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

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

1: 81 percent / BF3*Et2O / CH2Cl2 / 24 h / Ambient temperature 2: DMAP, pyridine / CH2Cl2 / 72 h / Ambient temperature 3: NBS, H2O / acetone / 0.17 h / -23 °C 4: 1.) n-Bu2BOTf, Et3N / 1.) CH2Cl2, 0 deg C, 1 h, 2.) CH2Cl2, -78 deg C, 1.5 h 5: 86 percent / trifluoromethanesulfonic acid / diethyl ether / 0.08 h / Ambient temperature 6: LiOH*H2O, aq. H2O2 / tetrahydrofuran / 11 h / Ambient temperature 7: diethylphosphoryl cyanide, Et3N / dimethylformamide / 2 h / Ambient temperature 8: 99 percent / tetrahydrofuran; diethyl ether / 0.33 h / -78 °C 9: 1.) LDA / 1.) THF, -78 deg C, 1 h, 2.) THF, -78 deg C, 1 h 10: 1.) 4-dimethylaminopyridine, 2.) DBU / 1.) CH2Cl2, RT, 12 h, 2.) CH2Cl2, from 0 to 20 deg C, 2 h 11: NaBH4, Te, AcOH / ethanol / 4 h / Ambient temperature 12: L-Selectride / tetrahydrofuran / -80 - -30 °C 13: 89 percent / i-Pr2NEt / CH2Cl2 / 0.67 h / -40 °C 14: 81 percent / NBS, AgNO3, 2,4,6-collidine / acetonitrile / 0.17 h / 0 °C 15: 100 percent / L-Selectride / tetrahydrofuran / -40 - -30 °C 16: 89 percent / i-Pr2NEt / CH2Cl2 / 20 h / Ambient temperature 17: 94 percent / H2 / Raney Ni (W2) / ethanol / 72 h / 760 Torr 18: 88 percent / i-Pr2NEt / CH2Cl2 / -40 - -20 °C 19: HF*pyridine / tetrahydrofuran / 60 h / Ambient temperature 20: i-Pr2NEt / CH2Cl2 / 0.5 h / -40 - -20 °C 21: DIBAL-H / CH2Cl2; hexane / 0.5 h / -78 °C 22: DMAP / toluene / 12 h / 50 °C 23: 76 percent / DDQ / CH2Cl2; H2O / 1.5 h / Ambient temperature 24: 87 percent / TPAP, NMO, MS4A / acetonitrile / 1 h / Ambient temperature 25: 1.) NBS, 2.) CrO3, H2SO4 / 1.) THF, phosphate buffer pH 7, 0 deg C, 15 min, 2.) acetone, 0 deg C, 15 min 26: MS 4A, PPC / CH2Cl2 / 12 h / Ambient temperature 27: HF*pyridine / tetrahydrofuran / Ambient temperature View Scheme

