1: 100 percent / 80percent m-CPBA, NaHCO3 / CH2Cl2 / 1.5 h / 25 °C 2: n-BuLi / diethyl ether; hexane / 1.) -78 deg C, 30 min, 2.) 25 deg C, 4.5 h 3: 1.) (COCl)2, DMSO, 2.) Et3N / 1.) CH2Cl2, -78 deg C, 30 min, 2.) 5 deg C, 30 min 4: 51 percent / SmI2 / tetrahydrofuran; methanol / 0.33 h / -78 °C 5: 91 percent / K2CO3 / methanol / 2.5 h / 60 °C 6: 79 percent / TMSBr / CH2Cl2 / 1.) -30 deg C, 5 min, 2.) 3 deg C, 30 min 7: 100 percent / TBAF / tetrahydrofuran / 5.5 h / 25 °C 8: 80 percent / Dess-Martin periodinane / CH2Cl2 / 2 h / 25 °C 9: 86 percent / molecular sieves 4 Angstroem / toluene / 1.) -78 deg C, 2 h, 2.) -78 deg C to r.t. 10: 85 percent / t-BuOOH / VO(acac)2 / CH2Cl2 / 7 h / 25 °C 11: 92 percent / Et3N, DMAP / CH2Cl2 / 2.5 h / 3 °C 12: 90 percent / LiEt3BH / tetrahydrofuran / 1 h / 3 °C 13: 95 percent / PDC, molecular sieves 3 Angstroem / CH2Cl2 / 1 h / 25 °C 14: Et3N / CH2Cl2 / 1 h / 3 °C 15: TiCl4 / CH2Cl2 / 3 h / -78 - -15 °C 16: aq. HF / acetonitrile / 2 h / Ambient temperature 17: 72 percent / O2, CuCl, H2O / PdCl2 / dimethylformamide / 15 h / 25 °C 18: 41 percent / TESOTf, 2,6-lutidine / CH2Cl2 / 4 h / 25 °C View Scheme

1: 100 percent / TBAF / tetrahydrofuran / 5.5 h / 25 °C 2: 80 percent / Dess-Martin periodinane / CH2Cl2 / 2 h / 25 °C 3: 86 percent / molecular sieves 4 Angstroem / toluene / 1.) -78 deg C, 2 h, 2.) -78 deg C to r.t. 4: 85 percent / t-BuOOH / VO(acac)2 / CH2Cl2 / 7 h / 25 °C 5: 92 percent / Et3N, DMAP / CH2Cl2 / 2.5 h / 3 °C 6: 90 percent / LiEt3BH / tetrahydrofuran / 1 h / 3 °C 7: 95 percent / PDC, molecular sieves 3 Angstroem / CH2Cl2 / 1 h / 25 °C 8: Et3N / CH2Cl2 / 1 h / 3 °C 9: TiCl4 / CH2Cl2 / 3 h / -78 - -15 °C 10: aq. HF / acetonitrile / 2 h / Ambient temperature 11: 72 percent / O2, CuCl, H2O / PdCl2 / dimethylformamide / 15 h / 25 °C 12: 41 percent / TESOTf, 2,6-lutidine / CH2Cl2 / 4 h / 25 °C View Scheme

