3,3-dimethyldioxirane in dichloromethane T=-50°C; 0.5 h;

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 18.1: 30 percent aq. H2O2; KHCO3 / methanol; acetonitrile / 24 h / 20 °C View Scheme

1.1: BH3*THF; cyclohexene / tetrahydrofuran / 3 h / 0 - 20 °C 1.2: 90 percent / NaOH; H2O2 / H2O; tetrahydrofuran / 0.75 h / 20 °C 2.1: Dess-Martin periodinane / CH2Cl2 / 0.25 h / 20 °C 3.1: tetrahydrofuran / 0.33 h / -78 - 20 °C 4.1: aqueous HF / acetonitrile / 16 h 5.1: 95 percent / DMAP; Et3N / CH2Cl2 / 2 h / 0 °C 6.1: 9-BBN / tetrahydrofuran / 4 h / 20 °C 6.2: 60 percent / Cs2CO3; AsPh3 / PdCl2(dppf) / H2O; tetrahydrofuran / 1.5 h 7.1: 93 percent / HF*pyridine / tetrahydrofuran / 36 h / 20 °C 8.1: 92 percent / Dess-Martin periodinane / CH2Cl2 / 1 h / 20 °C 9.1: 87 percent / TiCl4 / CH2Cl2 / 0.25 h / -78 °C 10.1: 89 percent / tetrabutylammonium fluoride / tetrahydrofuran / 0.17 h / 0 °C 11.1: 91 percent / imidazole / dimethylformamide / 36 h / 20 °C 12.1: 95 percent / Dess-Martin periodinane / CH2Cl2 / 2 h / 20 °C 13.1: 62 percent / 2 N NaOH / H2O / 1.5 h / Heating 14.1: Et3N; 2,4,6-trichlorobenzoyl chloride / tetrahydrofuran / 0.08 h / 0 °C 14.2: 73 percent / DMAP / toluene; tetrahydrofuran / 0.5 h / 20 °C 15.1: 82 percent / 2,3-dichloro-5,6-dicyano-1,4-benzoquinone / CH2Cl2; H2O / 2.5 h 16.1: 90 percent / trifluoroacetic acid / CH2Cl2 / 2.5 h / 20 °C 17.1: 30 percent aq. H2O2; KHCO3 / methanol; acetonitrile / 24 h / 20 °C View Scheme

1.1: aqueous HF / acetonitrile / 16 h 2.1: 95 percent / DMAP; Et3N / CH2Cl2 / 2 h / 0 °C 3.1: 9-BBN / tetrahydrofuran / 4 h / 20 °C 3.2: 60 percent / Cs2CO3; AsPh3 / PdCl2(dppf) / H2O; tetrahydrofuran / 1.5 h 4.1: 93 percent / HF*pyridine / tetrahydrofuran / 36 h / 20 °C 5.1: 92 percent / Dess-Martin periodinane / CH2Cl2 / 1 h / 20 °C 6.1: 87 percent / TiCl4 / CH2Cl2 / 0.25 h / -78 °C 7.1: 89 percent / tetrabutylammonium fluoride / tetrahydrofuran / 0.17 h / 0 °C 8.1: 91 percent / imidazole / dimethylformamide / 36 h / 20 °C 9.1: 95 percent / Dess-Martin periodinane / CH2Cl2 / 2 h / 20 °C 10.1: 62 percent / 2 N NaOH / H2O / 1.5 h / Heating 11.1: Et3N; 2,4,6-trichlorobenzoyl chloride / tetrahydrofuran / 0.08 h / 0 °C 11.2: 73 percent / DMAP / toluene; tetrahydrofuran / 0.5 h / 20 °C 12.1: 82 percent / 2,3-dichloro-5,6-dicyano-1,4-benzoquinone / CH2Cl2; H2O / 2.5 h 13.1: 90 percent / trifluoroacetic acid / CH2Cl2 / 2.5 h / 20 °C 14.1: 30 percent aq. H2O2; KHCO3 / methanol; acetonitrile / 24 h / 20 °C 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 15.1: 56 percent / methyl(trifluoromethyl)dioxirane / acetonitrile / 0 °C View Scheme

1: 88 percent / CF3COOH / CH2Cl2 / 1 h / 0 °C 2: 52 percent / 3,3-dimethyldioxirane / CH2Cl2; acetone / 1 h / -50 - -30 °C View Scheme

1: 88 percent / 3,3-dimethyldioxirane / acetone; CH2Cl2 / 2 h / -50 - -30 °C 2: 93 percent / 2,3-dichloro-5,6-dicyano-1,4-benzoquinone; H2O / CH2Cl2 / 1 h / 20 °C View Scheme

1.1: SmI2 / tetrahydrofuran / 0.33 h / 0 °C 2.1: 114 mg / H2O; B(OH)3 / tetrahydrofuran / 0.5 h / 20 °C 3.1: 91 percent / Et3B; NaBH4 / methanol; tetrahydrofuran / 17 h / -78 °C 4.1: SOCl2; Et3N / CH2Cl2 / 0.33 h / 0 °C 5.1: 58 mg / Bu4NF*3H2O / tetrahydrofuran / 6 h / Heating 6.1: 79 percent / Et3N; DMAP / CH2Cl2 / 15 h / 20 °C 7.1: NMO; OsO4 / tetrahydrofuran; 2-methyl-propan-2-ol; H2O / 18 h / 20 °C 8.1: 4.4 mg / Pb(OAc)4 / ethyl acetate / 0.25 h / 0 °C 9.1: 86 percent / LDA / tetrahydrofuran / 1 h / -78 °C 10.1: 91 percent / pyridine / CH2Cl2 / 2 h / 0 °C 11.1: NMO; OsO4 / tetrahydrofuran; 2-methyl-propan-2-ol; H2O / 18 h / 20 °C 12.1: 98.0 mg / Pb(OAc)4 / ethyl acetate / 0.13 h / 0 °C 13.1: HF*pyridine / pyridine; tetrahydrofuran / 0 - 20 °C 14.1: 63.2 mg / NaClO2; 2-methyl-2-butene / 2-methyl-propan-2-ol; aq. phosphate buffer / 1.5 h / 0 °C 15.1: 2,4,6-trichlorobenzoyl chloride; Et3N 15.2: 74 percent / 4-dimethylaminopyridine 16.1: 82 percent / Zn; NH4Cl / methanol / 0.08 h / 20 °C 17.1: 38 percent / HF*pyridine / pyridine / 168 h / 35 - 40 °C View Scheme