1: 1.) n-Bu2BOTf, Et3N / 1.) CH2Cl2, 0 deg C, 1 h, 2.) CH2Cl2, -78 deg C, 1.5 h 2: 86 percent / trifluoromethanesulfonic acid / diethyl ether / 0.08 h / Ambient temperature 3: LiOH*H2O, aq. H2O2 / tetrahydrofuran / 11 h / Ambient temperature 4: diethylphosphoryl cyanide, Et3N / dimethylformamide / 2 h / Ambient temperature 5: 99 percent / tetrahydrofuran; diethyl ether / 0.33 h / -78 °C 6: 1.) LDA / 1.) THF, -78 deg C, 1 h, 2.) THF, -78 deg C, 1 h 7: 1.) 4-dimethylaminopyridine, 2.) DBU / 1.) CH2Cl2, RT, 12 h, 2.) CH2Cl2, from 0 to 20 deg C, 2 h 8: NaBH4, Te, AcOH / ethanol / 4 h / Ambient temperature 9: L-Selectride / tetrahydrofuran / -80 - -30 °C 10: 89 percent / i-Pr2NEt / CH2Cl2 / 0.67 h / -40 °C 11: 81 percent / NBS, AgNO3, 2,4,6-collidine / acetonitrile / 0.17 h / 0 °C 12: 100 percent / L-Selectride / tetrahydrofuran / -40 - -30 °C 13: 89 percent / i-Pr2NEt / CH2Cl2 / 20 h / Ambient temperature 14: 94 percent / H2 / Raney Ni (W2) / ethanol / 72 h / 760 Torr 15: 88 percent / i-Pr2NEt / CH2Cl2 / -40 - -20 °C 16: HF*pyridine / tetrahydrofuran / 60 h / Ambient temperature 17: i-Pr2NEt / CH2Cl2 / 0.5 h / -40 - -20 °C 18: DIBAL-H / CH2Cl2; hexane / 0.5 h / -78 °C 19: DMAP / toluene / 12 h / 50 °C 20: 76 percent / DDQ / CH2Cl2; H2O / 1.5 h / Ambient temperature 21: 87 percent / TPAP, NMO, MS4A / acetonitrile / 1 h / Ambient temperature 22: 1.) NBS, 2.) CrO3, H2SO4 / 1.) THF, phosphate buffer pH 7, 0 deg C, 15 min, 2.) acetone, 0 deg C, 15 min 23: MS 4A, PPC / CH2Cl2 / 12 h / Ambient temperature 24: HF*pyridine / tetrahydrofuran / Ambient temperature View Scheme

1: 1.) LDA / 1.) THF, -78 deg C, 1 h, 2.) THF, -78 deg C, 1 h 2: 1.) 4-dimethylaminopyridine, 2.) DBU / 1.) CH2Cl2, RT, 12 h, 2.) CH2Cl2, from 0 to 20 deg C, 2 h 3: NaBH4, Te, AcOH / ethanol / 4 h / Ambient temperature 4: L-Selectride / tetrahydrofuran / -80 - -30 °C 5: 89 percent / i-Pr2NEt / CH2Cl2 / 0.67 h / -40 °C 6: 81 percent / NBS, AgNO3, 2,4,6-collidine / acetonitrile / 0.17 h / 0 °C 7: 100 percent / L-Selectride / tetrahydrofuran / -40 - -30 °C 8: 89 percent / i-Pr2NEt / CH2Cl2 / 20 h / Ambient temperature 9: 94 percent / H2 / Raney Ni (W2) / ethanol / 72 h / 760 Torr 10: 88 percent / i-Pr2NEt / CH2Cl2 / -40 - -20 °C 11: HF*pyridine / tetrahydrofuran / 60 h / Ambient temperature 12: i-Pr2NEt / CH2Cl2 / 0.5 h / -40 - -20 °C 13: DIBAL-H / CH2Cl2; hexane / 0.5 h / -78 °C 14: DMAP / toluene / 12 h / 50 °C 15: 76 percent / DDQ / CH2Cl2; H2O / 1.5 h / Ambient temperature 16: 87 percent / TPAP, NMO, MS4A / acetonitrile / 1 h / Ambient temperature 17: 1.) NBS, 2.) CrO3, H2SO4 / 1.) THF, phosphate buffer pH 7, 0 deg C, 15 min, 2.) acetone, 0 deg C, 15 min 18: MS 4A, PPC / CH2Cl2 / 12 h / Ambient temperature 19: HF*pyridine / tetrahydrofuran / Ambient temperature View Scheme