1: n-BuLi / diethyl ether; hexane / 1.) -78 deg C, 30 min, 2.) 25 deg C, 4.5 h 2: 1.) (COCl)2, DMSO, 2.) Et3N / 1.) CH2Cl2, -78 deg C, 30 min, 2.) 5 deg C, 30 min 3: 51 percent / SmI2 / tetrahydrofuran; methanol / 0.33 h / -78 °C 4: 91 percent / K2CO3 / methanol / 2.5 h / 60 °C 5: 79 percent / TMSBr / CH2Cl2 / 1.) -30 deg C, 5 min, 2.) 3 deg C, 30 min 6: 100 percent / TBAF / tetrahydrofuran / 5.5 h / 25 °C 7: 80 percent / Dess-Martin periodinane / CH2Cl2 / 2 h / 25 °C 8: 86 percent / molecular sieves 4 Angstroem / toluene / 1.) -78 deg C, 2 h, 2.) -78 deg C to r.t. 9: 85 percent / t-BuOOH / VO(acac)2 / CH2Cl2 / 7 h / 25 °C 10: 92 percent / Et3N, DMAP / CH2Cl2 / 2.5 h / 3 °C 11: 90 percent / LiEt3BH / tetrahydrofuran / 1 h / 3 °C 12: 95 percent / PDC, molecular sieves 3 Angstroem / CH2Cl2 / 1 h / 25 °C 13: Et3N / CH2Cl2 / 1 h / 3 °C 14: TiCl4 / CH2Cl2 / 3 h / -78 - -15 °C 15: aq. HF / acetonitrile / 2 h / Ambient temperature 16: 72 percent / O2, CuCl, H2O / PdCl2 / dimethylformamide / 15 h / 25 °C 17: 41 percent / TESOTf, 2,6-lutidine / CH2Cl2 / 4 h / 25 °C View Scheme

1: 1.) (COCl)2, DMSO, 2.) Et3N / 1.) CH2Cl2, -78 deg C, 30 min, 2.) 5 deg C, 30 min 2: 51 percent / SmI2 / tetrahydrofuran; methanol / 0.33 h / -78 °C 3: 91 percent / K2CO3 / methanol / 2.5 h / 60 °C 4: 79 percent / TMSBr / CH2Cl2 / 1.) -30 deg C, 5 min, 2.) 3 deg C, 30 min 5: 100 percent / TBAF / tetrahydrofuran / 5.5 h / 25 °C 6: 80 percent / Dess-Martin periodinane / CH2Cl2 / 2 h / 25 °C 7: 86 percent / molecular sieves 4 Angstroem / toluene / 1.) -78 deg C, 2 h, 2.) -78 deg C to r.t. 8: 85 percent / t-BuOOH / VO(acac)2 / CH2Cl2 / 7 h / 25 °C 9: 92 percent / Et3N, DMAP / CH2Cl2 / 2.5 h / 3 °C 10: 90 percent / LiEt3BH / tetrahydrofuran / 1 h / 3 °C 11: 95 percent / PDC, molecular sieves 3 Angstroem / CH2Cl2 / 1 h / 25 °C 12: Et3N / CH2Cl2 / 1 h / 3 °C 13: TiCl4 / CH2Cl2 / 3 h / -78 - -15 °C 14: aq. HF / acetonitrile / 2 h / Ambient temperature 15: 72 percent / O2, CuCl, H2O / PdCl2 / dimethylformamide / 15 h / 25 °C 16: 41 percent / TESOTf, 2,6-lutidine / CH2Cl2 / 4 h / 25 °C View Scheme

1: 100 percent / i-Pr2NEt / CH2Cl2 / 18 h / 25 °C 2: 1.) 9-BBN, 2.) 3 N aq. NaOH, 31percent aq. H2O2 / 1.) THF, 25 deg C, 17 h, 2.) 25 deg C, 7 h 3: 87 percent / pyridine, n-Bu3P / 45 h / 25 °C 4: 100 percent / 80percent m-CPBA, NaHCO3 / CH2Cl2 / 1.5 h / 25 °C 5: n-BuLi / diethyl ether; hexane / 1.) -78 deg C, 30 min, 2.) 25 deg C, 4.5 h 6: 1.) (COCl)2, DMSO, 2.) Et3N / 1.) CH2Cl2, -78 deg C, 30 min, 2.) 5 deg C, 30 min 7: 51 percent / SmI2 / tetrahydrofuran; methanol / 0.33 h / -78 °C 8: 91 percent / K2CO3 / methanol / 2.5 h / 60 °C 9: 79 percent / TMSBr / CH2Cl2 / 1.) -30 deg C, 5 min, 2.) 3 deg C, 30 min 10: 100 percent / TBAF / tetrahydrofuran / 5.5 h / 25 °C 11: 80 percent / Dess-Martin periodinane / CH2Cl2 / 2 h / 25 °C 12: 86 percent / molecular sieves 4 Angstroem / toluene / 1.) -78 deg C, 2 h, 2.) -78 deg C to r.t. 13: 85 percent / t-BuOOH / VO(acac)2 / CH2Cl2 / 7 h / 25 °C 14: 92 percent / Et3N, DMAP / CH2Cl2 / 2.5 h / 3 °C 15: 90 percent / LiEt3BH / tetrahydrofuran / 1 h / 3 °C 16: 95 percent / PDC, molecular sieves 3 Angstroem / CH2Cl2 / 1 h / 25 °C 17: Et3N / CH2Cl2 / 1 h / 3 °C 18: TiCl4 / CH2Cl2 / 3 h / -78 - -15 °C 19: aq. HF / acetonitrile / 2 h / Ambient temperature 20: 72 percent / O2, CuCl, H2O / PdCl2 / dimethylformamide / 15 h / 25 °C 21: 41 percent / TESOTf, 2,6-lutidine / CH2Cl2 / 4 h / 25 °C View Scheme

