tetrabutyl ammonium fluoride; acetic acid in tetrahydrofuran; water 29 h;

1: 92 percent / 48 h / 130 °C 2: 1) disiamylborane, BH3*SMe2, 2) 30percent H2O2 / 1) THF, r.t., 30 min, 2) MeOH 3: 84 percent / (COCl)2, DMSO / CH2Cl2 / 0.05 h / -30 °C 4: Me2AlCl, MeOH / CH2Cl2; hexane / 0.5 h / -40 deg C to r.t. 5: 99.4 percent / tetrahydrofuran / 2 h / Ambient temperature 6: 64 percent / NH3 liq., Li / tetrahydrofuran / 1 h 7: 1) KOtBu / 1) THF, r.t., 1 h, 2) THF, r.t., 15 min 8: Bu4NF / tetrahydrofuran / 3 h / Ambient temperature 9: pyridine, 4-(N,N-dimethylamino)pyridine / Ambient temperature 10: 87 percent / p-TsOH, H2O / acetone / 2 h / 56 °C 12: 66 percent / Et3N / 20 h / Ambient temperature 13: 1) s-Bu3BHLi, 2) H2O2 / 1) THF, -78 deg C, 30 min, 2) THF, H2O, to r.t. 14: KOH / methanol / 2 h / 60 °C 15: 99 percent / imidazole / dimethylformamide / 3 h / 80 °C 16: VO(acac)2, tert-butylhydroperoxide / CH2Cl2 / 3 h / 0 °C 17: 89 percent / pyridine, 4-(N,N-dimethylamino)pyridine / 48 h / Ambient temperature 18: 67 percent / CrO3, AcOH / CH2Cl2; H2O / 2 h 19: 1) 2,6-lutidine, trimethylsilyl trifluoromethanesulfonate, 2) Bu4NF, AcOH / 1) CH2Cl2, -60 deg C to 10 deg C, 2 h, 2) THF, 30 min 20: 86 percent / N,N-diethyl-N<<(methoxycarbonyl)amino>sulfonyl>ethanaminium hydroxide / benzene / 0.25 h / 80 °C 21: 85 percent / Bu4NF, AcOH / tetrahydrofuran; H2O / 29 h View Scheme

1: 1) KOtBu / 1) THF, 1 h, r.t., 2) THF, r.t., 1 h 2: 92 percent / 48 h / 130 °C 3: 1) disiamylborane, BH3*SMe2, 2) 30percent H2O2 / 1) THF, r.t., 30 min, 2) MeOH 4: 84 percent / (COCl)2, DMSO / CH2Cl2 / 0.05 h / -30 °C 5: Me2AlCl, MeOH / CH2Cl2; hexane / 0.5 h / -40 deg C to r.t. 6: 99.4 percent / tetrahydrofuran / 2 h / Ambient temperature 7: 64 percent / NH3 liq., Li / tetrahydrofuran / 1 h 8: 1) KOtBu / 1) THF, r.t., 1 h, 2) THF, r.t., 15 min 9: Bu4NF / tetrahydrofuran / 3 h / Ambient temperature 10: pyridine, 4-(N,N-dimethylamino)pyridine / Ambient temperature 11: 87 percent / p-TsOH, H2O / acetone / 2 h / 56 °C 13: 66 percent / Et3N / 20 h / Ambient temperature 14: 1) s-Bu3BHLi, 2) H2O2 / 1) THF, -78 deg C, 30 min, 2) THF, H2O, to r.t. 15: KOH / methanol / 2 h / 60 °C 16: 99 percent / imidazole / dimethylformamide / 3 h / 80 °C 17: VO(acac)2, tert-butylhydroperoxide / CH2Cl2 / 3 h / 0 °C 18: 89 percent / pyridine, 4-(N,N-dimethylamino)pyridine / 48 h / Ambient temperature 19: 67 percent / CrO3, AcOH / CH2Cl2; H2O / 2 h 20: 1) 2,6-lutidine, trimethylsilyl trifluoromethanesulfonate, 2) Bu4NF, AcOH / 1) CH2Cl2, -60 deg C to 10 deg C, 2 h, 2) THF, 30 min 21: 86 percent / N,N-diethyl-N<<(methoxycarbonyl)amino>sulfonyl>ethanaminium hydroxide / benzene / 0.25 h / 80 °C 22: 85 percent / Bu4NF, AcOH / tetrahydrofuran; H2O / 29 h View Scheme

