1.1: LiCl; diisopropylamine; n-butyllithium / tetrahydrofuran; petroleum ether / 1.33 h / -78 - 20 °C 1.2: 93 percent / tetrahydrofuran; various solvent(s) / 40 h / 0 °C 2.1: 93 percent / diisopropylamine; n-butyllithium; borane-ammonium complex / tetrahydrofuran; petroleum ether / 2.17 h / 0 - 20 °C 3.1: 95 percent / triphenylphosphine; imidazole; iodine / diethyl ether; acetonitrile / 0.17 h / 20 °C 4.1: tert-butyllithium; ZnCl2 / diethyl ether; petroleum ether / 1 h / 20 °C 4.2: 58 percent / Pd(PPh3)4 / diethyl ether; various solvent(s) / 16 h 5.1: 87 percent / TBAF / tetrahydrofuran / 20 h / 20 °C 6.1: 86 percent / H2 / Rh[(nbd)dppb]BF4 / CH2Cl2 / 4 h / 36201.3 Torr 7.1: 100 percent / 2,6-lutidine / CH2Cl2 / 1 h / 20 °C 8.1: 93 percent / DDQ / CH2Cl2 / 1 h / 20 °C / pH 7 9.1: triethylamine / CH2Cl2 / 1.5 h / 20 °C 10.1: HF / acetonitrile / 3 h / 20 °C 11.1: 98 percent / potassium carbonate / methanol / 0.75 h 12.1: 92 percent / lithium perchlorate / acetonitrile / 24 h / 70 °C 13.1: 81 percent / diisopropylethylamine / CH2Cl2 / 28 h / 20 °C 14.1: DIBAL-H / CH2Cl2; petroleum ether / 1 h / -78 °C 15.1: 2-methyl-2-butene; NaH2PO4; NaClO2 / H2O; 2-methyl-propan-2-ol / 1 h / 0 °C 16.1: K2CO3 / dimethylformamide / 3.5 h / 20 °C 17.1: H2 / Pd/C / tetrahydrofuran; ethanol / 3 h / 10343.2 Torr 18.1: 89 percent / Dess-Martin periodinane / CH2Cl2 / 1 h / 20 °C 19.1: 86 percent / potassium tert-butoxide / tetrahydrofuran / 18 h / -70 - 20 °C 20.1: 91 percent / c. HCl / methanol / 0.5 h / 20 °C 21.1: 94 percent / Pd(PPh3)4; CuI; triethylamine / 12 h / 20 °C 22.1: 94 percent / triethylamine; DAMP / CH2Cl2 / 2 h / 20 °C 23.1: PdCl2(PPh3)2; Bu3SnH / CH2Cl2 23.2: I2 / CH2Cl2 / 0 °C 23.3: potassium carbonate; methanol / -25 - 0 °C 24.1: 97 percent / Pd(PPh3)4; CuI / benzene / 4 h / 80 °C 25.1: 85 percent / P2O5 / 12 h / 20 °C 26.1: 77 percent / trisdimethylamino sulfonyl trimethylsilyldifluoride; water / dimethylformamide / 26 h / 0 °C 27.1: 84 percent / aq. NaOH / tetrahydrofuran / 30 h / 20 °C 28.1: 2,4,6-trichlorobenzoyl chloride; triethylamine; DMAP / tetrahydrofuran; toluene / 25.5 h / 0 - 20 °C 29.1: Me2BBr / CH2Cl2 / 1 h / -78 °C View Scheme

