1: 93 percent / NaClO2, 2-methyl-2-butene, NaH2PO4 / 2-methyl-propan-2-ol; tetrahydrofuran; H2O / 4 h / Ambient temperature 2: 1) LDA / 1) THF, -78 deg C, 15 min; -40 deg C, 0.5 h, 2) THF, -78 deg C, 15 min 3: 2,6-lutidine / CH2Cl2 / 2 h / 0 °C 4: 1.1 g / K2CO3 / methanol / 0.25 h / 25 °C 5: 78 percent / TBAF / tetrahydrofuran / 8 h / 25 °C 6: 1) Et3N, 2,4,6-trichlorobenzoyl chloride, 2) 4-DMAP / 1) THF, 0 deg C, 15 min, 2) toluene, 25 deg C, 0.5 h 7: 92 percent / CF3CO2H / CH2Cl2 / 1) -20 deg C -> 0 deg C, 2) 0 deg C, 1 h View Scheme

1.1: 100 percent / H2; quinoline / Lindlar's catalyst / ethanol / 20 °C 2.1: 89 percent / pyridine; DMAP / CH2Cl2 / 0 - 20 °C 3.1: 98 percent / 1,2-lutidine / CH2Cl2 / 0 - 20 °C 4.1: 94 percent / NaI / acetone / Heating 5.1: n-BuLi / tetrahydrofuran; hexamethylphosphoric acid triamide / -78 °C 5.2: 68 percent / tetrahydrofuran; hexamethylphosphoric acid triamide / -78 - -30 °C 6.1: DIBALH / CH2Cl2 / -30 °C 7.1: SO3*Py; TEA / CH2Cl2 / 0 °C 8.1: LDA; ZnCl2 / tetrahydrofuran / -78 - -40 °C 8.2: tetrahydrofuran / 1 h / -50 °C 9.1: 2,6-lutidine / CH2Cl2 / 0 - 20 °C 10.1: H2O; acetic acid / 20 °C 11.1: 2,4,6-trichlorobenzoyl chloride; TEA; DMAP / tetrahydrofuran; toluene / 1 h / 20 °C 11.2: 70 percent / H2SiF6 / 2-methyl-propan-2-ol; acetonitrile; CH2Cl2 / 24 h / 20 °C 12.1: 93 percent / oxalyl chloride; TEA; DMSO / CH2Cl2 / -78 °C 13.1: 60 percent / n-BuLi / tetrahydrofuran / -78 - 20 °C 14.1: 92 percent / TFA / CH2Cl2 / 1 h / 0 °C View Scheme

phosphate buffer in dimethyl sulfoxide T=30°C; pH=5.0; 22 h; Equilibrium constant;

1: 99 percent / polystyrene-supported chlorite; polystyrene-supported dihydrogenphosphate; 2,3-dimethylbutene / 2-methyl-propan-2-ol; H2O; tetrahydrofuran / 6 h / 20 °C 2: 100 percent / TBAF / tetrahydrofuran / 4 h / 20 °C 3: Et3N / tetrahydrofuran / 0.83 h / 20 °C 4: polystyrene-supported DMAP / toluene / 2 h / 80 °C 5: 2.2 mg / polymer-supported TsOH / CH2Cl2 / 1 h / 20 °C View Scheme

1: 95 percent / Et3N / CH2Cl2 / 12 h 2: 95 percent / H2 / Pd(OH)2 / tetrahydrofuran / 0.25 h / 25 °C / 2068.6 Torr 3: 91 percent / I2, imidazole, Ph3P / diethyl ether; acetonitrile / 0.5 h / 0 °C 4: 92 percent / 2 h / 100 °C 5: 1.) NaHMDS / 1.) THF, 0 deg C, 0.25 h, 2.) 0 deg C, 15 min 6: 86 percent / CSA / CH2Cl2; methanol / 1.) 0 deg C, 1 h, 2.) 25 deg C, 0.5 h 7: 82 percent / SO3*pyridine, DMSO, Et3N / CH2Cl2 / 0.5 h / 25 °C 8: LDA / tetrahydrofuran / 1.) -78 to -40 deg C, 0.5 h, 2.) -78 deg C 9: 2,6-lutidine / CH2Cl2 / 2 h / 0 °C 10: K2CO3 / methanol / 0.25 h / 25 °C 11: 79 percent / TBAF / tetrahydrofuran / 8 h / 25 °C 12: 1.) 2,4,6-trichlorobenzoylchloride, Et3N, 2.) 4-DMAP / 1.) THF, 25 deg C, 15 min, 2.) toluene, 25 deg C, 0.5 h 13: 92 percent / CF3COOH / CH2Cl2 / 1 h / 0 °C View Scheme