1: LiOH*H2O, aq. H2O2 / tetrahydrofuran / 11 h / Ambient temperature 2: diethylphosphoryl cyanide, Et3N / dimethylformamide / 2 h / Ambient temperature 3: 99 percent / tetrahydrofuran; diethyl ether / 0.33 h / -78 °C 4: 1.) LDA / 1.) THF, -78 deg C, 1 h, 2.) THF, -78 deg C, 1 h 5: 1.) 4-dimethylaminopyridine, 2.) DBU / 1.) CH2Cl2, RT, 12 h, 2.) CH2Cl2, from 0 to 20 deg C, 2 h 6: NaBH4, Te, AcOH / ethanol / 4 h / Ambient temperature 7: L-Selectride / tetrahydrofuran / -80 - -30 °C 8: 89 percent / i-Pr2NEt / CH2Cl2 / 0.67 h / -40 °C 9: 81 percent / NBS, AgNO3, 2,4,6-collidine / acetonitrile / 0.17 h / 0 °C 10: 100 percent / L-Selectride / tetrahydrofuran / -40 - -30 °C 11: 89 percent / i-Pr2NEt / CH2Cl2 / 20 h / Ambient temperature 12: 94 percent / H2 / Raney Ni (W2) / ethanol / 72 h / 760 Torr 13: 88 percent / i-Pr2NEt / CH2Cl2 / -40 - -20 °C 14: HF*pyridine / tetrahydrofuran / 60 h / Ambient temperature 15: i-Pr2NEt / CH2Cl2 / 0.5 h / -40 - -20 °C 16: DIBAL-H / CH2Cl2; hexane / 0.5 h / -78 °C 17: DMAP / toluene / 12 h / 50 °C 18: 76 percent / DDQ / CH2Cl2; H2O / 1.5 h / Ambient temperature 19: 87 percent / TPAP, NMO, MS4A / acetonitrile / 1 h / Ambient temperature 20: 1.) NBS, 2.) CrO3, H2SO4 / 1.) THF, phosphate buffer pH 7, 0 deg C, 15 min, 2.) acetone, 0 deg C, 15 min 21: MS 4A, PPC / CH2Cl2 / 12 h / Ambient temperature 22: HF*pyridine / tetrahydrofuran / Ambient temperature View Scheme

1: 100 percent / NaH / tetrahydrofuran; dimethylformamide / 12 h / Ambient temperature 2: 81 percent / BF3*Et2O / CH2Cl2 / 24 h / Ambient temperature 3: DMAP, pyridine / CH2Cl2 / 72 h / Ambient temperature 4: NBS, H2O / acetone / 0.17 h / -23 °C 5: 1.) n-Bu2BOTf, Et3N / 1.) CH2Cl2, 0 deg C, 1 h, 2.) CH2Cl2, -78 deg C, 1.5 h 6: 86 percent / trifluoromethanesulfonic acid / diethyl ether / 0.08 h / Ambient temperature 7: LiOH*H2O, aq. H2O2 / tetrahydrofuran / 11 h / Ambient temperature 8: diethylphosphoryl cyanide, Et3N / dimethylformamide / 2 h / Ambient temperature 9: 99 percent / tetrahydrofuran; diethyl ether / 0.33 h / -78 °C 10: 1.) LDA / 1.) THF, -78 deg C, 1 h, 2.) THF, -78 deg C, 1 h 11: 1.) 4-dimethylaminopyridine, 2.) DBU / 1.) CH2Cl2, RT, 12 h, 2.) CH2Cl2, from 0 to 20 deg C, 2 h 12: NaBH4, Te, AcOH / ethanol / 4 h / Ambient temperature 13: L-Selectride / tetrahydrofuran / -80 - -30 °C 14: 89 percent / i-Pr2NEt / CH2Cl2 / 0.67 h / -40 °C 15: 81 percent / NBS, AgNO3, 2,4,6-collidine / acetonitrile / 0.17 h / 0 °C 16: 100 percent / L-Selectride / tetrahydrofuran / -40 - -30 °C 17: 89 percent / i-Pr2NEt / CH2Cl2 / 20 h / Ambient temperature 18: 94 percent / H2 / Raney Ni (W2) / ethanol / 72 h / 760 Torr 19: 88 percent / i-Pr2NEt / CH2Cl2 / -40 - -20 °C 20: HF*pyridine / tetrahydrofuran / 60 h / Ambient temperature 21: i-Pr2NEt / CH2Cl2 / 0.5 h / -40 - -20 °C 22: DIBAL-H / CH2Cl2; hexane / 0.5 h / -78 °C 23: DMAP / toluene / 12 h / 50 °C 24: 76 percent / DDQ / CH2Cl2; H2O / 1.5 h / Ambient temperature 25: 87 percent / TPAP, NMO, MS4A / acetonitrile / 1 h / Ambient temperature 26: 1.) NBS, 2.) CrO3, H2SO4 / 1.) THF, phosphate buffer pH 7, 0 deg C, 15 min, 2.) acetone, 0 deg C, 15 min 27: MS 4A, PPC / CH2Cl2 / 12 h / Ambient temperature 28: HF*pyridine / tetrahydrofuran / Ambient temperature View Scheme