1.1: 94 percent / triphenylphosphine / CH2Cl2 / 0.67 h / -78 - 0 °C 2.1: n-butyllithium / tetrahydrofuran; petroleum ether / 1 h / -25 °C 2.2: 97 percent / tetrahydrofuran; various solvent(s) / 1 h / 20 °C 3.1: Cp2ZrHCl / CH2Cl2 / 2 h 3.2: 89 percent / I2 / CH2Cl2; CCl4 4.1: tert-butyllithium; ZnCl2 / diethyl ether; petroleum ether / 1 h / 20 °C 4.2: 58 percent / Pd(PPh3)4 / diethyl ether; various solvent(s) / 16 h 5.1: 87 percent / TBAF / tetrahydrofuran / 20 h / 20 °C 6.1: 86 percent / H2 / Rh[(nbd)dppb]BF4 / CH2Cl2 / 4 h / 36201.3 Torr 7.1: 100 percent / 2,6-lutidine / CH2Cl2 / 1 h / 20 °C 8.1: 93 percent / DDQ / CH2Cl2 / 1 h / 20 °C / pH 7 9.1: triethylamine / CH2Cl2 / 1.5 h / 20 °C 10.1: HF / acetonitrile / 3 h / 20 °C 11.1: 98 percent / potassium carbonate / methanol / 0.75 h 12.1: 92 percent / lithium perchlorate / acetonitrile / 24 h / 70 °C 13.1: 81 percent / diisopropylethylamine / CH2Cl2 / 28 h / 20 °C 14.1: DIBAL-H / CH2Cl2; petroleum ether / 1 h / -78 °C 15.1: 2-methyl-2-butene; NaH2PO4; NaClO2 / H2O; 2-methyl-propan-2-ol / 1 h / 0 °C 16.1: K2CO3 / dimethylformamide / 3.5 h / 20 °C 17.1: H2 / Pd/C / tetrahydrofuran; ethanol / 3 h / 10343.2 Torr 18.1: 89 percent / Dess-Martin periodinane / CH2Cl2 / 1 h / 20 °C 19.1: 86 percent / potassium tert-butoxide / tetrahydrofuran / 18 h / -70 - 20 °C 20.1: 91 percent / c. HCl / methanol / 0.5 h / 20 °C 21.1: 94 percent / Pd(PPh3)4; CuI; triethylamine / 12 h / 20 °C 22.1: 94 percent / triethylamine; DAMP / CH2Cl2 / 2 h / 20 °C 23.1: PdCl2(PPh3)2; Bu3SnH / CH2Cl2 23.2: I2 / CH2Cl2 / 0 °C 23.3: potassium carbonate; methanol / -25 - 0 °C 24.1: 97 percent / Pd(PPh3)4; CuI / benzene / 4 h / 80 °C 25.1: 85 percent / P2O5 / 12 h / 20 °C 26.1: 77 percent / trisdimethylamino sulfonyl trimethylsilyldifluoride; water / dimethylformamide / 26 h / 0 °C 27.1: 84 percent / aq. NaOH / tetrahydrofuran / 30 h / 20 °C 28.1: 2,4,6-trichlorobenzoyl chloride; triethylamine; DMAP / tetrahydrofuran; toluene / 25.5 h / 0 - 20 °C 29.1: Me2BBr / CH2Cl2 / 1 h / -78 °C View Scheme

1.1: 100 percent / 2,6-lutidine / CH2Cl2 / 1 h / 20 °C 2.1: 93 percent / DDQ / CH2Cl2 / 1 h / 20 °C / pH 7 3.1: triethylamine / CH2Cl2 / 1.5 h / 20 °C 4.1: HF / acetonitrile / 3 h / 20 °C 5.1: 98 percent / potassium carbonate / methanol / 0.75 h 6.1: 92 percent / lithium perchlorate / acetonitrile / 24 h / 70 °C 7.1: 81 percent / diisopropylethylamine / CH2Cl2 / 28 h / 20 °C 8.1: DIBAL-H / CH2Cl2; petroleum ether / 1 h / -78 °C 9.1: 2-methyl-2-butene; NaH2PO4; NaClO2 / H2O; 2-methyl-propan-2-ol / 1 h / 0 °C 10.1: K2CO3 / dimethylformamide / 3.5 h / 20 °C 11.1: H2 / Pd/C / tetrahydrofuran; ethanol / 3 h / 10343.2 Torr 12.1: 89 percent / Dess-Martin periodinane / CH2Cl2 / 1 h / 20 °C 13.1: 86 percent / potassium tert-butoxide / tetrahydrofuran / 18 h / -70 - 20 °C 14.1: 91 percent / c. HCl / methanol / 0.5 h / 20 °C 15.1: 94 percent / Pd(PPh3)4; CuI; triethylamine / 12 h / 20 °C 16.1: 94 percent / triethylamine; DAMP / CH2Cl2 / 2 h / 20 °C 17.1: PdCl2(PPh3)2; Bu3SnH / CH2Cl2 17.2: I2 / CH2Cl2 / 0 °C 17.3: potassium carbonate; methanol / -25 - 0 °C 18.1: 97 percent / Pd(PPh3)4; CuI / benzene / 4 h / 80 °C 19.1: 85 percent / P2O5 / 12 h / 20 °C 20.1: 77 percent / trisdimethylamino sulfonyl trimethylsilyldifluoride; water / dimethylformamide / 26 h / 0 °C 21.1: 84 percent / aq. NaOH / tetrahydrofuran / 30 h / 20 °C 22.1: 2,4,6-trichlorobenzoyl chloride; triethylamine; DMAP / tetrahydrofuran; toluene / 25.5 h / 0 - 20 °C 23.1: Me2BBr / CH2Cl2 / 1 h / -78 °C View Scheme

sodium tetrahydroborate; cerium(III) chloride in methanol T=0°C; Luche reaction; 1 h; Title compound not separated from byproducts;

1.1: 54 percent / tetrahydrofuran / 0.5 h / -78 °C 2.1: 99 percent / 2,6-lutidine / CH2Cl2 / 1 h / 0 °C 3.1: H2O; NMO; OsO4 / acetone / 4 h / 20 °C 4.1: 533 mg / NaIO4; H2O / methanol / 2 h / 0 °C 5.1: 73 percent / benzene / 48 h / 80 °C 6.1: 84 percent / benzene / 39 h / 70 °C 7.1: 96 percent / HF*pyridine; pyridine / tetrahydrofuran / 228 h / 20 °C 8.1: 452 mg / Et3N; DMAP / benzene / 2 h / 20 °C 9.1: 96 percent / PPTS / ethanol / 16 h / 50 °C 10.1: TPAP; NMO; 4 Angstroem molecular sieves / CH2Cl2 / 1.5 h / 20 °C 11.1: SmI2 / tetrahydrofuran / 1 h / -78 °C 11.2: Dess-Martin periodinane / CH2Cl2 / 0.5 h / 20 °C 12.1: DMAP / pentane / 168 h / 20 °C 12.2: 31.2 mg / NaBH4; CeCl3*7H2O / methanol / 0.5 h / 0 °C 13.1: 85 percent / 2,6-lutidine / CH2Cl2 / 0.5 h / 0 °C 14.1: 85 percent / NaBH4 / Pd(PPh3)4 / methanol / 0.5 h / 0 °C 15.1: 69 percent / NH3; Et3N; BOP / dioxane; tetrahydrofuran / 48 h / 23 °C 16.1: 31 percent / 2-chloro-1,3-dimethylimidazolinium chloride / CH2Cl2 / 1.5 h / 20 °C 17.1: 73 percent / K2CO3; MeOH / 1.5 h / 20 °C 18.1: Dess-Martin periodinane / CH2Cl2 / 0.5 h / 20 °C 19.1: 8.50 mg / NaBH4; CeCl3*7H2O / methanol / 0.08 h / 0 °C 20.1: 75 percent / 2,6-lutidine / CH2Cl2 / 1 h / 0 °C 21.1: 90 percent / DDQ; H2O / CH2Cl2 / 0.25 h / 0 °C 22.1: Dess-Martin periodinane / CH2Cl2 / 0.5 h / 20 °C 23.1: NaClO2; NaH2PO4*2H2O; 2-methyl-2-butene / 2-methyl-propan-2-ol; H2O / 0.5 h / 20 °C 24.1: 5.20 mg / HF*pyridine; pyridine / tetrahydrofuran / 48 h / 20 °C View Scheme