1: 80 percent / pyridine, DMAP / CH2Cl2 / 2 h / 25 °C 2: 100 percent / TBAF / tetrahydrofuran / 15 h / 25 °C 3: 100 percent / pyridine, DMAP / CH2Cl2 / 13 h / 25 °C 4: 88 percent / LiBr*H2O / dimethylformamide / 7.5 h / 70 °C 5: 87 percent / Zn / aq. ethanol / 22 h / Heating 6: 67 percent / PPh3, DEAD / benzene / 15 h / 25 °C 7: 80 percent / NaH / methanol / 2 h / 5 °C 8: 1.) (COCl)2, DMSO, 2.) Et3N / 1.) CH2Cl2, -78 deg C, 30 min, 2.) 0 deg C, 10 min 9: n-BuLi / diethyl ether; hexane / 1.) -78 deg C, 30 min, 2.) 25 deg C, 4.5 h 10: 1.) (COCl)2, DMSO, 2.) Et3N / 1.) CH2Cl2, -78 deg C, 30 min, 2.) 5 deg C, 30 min 11: 51 percent / SmI2 / tetrahydrofuran; methanol / 0.33 h / -78 °C 12: 91 percent / K2CO3 / methanol / 2.5 h / 60 °C 13: 79 percent / TMSBr / CH2Cl2 / 1.) -30 deg C, 5 min, 2.) 3 deg C, 30 min 14: 100 percent / TBAF / tetrahydrofuran / 5.5 h / 25 °C 15: 80 percent / Dess-Martin periodinane / CH2Cl2 / 2 h / 25 °C 16: 86 percent / molecular sieves 4 Angstroem / toluene / 1.) -78 deg C, 2 h, 2.) -78 deg C to r.t. 17: 85 percent / t-BuOOH / VO(acac)2 / CH2Cl2 / 7 h / 25 °C 18: 92 percent / Et3N, DMAP / CH2Cl2 / 2.5 h / 3 °C 19: 90 percent / LiEt3BH / tetrahydrofuran / 1 h / 3 °C 20: 95 percent / PDC, molecular sieves 3 Angstroem / CH2Cl2 / 1 h / 25 °C 21: Et3N / CH2Cl2 / 1 h / 3 °C 22: TiCl4 / CH2Cl2 / 3 h / -78 - -15 °C 23: aq. HF / acetonitrile / 2 h / Ambient temperature 24: 72 percent / O2, CuCl, H2O / PdCl2 / dimethylformamide / 15 h / 25 °C 25: 41 percent / TESOTf, 2,6-lutidine / CH2Cl2 / 4 h / 25 °C View Scheme

