1: 26 g / pyridine / CH2Cl2 / 1 h / 0 °C 2: 26.8 g / NBS, AIBN / CCl4 / 3 h / Heating 3: 34 g / toluene / 36 h / Heating 4: 1) t-BuOK / 1) THF, 0 deg C, 30 min, 2) THF, 0 deg C, 4 h 5: H2, NaHCO3 / 10percent Pd/C / methanol / 760 Torr 6: 14.2 g / KOH / ethanol / Heating 7: 83 percent Turnov. / pyridine / CH2Cl2 / 1.) 0 deg C, 2 h, 2.) r.t., 3 h 8: DOWEX-50X8-400R, MeOH / 20 h / 50 °C 9: Et3N / CH2Cl2 / 1 h / 0 °C 10: 10.6 g / LiI / dimethylformamide / 3.5 h / 90 °C 11: 72 percent Turnov. / AgNO2 / diethyl ether / 1.) 0 deg C, 1 d, 2.) r.t., 12 d, in darkness View Scheme

1: 2) BH3-Me2S / 1) THF, r.t., 2 h, 2) THF, reflux, 3 h 2: 26 g / pyridine / CH2Cl2 / 1 h / 0 °C 3: 26.8 g / NBS, AIBN / CCl4 / 3 h / Heating 4: 34 g / toluene / 36 h / Heating 5: 1) t-BuOK / 1) THF, 0 deg C, 30 min, 2) THF, 0 deg C, 4 h 6: H2, NaHCO3 / 10percent Pd/C / methanol / 760 Torr 7: 14.2 g / KOH / ethanol / Heating 8: 83 percent Turnov. / pyridine / CH2Cl2 / 1.) 0 deg C, 2 h, 2.) r.t., 3 h 9: DOWEX-50X8-400R, MeOH / 20 h / 50 °C 10: Et3N / CH2Cl2 / 1 h / 0 °C 11: 10.6 g / LiI / dimethylformamide / 3.5 h / 90 °C 12: 72 percent Turnov. / AgNO2 / diethyl ether / 1.) 0 deg C, 1 d, 2.) r.t., 12 d, in darkness View Scheme

1: 1) t-BuOK / 1) THF, 0 deg C, 30 min, 2) THF, 0 deg C, 4 h 2: H2, NaHCO3 / 10percent Pd/C / methanol / 760 Torr 3: 14.2 g / KOH / ethanol / Heating 4: 83 percent Turnov. / pyridine / CH2Cl2 / 1.) 0 deg C, 2 h, 2.) r.t., 3 h 5: DOWEX-50X8-400R, MeOH / 20 h / 50 °C 6: Et3N / CH2Cl2 / 1 h / 0 °C 7: 10.6 g / LiI / dimethylformamide / 3.5 h / 90 °C 8: 72 percent Turnov. / AgNO2 / diethyl ether / 1.) 0 deg C, 1 d, 2.) r.t., 12 d, in darkness View Scheme

1: 26.8 g / NBS, AIBN / CCl4 / 3 h / Heating 2: 34 g / toluene / 36 h / Heating 3: 1) t-BuOK / 1) THF, 0 deg C, 30 min, 2) THF, 0 deg C, 4 h 4: H2, NaHCO3 / 10percent Pd/C / methanol / 760 Torr 5: 14.2 g / KOH / ethanol / Heating 6: 83 percent Turnov. / pyridine / CH2Cl2 / 1.) 0 deg C, 2 h, 2.) r.t., 3 h 7: DOWEX-50X8-400R, MeOH / 20 h / 50 °C 8: Et3N / CH2Cl2 / 1 h / 0 °C 9: 10.6 g / LiI / dimethylformamide / 3.5 h / 90 °C 10: 72 percent Turnov. / AgNO2 / diethyl ether / 1.) 0 deg C, 1 d, 2.) r.t., 12 d, in darkness View Scheme

1: 34 g / toluene / 36 h / Heating 2: 1) t-BuOK / 1) THF, 0 deg C, 30 min, 2) THF, 0 deg C, 4 h 3: H2, NaHCO3 / 10percent Pd/C / methanol / 760 Torr 4: 14.2 g / KOH / ethanol / Heating 5: 83 percent Turnov. / pyridine / CH2Cl2 / 1.) 0 deg C, 2 h, 2.) r.t., 3 h 6: DOWEX-50X8-400R, MeOH / 20 h / 50 °C 7: Et3N / CH2Cl2 / 1 h / 0 °C 8: 10.6 g / LiI / dimethylformamide / 3.5 h / 90 °C 9: 72 percent Turnov. / AgNO2 / diethyl ether / 1.) 0 deg C, 1 d, 2.) r.t., 12 d, in darkness View Scheme

1: H2, NaHCO3 / 10percent Pd/C / methanol / 760 Torr 2: 14.2 g / KOH / ethanol / Heating 3: 83 percent Turnov. / pyridine / CH2Cl2 / 1.) 0 deg C, 2 h, 2.) r.t., 3 h 4: DOWEX-50X8-400R, MeOH / 20 h / 50 °C 5: Et3N / CH2Cl2 / 1 h / 0 °C 6: 10.6 g / LiI / dimethylformamide / 3.5 h / 90 °C 7: 72 percent Turnov. / AgNO2 / diethyl ether / 1.) 0 deg C, 1 d, 2.) r.t., 12 d, in darkness View Scheme

1: 1) t-BuOK / 1) THF, 0 deg C, 30 min, 2) THF, 0 deg C, 4 h 2: H2, NaHCO3 / 10percent Pd/C / methanol / 760 Torr 3: 14.2 g / KOH / ethanol / Heating 4: 83 percent Turnov. / pyridine / CH2Cl2 / 1.) 0 deg C, 2 h, 2.) r.t., 3 h 5: DOWEX-50X8-400R, MeOH / 20 h / 50 °C 6: Et3N / CH2Cl2 / 1 h / 0 °C 7: 10.6 g / LiI / dimethylformamide / 3.5 h / 90 °C 8: 72 percent Turnov. / AgNO2 / diethyl ether / 1.) 0 deg C, 1 d, 2.) r.t., 12 d, in darkness View Scheme

AgNO2 in diethyl ether 1.) 0 deg C, 1 d, 2.) r.t., 12 d, in darkness;

1: 6.4 g / SOCl2 / 1.) r.t., overnight, 2.) 40 deg C, 2 h 2: 83 percent Turnov. / pyridine / CH2Cl2 / 1.) 0 deg C, 2 h, 2.) r.t., 3 h 3: DOWEX-50X8-400R, MeOH / 20 h / 50 °C 4: Et3N / CH2Cl2 / 1 h / 0 °C 5: 10.6 g / LiI / dimethylformamide / 3.5 h / 90 °C 6: 72 percent Turnov. / AgNO2 / diethyl ether / 1.) 0 deg C, 1 d, 2.) r.t., 12 d, in darkness View Scheme

1: 83 percent Turnov. / pyridine / CH2Cl2 / 1.) 0 deg C, 2 h, 2.) r.t., 3 h 2: DOWEX-50X8-400R, MeOH / 20 h / 50 °C 3: Et3N / CH2Cl2 / 1 h / 0 °C 4: 10.6 g / LiI / dimethylformamide / 3.5 h / 90 °C 5: 72 percent Turnov. / AgNO2 / diethyl ether / 1.) 0 deg C, 1 d, 2.) r.t., 12 d, in darkness View Scheme