1: 98 percent / NaBH4 / methanol / 0.25 h / 0 °C 2: 95 percent / Et3N / CH2Cl2 / 12 h 3: 95 percent / H2 / Pd(OH)2 / tetrahydrofuran / 0.25 h / 25 °C / 2068.6 Torr 4: 91 percent / I2, imidazole, Ph3P / diethyl ether; acetonitrile / 0.5 h / 0 °C 5: 92 percent / 2 h / 100 °C 6: 1.) NaHMDS / 1.) THF, 0 deg C, 0.25 h, 2.) 0 deg C, 15 min 7: 86 percent / CSA / CH2Cl2; methanol / 1.) 0 deg C, 1 h, 2.) 25 deg C, 0.5 h 8: 82 percent / SO3*pyridine, DMSO, Et3N / CH2Cl2 / 0.5 h / 25 °C 9: LDA / tetrahydrofuran / 1.) -78 to -40 deg C, 0.5 h, 2.) -78 deg C 10: 2,6-lutidine / CH2Cl2 / 2 h / 0 °C 11: K2CO3 / methanol / 0.25 h / 25 °C 12: 79 percent / TBAF / tetrahydrofuran / 8 h / 25 °C 13: 1.) 2,4,6-trichlorobenzoylchloride, Et3N, 2.) 4-DMAP / 1.) THF, 25 deg C, 15 min, 2.) toluene, 25 deg C, 0.5 h 14: 92 percent / CF3COOH / CH2Cl2 / 1 h / 0 °C View Scheme

pyridine hydrogenfluoride in tetrahydrofuran T=22°C; 36 h; Inert atmosphere; Overall yield = 81percent; Overall yield = 15.2 mg; stereoselective reaction;

1.1: Dess-Martin periodinane / CH2Cl2 / 0.25 h / 20 °C 2.1: tetrahydrofuran / 0.33 h / -78 - 20 °C 3.1: aqueous HF / acetonitrile / 16 h 4.1: 95 percent / DMAP; Et3N / CH2Cl2 / 2 h / 0 °C 5.1: 9-BBN / tetrahydrofuran / 4 h / 20 °C 5.2: 60 percent / Cs2CO3; AsPh3 / PdCl2(dppf) / H2O; tetrahydrofuran / 1.5 h 6.1: 93 percent / HF*pyridine / tetrahydrofuran / 36 h / 20 °C 7.1: 92 percent / Dess-Martin periodinane / CH2Cl2 / 1 h / 20 °C 8.1: 87 percent / TiCl4 / CH2Cl2 / 0.25 h / -78 °C 9.1: 89 percent / tetrabutylammonium fluoride / tetrahydrofuran / 0.17 h / 0 °C 10.1: 91 percent / imidazole / dimethylformamide / 36 h / 20 °C 11.1: 95 percent / Dess-Martin periodinane / CH2Cl2 / 2 h / 20 °C 12.1: 62 percent / 2 N NaOH / H2O / 1.5 h / Heating 13.1: Et3N; 2,4,6-trichlorobenzoyl chloride / tetrahydrofuran / 0.08 h / 0 °C 13.2: 73 percent / DMAP / toluene; tetrahydrofuran / 0.5 h / 20 °C 14.1: 82 percent / 2,3-dichloro-5,6-dicyano-1,4-benzoquinone / CH2Cl2; H2O / 2.5 h 15.1: 90 percent / trifluoroacetic acid / CH2Cl2 / 2.5 h / 20 °C View Scheme