1.1: Mg / diethyl ether / 2 h / Heating 1.2: 43 percent / Li2CuCl4 / diethyl ether; tetrahydrofuran / 2 h / -78 °C 2.1: nBuLi / diethyl ether; various solvent(s) / 0.17 h / -40 °C 2.2: 85 percent / diethyl ether / 12 h / -18 °C 3.1: 76 percent / EtMgBr; i-PrOH / CH2Cl2 / 18 h / 20 °C 4.1: 90 percent / diisopropylethylamine / CH2Cl2 / 0.42 h / 0 °C 5.1: LiHMDS / tetrahydrofuran / 0.33 h / -78 °C 5.2: 87 percent / tetrahydrofuran / -78 - 20 °C 6.1: SmI2 / tetrahydrofuran / 0.33 h / 0 °C 7.1: 114 mg / H2O; B(OH)3 / tetrahydrofuran / 0.5 h / 20 °C 8.1: 91 percent / Et3B; NaBH4 / methanol; tetrahydrofuran / 17 h / -78 °C 9.1: SOCl2; Et3N / CH2Cl2 / 0.33 h / 0 °C 10.1: 58 mg / Bu4NF*3H2O / tetrahydrofuran / 6 h / Heating 11.1: 79 percent / Et3N; DMAP / CH2Cl2 / 15 h / 20 °C 12.1: NMO; OsO4 / tetrahydrofuran; 2-methyl-propan-2-ol; H2O / 18 h / 20 °C 13.1: 4.4 mg / Pb(OAc)4 / ethyl acetate / 0.25 h / 0 °C 14.1: 86 percent / LDA / tetrahydrofuran / 1 h / -78 °C 15.1: 91 percent / pyridine / CH2Cl2 / 2 h / 0 °C 16.1: NMO; OsO4 / tetrahydrofuran; 2-methyl-propan-2-ol; H2O / 18 h / 20 °C 17.1: 98.0 mg / Pb(OAc)4 / ethyl acetate / 0.13 h / 0 °C 18.1: HF*pyridine / pyridine; tetrahydrofuran / 0 - 20 °C 19.1: 63.2 mg / NaClO2; 2-methyl-2-butene / 2-methyl-propan-2-ol; aq. phosphate buffer / 1.5 h / 0 °C 20.1: 2,4,6-trichlorobenzoyl chloride; Et3N 20.2: 74 percent / 4-dimethylaminopyridine 21.1: 82 percent / Zn; NH4Cl / methanol / 0.08 h / 20 °C 22.1: 38 percent / HF*pyridine / pyridine / 168 h / 35 - 40 °C View Scheme

1.1: 76 percent / EtMgBr; i-PrOH / CH2Cl2 / 18 h / 20 °C 2.1: 90 percent / diisopropylethylamine / CH2Cl2 / 0.42 h / 0 °C 3.1: LiHMDS / tetrahydrofuran / 0.33 h / -78 °C 3.2: 87 percent / tetrahydrofuran / -78 - 20 °C 4.1: SmI2 / tetrahydrofuran / 0.33 h / 0 °C 5.1: 114 mg / H2O; B(OH)3 / tetrahydrofuran / 0.5 h / 20 °C 6.1: 91 percent / Et3B; NaBH4 / methanol; tetrahydrofuran / 17 h / -78 °C 7.1: SOCl2; Et3N / CH2Cl2 / 0.33 h / 0 °C 8.1: 58 mg / Bu4NF*3H2O / tetrahydrofuran / 6 h / Heating 9.1: 79 percent / Et3N; DMAP / CH2Cl2 / 15 h / 20 °C 10.1: NMO; OsO4 / tetrahydrofuran; 2-methyl-propan-2-ol; H2O / 18 h / 20 °C 11.1: 4.4 mg / Pb(OAc)4 / ethyl acetate / 0.25 h / 0 °C 12.1: 86 percent / LDA / tetrahydrofuran / 1 h / -78 °C 13.1: 91 percent / pyridine / CH2Cl2 / 2 h / 0 °C 14.1: NMO; OsO4 / tetrahydrofuran; 2-methyl-propan-2-ol; H2O / 18 h / 20 °C 15.1: 98.0 mg / Pb(OAc)4 / ethyl acetate / 0.13 h / 0 °C 16.1: HF*pyridine / pyridine; tetrahydrofuran / 0 - 20 °C 17.1: 63.2 mg / NaClO2; 2-methyl-2-butene / 2-methyl-propan-2-ol; aq. phosphate buffer / 1.5 h / 0 °C 18.1: 2,4,6-trichlorobenzoyl chloride; Et3N 18.2: 74 percent / 4-dimethylaminopyridine 19.1: 82 percent / Zn; NH4Cl / methanol / 0.08 h / 20 °C 20.1: 38 percent / HF*pyridine / pyridine / 168 h / 35 - 40 °C View Scheme