1: 1.) Et3SiH, SnCl4, 2.) aq. AcOH / 1.) CH2Cl2, -78 to -60 deg C, 2 h, 2.) THF, 25 deg C, 1 h 2: 80 percent / pyridine, DMAP / CH2Cl2 / 2 h / 25 °C 3: 100 percent / TBAF / tetrahydrofuran / 15 h / 25 °C 4: 100 percent / pyridine, DMAP / CH2Cl2 / 13 h / 25 °C 5: 88 percent / LiBr*H2O / dimethylformamide / 7.5 h / 70 °C 6: 87 percent / Zn / aq. ethanol / 22 h / Heating 7: 67 percent / PPh3, DEAD / benzene / 15 h / 25 °C 8: 80 percent / NaH / methanol / 2 h / 5 °C 9: 1.) (COCl)2, DMSO, 2.) Et3N / 1.) CH2Cl2, -78 deg C, 30 min, 2.) 0 deg C, 10 min 10: n-BuLi / diethyl ether; hexane / 1.) -78 deg C, 30 min, 2.) 25 deg C, 4.5 h 11: 1.) (COCl)2, DMSO, 2.) Et3N / 1.) CH2Cl2, -78 deg C, 30 min, 2.) 5 deg C, 30 min 12: 51 percent / SmI2 / tetrahydrofuran; methanol / 0.33 h / -78 °C 13: 91 percent / K2CO3 / methanol / 2.5 h / 60 °C 14: 79 percent / TMSBr / CH2Cl2 / 1.) -30 deg C, 5 min, 2.) 3 deg C, 30 min 15: 100 percent / TBAF / tetrahydrofuran / 5.5 h / 25 °C 16: 80 percent / Dess-Martin periodinane / CH2Cl2 / 2 h / 25 °C 17: 86 percent / molecular sieves 4 Angstroem / toluene / 1.) -78 deg C, 2 h, 2.) -78 deg C to r.t. 18: 85 percent / t-BuOOH / VO(acac)2 / CH2Cl2 / 7 h / 25 °C 19: 92 percent / Et3N, DMAP / CH2Cl2 / 2.5 h / 3 °C 20: 90 percent / LiEt3BH / tetrahydrofuran / 1 h / 3 °C 21: 95 percent / PDC, molecular sieves 3 Angstroem / CH2Cl2 / 1 h / 25 °C 22: Et3N / CH2Cl2 / 1 h / 3 °C 23: TiCl4 / CH2Cl2 / 3 h / -78 - -15 °C 24: aq. HF / acetonitrile / 2 h / Ambient temperature 25: 72 percent / O2, CuCl, H2O / PdCl2 / dimethylformamide / 15 h / 25 °C 26: 41 percent / TESOTf, 2,6-lutidine / CH2Cl2 / 4 h / 25 °C View Scheme