1.1: 92 percent / SmI2 / tetrahydrofuran / 0.33 h / -78 °C 2.1: 2,6-lutidine / CH2Cl2 / 0.5 h / 0 °C 3.1: 347 mg / LiOH; aq. H2O2 / tetrahydrofuran / 3 h / 0 °C 4.1: Et3N / benzene / 1 h / 20 °C 5.1: 452 mg / Et3N; DMAP / benzene / 2 h / 20 °C 6.1: 96 percent / PPTS / ethanol / 16 h / 50 °C 7.1: TPAP; NMO; 4 Angstroem molecular sieves / CH2Cl2 / 1.5 h / 20 °C 8.1: SmI2 / tetrahydrofuran / 1 h / -78 °C 8.2: Dess-Martin periodinane / CH2Cl2 / 0.5 h / 20 °C 9.1: DMAP / pentane / 168 h / 20 °C 9.2: 31.2 mg / NaBH4; CeCl3*7H2O / methanol / 0.5 h / 0 °C 10.1: 85 percent / 2,6-lutidine / CH2Cl2 / 0.5 h / 0 °C 11.1: 85 percent / NaBH4 / Pd(PPh3)4 / methanol / 0.5 h / 0 °C 12.1: 69 percent / NH3; Et3N; BOP / dioxane; tetrahydrofuran / 48 h / 23 °C 13.1: 31 percent / 2-chloro-1,3-dimethylimidazolinium chloride / CH2Cl2 / 1.5 h / 20 °C 14.1: 73 percent / K2CO3; MeOH / 1.5 h / 20 °C 15.1: Dess-Martin periodinane / CH2Cl2 / 0.5 h / 20 °C 16.1: 8.50 mg / NaBH4; CeCl3*7H2O / methanol / 0.08 h / 0 °C 17.1: 75 percent / 2,6-lutidine / CH2Cl2 / 1 h / 0 °C 18.1: 90 percent / DDQ; H2O / CH2Cl2 / 0.25 h / 0 °C 19.1: Dess-Martin periodinane / CH2Cl2 / 0.5 h / 20 °C 20.1: NaClO2; NaH2PO4*2H2O; 2-methyl-2-butene / 2-methyl-propan-2-ol; H2O / 0.5 h / 20 °C 21.1: 5.20 mg / HF*pyridine; pyridine / tetrahydrofuran / 48 h / 20 °C View Scheme

1.1: 99 percent / 2,6-lutidine / CH2Cl2 / 1 h / 0 °C 2.1: H2O; NMO; OsO4 / acetone / 4 h / 20 °C 3.1: 533 mg / NaIO4; H2O / methanol / 2 h / 0 °C 4.1: 73 percent / benzene / 48 h / 80 °C 5.1: 84 percent / benzene / 39 h / 70 °C 6.1: 96 percent / HF*pyridine; pyridine / tetrahydrofuran / 228 h / 20 °C 7.1: 452 mg / Et3N; DMAP / benzene / 2 h / 20 °C 8.1: 96 percent / PPTS / ethanol / 16 h / 50 °C 9.1: TPAP; NMO; 4 Angstroem molecular sieves / CH2Cl2 / 1.5 h / 20 °C 10.1: SmI2 / tetrahydrofuran / 1 h / -78 °C 10.2: Dess-Martin periodinane / CH2Cl2 / 0.5 h / 20 °C 11.1: DMAP / pentane / 168 h / 20 °C 11.2: 31.2 mg / NaBH4; CeCl3*7H2O / methanol / 0.5 h / 0 °C 12.1: 85 percent / 2,6-lutidine / CH2Cl2 / 0.5 h / 0 °C 13.1: 85 percent / NaBH4 / Pd(PPh3)4 / methanol / 0.5 h / 0 °C 14.1: 69 percent / NH3; Et3N; BOP / dioxane; tetrahydrofuran / 48 h / 23 °C 15.1: 31 percent / 2-chloro-1,3-dimethylimidazolinium chloride / CH2Cl2 / 1.5 h / 20 °C 16.1: 73 percent / K2CO3; MeOH / 1.5 h / 20 °C 17.1: Dess-Martin periodinane / CH2Cl2 / 0.5 h / 20 °C 18.1: 8.50 mg / NaBH4; CeCl3*7H2O / methanol / 0.08 h / 0 °C 19.1: 75 percent / 2,6-lutidine / CH2Cl2 / 1 h / 0 °C 20.1: 90 percent / DDQ; H2O / CH2Cl2 / 0.25 h / 0 °C 21.1: Dess-Martin periodinane / CH2Cl2 / 0.5 h / 20 °C 22.1: NaClO2; NaH2PO4*2H2O; 2-methyl-2-butene / 2-methyl-propan-2-ol; H2O / 0.5 h / 20 °C 23.1: 5.20 mg / HF*pyridine; pyridine / tetrahydrofuran / 48 h / 20 °C View Scheme

1.1: 89 percent / TPAP; 4 Angstroem molecular sieves; NMO / CH2Cl2 / 0.5 h / 20 °C 2.1: 92 percent / SmI2 / tetrahydrofuran / 0.33 h / -78 °C 3.1: 2,6-lutidine / CH2Cl2 / 0.5 h / 0 °C 4.1: 347 mg / LiOH; aq. H2O2 / tetrahydrofuran / 3 h / 0 °C 5.1: Et3N / benzene / 1 h / 20 °C 6.1: 452 mg / Et3N; DMAP / benzene / 2 h / 20 °C 7.1: 96 percent / PPTS / ethanol / 16 h / 50 °C 8.1: TPAP; NMO; 4 Angstroem molecular sieves / CH2Cl2 / 1.5 h / 20 °C 9.1: SmI2 / tetrahydrofuran / 1 h / -78 °C 9.2: Dess-Martin periodinane / CH2Cl2 / 0.5 h / 20 °C 10.1: DMAP / pentane / 168 h / 20 °C 10.2: 31.2 mg / NaBH4; CeCl3*7H2O / methanol / 0.5 h / 0 °C 11.1: 85 percent / 2,6-lutidine / CH2Cl2 / 0.5 h / 0 °C 12.1: 85 percent / NaBH4 / Pd(PPh3)4 / methanol / 0.5 h / 0 °C 13.1: 69 percent / NH3; Et3N; BOP / dioxane; tetrahydrofuran / 48 h / 23 °C 14.1: 31 percent / 2-chloro-1,3-dimethylimidazolinium chloride / CH2Cl2 / 1.5 h / 20 °C 15.1: 73 percent / K2CO3; MeOH / 1.5 h / 20 °C 16.1: Dess-Martin periodinane / CH2Cl2 / 0.5 h / 20 °C 17.1: 8.50 mg / NaBH4; CeCl3*7H2O / methanol / 0.08 h / 0 °C 18.1: 75 percent / 2,6-lutidine / CH2Cl2 / 1 h / 0 °C 19.1: 90 percent / DDQ; H2O / CH2Cl2 / 0.25 h / 0 °C 20.1: Dess-Martin periodinane / CH2Cl2 / 0.5 h / 20 °C 21.1: NaClO2; NaH2PO4*2H2O; 2-methyl-2-butene / 2-methyl-propan-2-ol; H2O / 0.5 h / 20 °C 22.1: 5.20 mg / HF*pyridine; pyridine / tetrahydrofuran / 48 h / 20 °C View Scheme