1: 1) KOtBu / 1) THF, r.t., 1 h, 2) THF, r.t., 15 min 2: Bu4NF / tetrahydrofuran / 3 h / Ambient temperature 3: pyridine, 4-(N,N-dimethylamino)pyridine / Ambient temperature 4: 87 percent / p-TsOH, H2O / acetone / 2 h / 56 °C 6: 66 percent / Et3N / 20 h / Ambient temperature 7: 1) s-Bu3BHLi, 2) H2O2 / 1) THF, -78 deg C, 30 min, 2) THF, H2O, to r.t. 8: KOH / methanol / 2 h / 60 °C 9: 99 percent / imidazole / dimethylformamide / 3 h / 80 °C 10: VO(acac)2, tert-butylhydroperoxide / CH2Cl2 / 3 h / 0 °C 11: 89 percent / pyridine, 4-(N,N-dimethylamino)pyridine / 48 h / Ambient temperature 12: 67 percent / CrO3, AcOH / CH2Cl2; H2O / 2 h 13: 1) 2,6-lutidine, trimethylsilyl trifluoromethanesulfonate, 2) Bu4NF, AcOH / 1) CH2Cl2, -60 deg C to 10 deg C, 2 h, 2) THF, 30 min 14: 86 percent / N,N-diethyl-N<<(methoxycarbonyl)amino>sulfonyl>ethanaminium hydroxide / benzene / 0.25 h / 80 °C 15: 85 percent / Bu4NF, AcOH / tetrahydrofuran; H2O / 29 h View Scheme

1: 99 percent / imidazole / dimethylformamide / 3 h / 80 °C 2: VO(acac)2, tert-butylhydroperoxide / CH2Cl2 / 3 h / 0 °C 3: 89 percent / pyridine, 4-(N,N-dimethylamino)pyridine / 48 h / Ambient temperature 4: 67 percent / CrO3, AcOH / CH2Cl2; H2O / 2 h 5: 1) 2,6-lutidine, trimethylsilyl trifluoromethanesulfonate, 2) Bu4NF, AcOH / 1) CH2Cl2, -60 deg C to 10 deg C, 2 h, 2) THF, 30 min 6: 86 percent / N,N-diethyl-N<<(methoxycarbonyl)amino>sulfonyl>ethanaminium hydroxide / benzene / 0.25 h / 80 °C 7: 85 percent / Bu4NF, AcOH / tetrahydrofuran; H2O / 29 h View Scheme