1.1: 96 percent / imidazole / dimethylformamide / 2 h / 0 °C 2.1: BH3*THF; cyclohexene / tetrahydrofuran / 3 h / 0 - 20 °C 2.2: 90 percent / NaOH; H2O2 / H2O; tetrahydrofuran / 0.75 h / 20 °C 3.1: Dess-Martin periodinane / CH2Cl2 / 0.25 h / 20 °C 4.1: tetrahydrofuran / 0.33 h / -78 - 20 °C 5.1: aqueous HF / acetonitrile / 16 h 6.1: 95 percent / DMAP; Et3N / CH2Cl2 / 2 h / 0 °C 7.1: 9-BBN / tetrahydrofuran / 4 h / 20 °C 7.2: 60 percent / Cs2CO3; AsPh3 / PdCl2(dppf) / H2O; tetrahydrofuran / 1.5 h 8.1: 93 percent / HF*pyridine / tetrahydrofuran / 36 h / 20 °C 9.1: 92 percent / Dess-Martin periodinane / CH2Cl2 / 1 h / 20 °C 10.1: 87 percent / TiCl4 / CH2Cl2 / 0.25 h / -78 °C 11.1: 89 percent / tetrabutylammonium fluoride / tetrahydrofuran / 0.17 h / 0 °C 12.1: 91 percent / imidazole / dimethylformamide / 36 h / 20 °C 13.1: 95 percent / Dess-Martin periodinane / CH2Cl2 / 2 h / 20 °C 14.1: 62 percent / 2 N NaOH / H2O / 1.5 h / Heating 15.1: Et3N; 2,4,6-trichlorobenzoyl chloride / tetrahydrofuran / 0.08 h / 0 °C 15.2: 73 percent / DMAP / toluene; tetrahydrofuran / 0.5 h / 20 °C 16.1: 82 percent / 2,3-dichloro-5,6-dicyano-1,4-benzoquinone / CH2Cl2; H2O / 2.5 h 17.1: 90 percent / trifluoroacetic acid / CH2Cl2 / 2.5 h / 20 °C View Scheme

1.1: 95 percent / DMAP; Et3N / CH2Cl2 / 16 h / 20 °C 2.1: 80 percent / I2; nBuLi / hexane; tetrahydrofuran / -78 - 20 °C 3.1: 60 percent / BH3*Me2S / various solvent(s); diethyl ether / 1.5 h / 20 °C 4.1: 9-BBN / tetrahydrofuran / 4 h / 20 °C 4.2: 60 percent / Cs2CO3; AsPh3 / PdCl2(dppf) / H2O; tetrahydrofuran / 1.5 h 5.1: 93 percent / HF*pyridine / tetrahydrofuran / 36 h / 20 °C 6.1: 92 percent / Dess-Martin periodinane / CH2Cl2 / 1 h / 20 °C 7.1: 87 percent / TiCl4 / CH2Cl2 / 0.25 h / -78 °C 8.1: 89 percent / tetrabutylammonium fluoride / tetrahydrofuran / 0.17 h / 0 °C 9.1: 91 percent / imidazole / dimethylformamide / 36 h / 20 °C 10.1: 95 percent / Dess-Martin periodinane / CH2Cl2 / 2 h / 20 °C 11.1: 62 percent / 2 N NaOH / H2O / 1.5 h / Heating 12.1: Et3N; 2,4,6-trichlorobenzoyl chloride / tetrahydrofuran / 0.08 h / 0 °C 12.2: 73 percent / DMAP / toluene; tetrahydrofuran / 0.5 h / 20 °C 13.1: 82 percent / 2,3-dichloro-5,6-dicyano-1,4-benzoquinone / CH2Cl2; H2O / 2.5 h 14.1: 90 percent / trifluoroacetic acid / CH2Cl2 / 2.5 h / 20 °C View Scheme