / 14 h / Heating 3: 93 percent / Et3N / methanol / 14 h / Ambient temperature 4: 85 percent / KHMDS / tetrahydrofuran / 6 h / -78 °C 5: 87 percent / NaI / pyridine / 7.5 h 6: 88 percent / methanol / 2 h / Ambient temperature 7: 70 percent / NaH / toluene / 1.) room temperature, 30 min, 2.) reflux, 5 h 8: 78 percent / Na2CO3*H2O / tetrahydrofuran; H2O / 16 h 9: 96 percent / aq. NaOH / ethanol / 1.) 0 deg C, 1 h, 2.) room temperature, 1.5 h 10: 80 percent / 0.67 h / 105 - 110 °C 11: 94 percent / Na2CO3, aq. H2O2 / H2O / 24 h / Ambient temperature 12: 96 percent / DMAP / CH2Cl2 / 12 h / Ambient temperature 13: 90 percent / TFA / CH2Cl2 / 1 h / Ambient temperature 14: 75 percent / NaBH3CN / acetonitrile / 1 h / Ambient temperature 15: 93 percent / NaNO2 / acetic acid; acetic anhydride / 1.) 0 deg C, 16 h, 2.) room temperature, 8 h View Scheme

1: 96 percent / H2 / Pd/C / methanol / 5 h 2: 88 percent / methanol / 2 h / Ambient temperature 3: 70 percent / NaH / toluene / 1.) room temperature, 30 min, 2.) reflux, 5 h 4: 78 percent / Na2CO3*H2O / tetrahydrofuran; H2O / 16 h 5: 96 percent / aq. NaOH / ethanol / 1.) 0 deg C, 1 h, 2.) room temperature, 1.5 h 6: 80 percent / 0.67 h / 105 - 110 °C 7: 94 percent / Na2CO3, aq. H2O2 / H2O / 24 h / Ambient temperature 8: 96 percent / DMAP / CH2Cl2 / 12 h / Ambient temperature 9: 90 percent / TFA / CH2Cl2 / 1 h / Ambient temperature 10: 75 percent / NaBH3CN / acetonitrile / 1 h / Ambient temperature 11: 93 percent / NaNO2 / acetic acid; acetic anhydride / 1.) 0 deg C, 16 h, 2.) room temperature, 8 h View Scheme

1: 90 percent / NaI / pyridine / 8 h / Heating 2: 96 percent / H2 / Pd/C / methanol / 5 h 3: 88 percent / methanol / 2 h / Ambient temperature 4: 70 percent / NaH / toluene / 1.) room temperature, 30 min, 2.) reflux, 5 h 5: 78 percent / Na2CO3*H2O / tetrahydrofuran; H2O / 16 h 6: 96 percent / aq. NaOH / ethanol / 1.) 0 deg C, 1 h, 2.) room temperature, 1.5 h 7: 80 percent / 0.67 h / 105 - 110 °C 8: 94 percent / Na2CO3, aq. H2O2 / H2O / 24 h / Ambient temperature 9: 96 percent / DMAP / CH2Cl2 / 12 h / Ambient temperature 10: 90 percent / TFA / CH2Cl2 / 1 h / Ambient temperature 11: 75 percent / NaBH3CN / acetonitrile / 1 h / Ambient temperature 12: 93 percent / NaNO2 / acetic acid; acetic anhydride / 1.) 0 deg C, 16 h, 2.) room temperature, 8 h View Scheme

1: 90 percent / KHMDS / tetrahydrofuran / 1 h / -78 °C 2: 90 percent / NaI / pyridine / 8 h / Heating 3: 96 percent / H2 / Pd/C / methanol / 5 h 4: 88 percent / methanol / 2 h / Ambient temperature 5: 70 percent / NaH / toluene / 1.) room temperature, 30 min, 2.) reflux, 5 h 6: 78 percent / Na2CO3*H2O / tetrahydrofuran; H2O / 16 h 7: 96 percent / aq. NaOH / ethanol / 1.) 0 deg C, 1 h, 2.) room temperature, 1.5 h 8: 80 percent / 0.67 h / 105 - 110 °C 9: 94 percent / Na2CO3, aq. H2O2 / H2O / 24 h / Ambient temperature 10: 96 percent / DMAP / CH2Cl2 / 12 h / Ambient temperature 11: 90 percent / TFA / CH2Cl2 / 1 h / Ambient temperature 12: 75 percent / NaBH3CN / acetonitrile / 1 h / Ambient temperature 13: 93 percent / NaNO2 / acetic acid; acetic anhydride / 1.) 0 deg C, 16 h, 2.) room temperature, 8 h View Scheme