1: 100 percent / SO3*pyridine, Et3N / dimethylsulfoxide / 2 h / Ambient temperature 2: 1.) LDA / 1.) THF, -78 deg C, 1 h, 2.) THF, -78 deg C, 1 h 3: 1.) 4-dimethylaminopyridine, 2.) DBU / 1.) CH2Cl2, RT, 12 h, 2.) CH2Cl2, from 0 to 20 deg C, 2 h 4: NaBH4, Te, AcOH / ethanol / 4 h / Ambient temperature 5: L-Selectride / tetrahydrofuran / -80 - -30 °C 6: 89 percent / i-Pr2NEt / CH2Cl2 / 0.67 h / -40 °C 7: 81 percent / NBS, AgNO3, 2,4,6-collidine / acetonitrile / 0.17 h / 0 °C 8: 100 percent / L-Selectride / tetrahydrofuran / -40 - -30 °C 9: 89 percent / i-Pr2NEt / CH2Cl2 / 20 h / Ambient temperature 10: 94 percent / H2 / Raney Ni (W2) / ethanol / 72 h / 760 Torr 11: 88 percent / i-Pr2NEt / CH2Cl2 / -40 - -20 °C 12: HF*pyridine / tetrahydrofuran / 60 h / Ambient temperature 13: i-Pr2NEt / CH2Cl2 / 0.5 h / -40 - -20 °C 14: DIBAL-H / CH2Cl2; hexane / 0.5 h / -78 °C 15: DMAP / toluene / 12 h / 50 °C 16: 76 percent / DDQ / CH2Cl2; H2O / 1.5 h / Ambient temperature 17: 87 percent / TPAP, NMO, MS4A / acetonitrile / 1 h / Ambient temperature 18: 1.) NBS, 2.) CrO3, H2SO4 / 1.) THF, phosphate buffer pH 7, 0 deg C, 15 min, 2.) acetone, 0 deg C, 15 min 19: MS 4A, PPC / CH2Cl2 / 12 h / Ambient temperature 20: HF*pyridine / tetrahydrofuran / Ambient temperature View Scheme