1: 1) disiamylborane, BH3*SMe2, 2) 30percent H2O2 / 1) THF, r.t., 30 min, 2) MeOH 2: 84 percent / (COCl)2, DMSO / CH2Cl2 / 0.05 h / -30 °C 3: Me2AlCl, MeOH / CH2Cl2; hexane / 0.5 h / -40 deg C to r.t. 4: 99.4 percent / tetrahydrofuran / 2 h / Ambient temperature 5: 64 percent / NH3 liq., Li / tetrahydrofuran / 1 h 6: 1) KOtBu / 1) THF, r.t., 1 h, 2) THF, r.t., 15 min 7: Bu4NF / tetrahydrofuran / 3 h / Ambient temperature 8: pyridine, 4-(N,N-dimethylamino)pyridine / Ambient temperature 9: 87 percent / p-TsOH, H2O / acetone / 2 h / 56 °C 11: 66 percent / Et3N / 20 h / Ambient temperature 12: 1) s-Bu3BHLi, 2) H2O2 / 1) THF, -78 deg C, 30 min, 2) THF, H2O, to r.t. 13: KOH / methanol / 2 h / 60 °C 14: 99 percent / imidazole / dimethylformamide / 3 h / 80 °C 15: VO(acac)2, tert-butylhydroperoxide / CH2Cl2 / 3 h / 0 °C 16: 89 percent / pyridine, 4-(N,N-dimethylamino)pyridine / 48 h / Ambient temperature 17: 67 percent / CrO3, AcOH / CH2Cl2; H2O / 2 h 18: 1) 2,6-lutidine, trimethylsilyl trifluoromethanesulfonate, 2) Bu4NF, AcOH / 1) CH2Cl2, -60 deg C to 10 deg C, 2 h, 2) THF, 30 min 19: 86 percent / N,N-diethyl-N<<(methoxycarbonyl)amino>sulfonyl>ethanaminium hydroxide / benzene / 0.25 h / 80 °C 20: 85 percent / Bu4NF, AcOH / tetrahydrofuran; H2O / 29 h View Scheme

1: Me2AlCl, MeOH / CH2Cl2; hexane / 0.5 h / -40 deg C to r.t. 2: 99.4 percent / tetrahydrofuran / 2 h / Ambient temperature 3: 64 percent / NH3 liq., Li / tetrahydrofuran / 1 h 4: 1) KOtBu / 1) THF, r.t., 1 h, 2) THF, r.t., 15 min 5: Bu4NF / tetrahydrofuran / 3 h / Ambient temperature 6: pyridine, 4-(N,N-dimethylamino)pyridine / Ambient temperature 7: 87 percent / p-TsOH, H2O / acetone / 2 h / 56 °C 9: 66 percent / Et3N / 20 h / Ambient temperature 10: 1) s-Bu3BHLi, 2) H2O2 / 1) THF, -78 deg C, 30 min, 2) THF, H2O, to r.t. 11: KOH / methanol / 2 h / 60 °C 12: 99 percent / imidazole / dimethylformamide / 3 h / 80 °C 13: VO(acac)2, tert-butylhydroperoxide / CH2Cl2 / 3 h / 0 °C 14: 89 percent / pyridine, 4-(N,N-dimethylamino)pyridine / 48 h / Ambient temperature 15: 67 percent / CrO3, AcOH / CH2Cl2; H2O / 2 h 16: 1) 2,6-lutidine, trimethylsilyl trifluoromethanesulfonate, 2) Bu4NF, AcOH / 1) CH2Cl2, -60 deg C to 10 deg C, 2 h, 2) THF, 30 min 17: 86 percent / N,N-diethyl-N<<(methoxycarbonyl)amino>sulfonyl>ethanaminium hydroxide / benzene / 0.25 h / 80 °C 18: 85 percent / Bu4NF, AcOH / tetrahydrofuran; H2O / 29 h View Scheme

2: 66 percent / Et3N / 20 h / Ambient temperature 3: 1) s-Bu3BHLi, 2) H2O2 / 1) THF, -78 deg C, 30 min, 2) THF, H2O, to r.t. 4: KOH / methanol / 2 h / 60 °C 5: 99 percent / imidazole / dimethylformamide / 3 h / 80 °C 6: VO(acac)2, tert-butylhydroperoxide / CH2Cl2 / 3 h / 0 °C 7: 89 percent / pyridine, 4-(N,N-dimethylamino)pyridine / 48 h / Ambient temperature 8: 67 percent / CrO3, AcOH / CH2Cl2; H2O / 2 h 9: 1) 2,6-lutidine, trimethylsilyl trifluoromethanesulfonate, 2) Bu4NF, AcOH / 1) CH2Cl2, -60 deg C to 10 deg C, 2 h, 2) THF, 30 min 10: 86 percent / N,N-diethyl-N<<(methoxycarbonyl)amino>sulfonyl>ethanaminium hydroxide / benzene / 0.25 h / 80 °C 11: 85 percent / Bu4NF, AcOH / tetrahydrofuran; H2O / 29 h View Scheme