1: 88 percent / Raney-Ni W-2 / ethanol / 22 h / Heating 2: 1.) Et3SiH, SnCl4, 2.) aq. AcOH / 1.) CH2Cl2, -78 to -60 deg C, 2 h, 2.) THF, 25 deg C, 1 h 3: 80 percent / pyridine, DMAP / CH2Cl2 / 2 h / 25 °C 4: 100 percent / TBAF / tetrahydrofuran / 15 h / 25 °C 5: 100 percent / pyridine, DMAP / CH2Cl2 / 13 h / 25 °C 6: 88 percent / LiBr*H2O / dimethylformamide / 7.5 h / 70 °C 7: 87 percent / Zn / aq. ethanol / 22 h / Heating 8: 67 percent / PPh3, DEAD / benzene / 15 h / 25 °C 9: 80 percent / NaH / methanol / 2 h / 5 °C 10: 1.) (COCl)2, DMSO, 2.) Et3N / 1.) CH2Cl2, -78 deg C, 30 min, 2.) 0 deg C, 10 min 11: n-BuLi / diethyl ether; hexane / 1.) -78 deg C, 30 min, 2.) 25 deg C, 4.5 h 12: 1.) (COCl)2, DMSO, 2.) Et3N / 1.) CH2Cl2, -78 deg C, 30 min, 2.) 5 deg C, 30 min 13: 51 percent / SmI2 / tetrahydrofuran; methanol / 0.33 h / -78 °C 14: 91 percent / K2CO3 / methanol / 2.5 h / 60 °C 15: 79 percent / TMSBr / CH2Cl2 / 1.) -30 deg C, 5 min, 2.) 3 deg C, 30 min 16: 100 percent / TBAF / tetrahydrofuran / 5.5 h / 25 °C 17: 80 percent / Dess-Martin periodinane / CH2Cl2 / 2 h / 25 °C 18: 86 percent / molecular sieves 4 Angstroem / toluene / 1.) -78 deg C, 2 h, 2.) -78 deg C to r.t. 19: 85 percent / t-BuOOH / VO(acac)2 / CH2Cl2 / 7 h / 25 °C 20: 92 percent / Et3N, DMAP / CH2Cl2 / 2.5 h / 3 °C 21: 90 percent / LiEt3BH / tetrahydrofuran / 1 h / 3 °C 22: 95 percent / PDC, molecular sieves 3 Angstroem / CH2Cl2 / 1 h / 25 °C 23: Et3N / CH2Cl2 / 1 h / 3 °C 24: TiCl4 / CH2Cl2 / 3 h / -78 - -15 °C 25: aq. HF / acetonitrile / 2 h / Ambient temperature 26: 72 percent / O2, CuCl, H2O / PdCl2 / dimethylformamide / 15 h / 25 °C 27: 41 percent / TESOTf, 2,6-lutidine / CH2Cl2 / 4 h / 25 °C View Scheme

1: 86 percent / molecular sieves 4 Angstroem / toluene / 1.) -78 deg C, 2 h, 2.) -78 deg C to r.t. 2: 85 percent / t-BuOOH / VO(acac)2 / CH2Cl2 / 7 h / 25 °C 3: 92 percent / Et3N, DMAP / CH2Cl2 / 2.5 h / 3 °C 4: 90 percent / LiEt3BH / tetrahydrofuran / 1 h / 3 °C 5: 95 percent / PDC, molecular sieves 3 Angstroem / CH2Cl2 / 1 h / 25 °C 6: Et3N / CH2Cl2 / 1 h / 3 °C 7: TiCl4 / CH2Cl2 / 3 h / -78 - -15 °C 8: aq. HF / acetonitrile / 2 h / Ambient temperature 9: 72 percent / O2, CuCl, H2O / PdCl2 / dimethylformamide / 15 h / 25 °C 10: 41 percent / TESOTf, 2,6-lutidine / CH2Cl2 / 4 h / 25 °C View Scheme

1: t-BuOK / tetrahydrofuran / 1.) r.t., 40 min, 2.) -60 to -40 deg C, 1 h; -42 to -20 deg C, 3 h 2: 98 percent / PPTS / methanol / 3.5 h / 25 °C 3: 89 percent / imidazole / CH2Cl2 / 18 h / 25 °C 4: 95 percent / aq. AcOH / tetrahydrofuran / 4 h / 25 °C 5: 87 percent / Dess-Martin periodinane / CH2Cl2 / 0.42 h / 25 °C 6: 91 percent / 2-methyl-2-butene, aq. NaClO2, aq. NaH2PO4 / 2-methyl-propan-2-ol / 0.67 h / 25 °C 7: Et3N / toluene / 2 h / 25 °C 8: DMAP / toluene / 3 h / 60 °C 9: 89 percent / aq. NaIO4 / methanol / 2.5 h / 35 °C 10: 1.) pyridine, TFAA, 2.) NaHCO3 / 1.) CH2Cl2, 25 deg C, 1 h, 2.) MeOH, 3 deg C, 1 h 11: TiCl4 / CH2Cl2 / 3 h / -78 - -15 °C 12: aq. HF / acetonitrile / 2 h / Ambient temperature 13: 72 percent / O2, CuCl, H2O / PdCl2 / dimethylformamide / 15 h / 25 °C 14: 41 percent / TESOTf, 2,6-lutidine / CH2Cl2 / 4 h / 25 °C View Scheme