1: DMAP, pyridine / CH2Cl2 / 72 h / Ambient temperature 2: NBS, H2O / acetone / 0.17 h / -23 °C 3: 1.) n-Bu2BOTf, Et3N / 1.) CH2Cl2, 0 deg C, 1 h, 2.) CH2Cl2, -78 deg C, 1.5 h 4: 86 percent / trifluoromethanesulfonic acid / diethyl ether / 0.08 h / Ambient temperature 5: LiOH*H2O, aq. H2O2 / tetrahydrofuran / 11 h / Ambient temperature 6: diethylphosphoryl cyanide, Et3N / dimethylformamide / 2 h / Ambient temperature 7: 99 percent / tetrahydrofuran; diethyl ether / 0.33 h / -78 °C 8: 1.) LDA / 1.) THF, -78 deg C, 1 h, 2.) THF, -78 deg C, 1 h 9: 1.) 4-dimethylaminopyridine, 2.) DBU / 1.) CH2Cl2, RT, 12 h, 2.) CH2Cl2, from 0 to 20 deg C, 2 h 10: NaBH4, Te, AcOH / ethanol / 4 h / Ambient temperature 11: L-Selectride / tetrahydrofuran / -80 - -30 °C 12: 89 percent / i-Pr2NEt / CH2Cl2 / 0.67 h / -40 °C 13: 81 percent / NBS, AgNO3, 2,4,6-collidine / acetonitrile / 0.17 h / 0 °C 14: 100 percent / L-Selectride / tetrahydrofuran / -40 - -30 °C 15: 89 percent / i-Pr2NEt / CH2Cl2 / 20 h / Ambient temperature 16: 94 percent / H2 / Raney Ni (W2) / ethanol / 72 h / 760 Torr 17: 88 percent / i-Pr2NEt / CH2Cl2 / -40 - -20 °C 18: HF*pyridine / tetrahydrofuran / 60 h / Ambient temperature 19: i-Pr2NEt / CH2Cl2 / 0.5 h / -40 - -20 °C 20: DIBAL-H / CH2Cl2; hexane / 0.5 h / -78 °C 21: DMAP / toluene / 12 h / 50 °C 22: 76 percent / DDQ / CH2Cl2; H2O / 1.5 h / Ambient temperature 23: 87 percent / TPAP, NMO, MS4A / acetonitrile / 1 h / Ambient temperature 24: 1.) NBS, 2.) CrO3, H2SO4 / 1.) THF, phosphate buffer pH 7, 0 deg C, 15 min, 2.) acetone, 0 deg C, 15 min 25: MS 4A, PPC / CH2Cl2 / 12 h / Ambient temperature 26: HF*pyridine / tetrahydrofuran / Ambient temperature View Scheme

1: 1.) LDA / 1.) THF, -78 deg C, 1 h, 2.) THF, -78 deg C, 1 h 2: 1.) 4-dimethylaminopyridine, 2.) DBU / 1.) CH2Cl2, RT, 12 h, 2.) CH2Cl2, from 0 to 20 deg C, 2 h 3: NaBH4, Te, AcOH / ethanol / 4 h / Ambient temperature 4: L-Selectride / tetrahydrofuran / -80 - -30 °C 5: 89 percent / i-Pr2NEt / CH2Cl2 / 0.67 h / -40 °C 6: 81 percent / NBS, AgNO3, 2,4,6-collidine / acetonitrile / 0.17 h / 0 °C 7: 100 percent / L-Selectride / tetrahydrofuran / -40 - -30 °C 8: 89 percent / i-Pr2NEt / CH2Cl2 / 20 h / Ambient temperature 9: 94 percent / H2 / Raney Ni (W2) / ethanol / 72 h / 760 Torr 10: 88 percent / i-Pr2NEt / CH2Cl2 / -40 - -20 °C 11: HF*pyridine / tetrahydrofuran / 60 h / Ambient temperature 12: i-Pr2NEt / CH2Cl2 / 0.5 h / -40 - -20 °C 13: DIBAL-H / CH2Cl2; hexane / 0.5 h / -78 °C 14: DMAP / toluene / 12 h / 50 °C 15: 76 percent / DDQ / CH2Cl2; H2O / 1.5 h / Ambient temperature 16: 87 percent / TPAP, NMO, MS4A / acetonitrile / 1 h / Ambient temperature 17: 1.) NBS, 2.) CrO3, H2SO4 / 1.) THF, phosphate buffer pH 7, 0 deg C, 15 min, 2.) acetone, 0 deg C, 15 min 18: MS 4A, PPC / CH2Cl2 / 12 h / Ambient temperature 19: HF*pyridine / tetrahydrofuran / Ambient temperature View Scheme