1.1: 73 percent / benzene / 48 h / 80 °C 2.1: 84 percent / benzene / 39 h / 70 °C 3.1: 96 percent / HF*pyridine; pyridine / tetrahydrofuran / 228 h / 20 °C 4.1: 452 mg / Et3N; DMAP / benzene / 2 h / 20 °C 5.1: 96 percent / PPTS / ethanol / 16 h / 50 °C 6.1: TPAP; NMO; 4 Angstroem molecular sieves / CH2Cl2 / 1.5 h / 20 °C 7.1: SmI2 / tetrahydrofuran / 1 h / -78 °C 7.2: Dess-Martin periodinane / CH2Cl2 / 0.5 h / 20 °C 8.1: DMAP / pentane / 168 h / 20 °C 8.2: 31.2 mg / NaBH4; CeCl3*7H2O / methanol / 0.5 h / 0 °C 9.1: 85 percent / 2,6-lutidine / CH2Cl2 / 0.5 h / 0 °C 10.1: 85 percent / NaBH4 / Pd(PPh3)4 / methanol / 0.5 h / 0 °C 11.1: 69 percent / NH3; Et3N; BOP / dioxane; tetrahydrofuran / 48 h / 23 °C 12.1: 31 percent / 2-chloro-1,3-dimethylimidazolinium chloride / CH2Cl2 / 1.5 h / 20 °C 13.1: 73 percent / K2CO3; MeOH / 1.5 h / 20 °C 14.1: Dess-Martin periodinane / CH2Cl2 / 0.5 h / 20 °C 15.1: 8.50 mg / NaBH4; CeCl3*7H2O / methanol / 0.08 h / 0 °C 16.1: 75 percent / 2,6-lutidine / CH2Cl2 / 1 h / 0 °C 17.1: 90 percent / DDQ; H2O / CH2Cl2 / 0.25 h / 0 °C 18.1: Dess-Martin periodinane / CH2Cl2 / 0.5 h / 20 °C 19.1: NaClO2; NaH2PO4*2H2O; 2-methyl-2-butene / 2-methyl-propan-2-ol; H2O / 0.5 h / 20 °C 20.1: 5.20 mg / HF*pyridine; pyridine / tetrahydrofuran / 48 h / 20 °C View Scheme

1.1: H2O; NMO; OsO4 / acetone / 4 h / 20 °C 2.1: 533 mg / NaIO4; H2O / methanol / 2 h / 0 °C 3.1: 73 percent / benzene / 48 h / 80 °C 4.1: 84 percent / benzene / 39 h / 70 °C 5.1: 96 percent / HF*pyridine; pyridine / tetrahydrofuran / 228 h / 20 °C 6.1: 452 mg / Et3N; DMAP / benzene / 2 h / 20 °C 7.1: 96 percent / PPTS / ethanol / 16 h / 50 °C 8.1: TPAP; NMO; 4 Angstroem molecular sieves / CH2Cl2 / 1.5 h / 20 °C 9.1: SmI2 / tetrahydrofuran / 1 h / -78 °C 9.2: Dess-Martin periodinane / CH2Cl2 / 0.5 h / 20 °C 10.1: DMAP / pentane / 168 h / 20 °C 10.2: 31.2 mg / NaBH4; CeCl3*7H2O / methanol / 0.5 h / 0 °C 11.1: 85 percent / 2,6-lutidine / CH2Cl2 / 0.5 h / 0 °C 12.1: 85 percent / NaBH4 / Pd(PPh3)4 / methanol / 0.5 h / 0 °C 13.1: 69 percent / NH3; Et3N; BOP / dioxane; tetrahydrofuran / 48 h / 23 °C 14.1: 31 percent / 2-chloro-1,3-dimethylimidazolinium chloride / CH2Cl2 / 1.5 h / 20 °C 15.1: 73 percent / K2CO3; MeOH / 1.5 h / 20 °C 16.1: Dess-Martin periodinane / CH2Cl2 / 0.5 h / 20 °C 17.1: 8.50 mg / NaBH4; CeCl3*7H2O / methanol / 0.08 h / 0 °C 18.1: 75 percent / 2,6-lutidine / CH2Cl2 / 1 h / 0 °C 19.1: 90 percent / DDQ; H2O / CH2Cl2 / 0.25 h / 0 °C 20.1: Dess-Martin periodinane / CH2Cl2 / 0.5 h / 20 °C 21.1: NaClO2; NaH2PO4*2H2O; 2-methyl-2-butene / 2-methyl-propan-2-ol; H2O / 0.5 h / 20 °C 22.1: 5.20 mg / HF*pyridine; pyridine / tetrahydrofuran / 48 h / 20 °C View Scheme