1: 84 percent / (COCl)2, DMSO / CH2Cl2 / 0.05 h / -30 °C 2: Me2AlCl, MeOH / CH2Cl2; hexane / 0.5 h / -40 deg C to r.t. 3: 99.4 percent / tetrahydrofuran / 2 h / Ambient temperature 4: 64 percent / NH3 liq., Li / tetrahydrofuran / 1 h 5: 1) KOtBu / 1) THF, r.t., 1 h, 2) THF, r.t., 15 min 6: Bu4NF / tetrahydrofuran / 3 h / Ambient temperature 7: pyridine, 4-(N,N-dimethylamino)pyridine / Ambient temperature 8: 87 percent / p-TsOH, H2O / acetone / 2 h / 56 °C 10: 66 percent / Et3N / 20 h / Ambient temperature 11: 1) s-Bu3BHLi, 2) H2O2 / 1) THF, -78 deg C, 30 min, 2) THF, H2O, to r.t. 12: KOH / methanol / 2 h / 60 °C 13: 99 percent / imidazole / dimethylformamide / 3 h / 80 °C 14: VO(acac)2, tert-butylhydroperoxide / CH2Cl2 / 3 h / 0 °C 15: 89 percent / pyridine, 4-(N,N-dimethylamino)pyridine / 48 h / Ambient temperature 16: 67 percent / CrO3, AcOH / CH2Cl2; H2O / 2 h 17: 1) 2,6-lutidine, trimethylsilyl trifluoromethanesulfonate, 2) Bu4NF, AcOH / 1) CH2Cl2, -60 deg C to 10 deg C, 2 h, 2) THF, 30 min 18: 86 percent / N,N-diethyl-N<<(methoxycarbonyl)amino>sulfonyl>ethanaminium hydroxide / benzene / 0.25 h / 80 °C 19: 85 percent / Bu4NF, AcOH / tetrahydrofuran; H2O / 29 h View Scheme

1: 99.4 percent / tetrahydrofuran / 2 h / Ambient temperature 2: 64 percent / NH3 liq., Li / tetrahydrofuran / 1 h 3: 1) KOtBu / 1) THF, r.t., 1 h, 2) THF, r.t., 15 min 4: Bu4NF / tetrahydrofuran / 3 h / Ambient temperature 5: pyridine, 4-(N,N-dimethylamino)pyridine / Ambient temperature 6: 87 percent / p-TsOH, H2O / acetone / 2 h / 56 °C 8: 66 percent / Et3N / 20 h / Ambient temperature 9: 1) s-Bu3BHLi, 2) H2O2 / 1) THF, -78 deg C, 30 min, 2) THF, H2O, to r.t. 10: KOH / methanol / 2 h / 60 °C 11: 99 percent / imidazole / dimethylformamide / 3 h / 80 °C 12: VO(acac)2, tert-butylhydroperoxide / CH2Cl2 / 3 h / 0 °C 13: 89 percent / pyridine, 4-(N,N-dimethylamino)pyridine / 48 h / Ambient temperature 14: 67 percent / CrO3, AcOH / CH2Cl2; H2O / 2 h 15: 1) 2,6-lutidine, trimethylsilyl trifluoromethanesulfonate, 2) Bu4NF, AcOH / 1) CH2Cl2, -60 deg C to 10 deg C, 2 h, 2) THF, 30 min 16: 86 percent / N,N-diethyl-N<<(methoxycarbonyl)amino>sulfonyl>ethanaminium hydroxide / benzene / 0.25 h / 80 °C 17: 85 percent / Bu4NF, AcOH / tetrahydrofuran; H2O / 29 h View Scheme