1: 92 percent / 1.15 equiv Bu3SnH / 0.2 equiv bisazoisobutyronitrile / benzene / 24 h / Heating 2: 1.) dimethyl sulfoxide (1.1 equiv), (CF3CO)2O / 1.) CH2Cl2, -65 deg C, 2.) Et3N, 25 deg C, 1 h 3: K2CO3 / dimethylformamide / 48 h / 23 °C 4: 1.) CpZrHCl, 2.) Ni(acac)2, diisobutylaluminium hydride / 1.) THF, 0 deg C, 2.) THF, -10 deg C then 0 deg C, 8 h 5: 1.) Li-sec-Bu3BH (L-Selectride), 2.) tosic acid / 1.) THF, -78 deg C, 2 h, 2.) toluene, reflux, 10 h 6: 97 percent / diisopropylethylamine / CH2Cl2 / 10 h / 23 °C 7: 98 percent / i-Bu2AlH / CH2Cl2 / 1.5 h / -78 °C 8: 94 percent / piperidine / acetonitrile / 48 h / 5 °C 9: 90 percent / diisopropylethylamine / CH2Cl2 / 23 °C 10: 87 percent / HOAc, H2O (3:1) / 5 h / 23 °C 11: 93 percent / 0.15 M LiOH / 24 h / 23 °C / MeOH, H2O (6:1) 12: 1.) lactonization, 2.) MEM ether cleavage View Scheme

1.1: TMSOTf / CH2Cl2; petroleum ether / 2 h 2.1: 2.70 g / NaOMe / methanol / 3 h / 20 °C 3.1: 73.3 percent / DMAP; Et3N / CH2Cl2 / 20 °C 4.1: 86.1 percent / dimethylsulfoxide / 20 °C 5.1: 72.4 percent / cateholborane / 36 h / 20 °C 6.1: 95.4 percent / I2; aq. NaOH / diethyl ether / 0.33 h / 20 °C 7.1: BuLi / tetrahydrofuran; hexane / 1 h / -78 °C 7.2: MeCuCNLi / tetrahydrofuran; hexane; diethyl ether / 1 h / -78 °C 7.3: 92.6 percent / tetrahydrofuran; hexane; diethyl ether / 1 h / -78 °C 8.1: 131 mg / (S)-2-methyl-CBS-oxazaborolidine; BH3*Me2S / tetrahydrofuran; toluene / 0.25 h / 0 °C 9.1: 96.4 percent / diethyl ether / 1 h / 0 °C 10.1: 72 percent / Li-naphthalene / tetrahydrofuran / -25 °C 11.1: MnO2 / CH2Cl2 / 3 h / Heating 12.1: 33.6 mg / NaH2PO4; 2-methyl-2-butene; NaClO2 / 2-methyl-propan-2-ol; H2O / 20 °C 13.1: NEt3; 2,4,6-trichlorobenzoyl chloride / tetrahydrofuran / 6 h 13.2: 81 percent / DMAP / tetrahydrofuran; toluene / Heating 14.1: 91 percent / aq. HCl / tetrahydrofuran; H2O / 48 h / 20 °C View Scheme

1.1: 73.3 percent / DMAP; Et3N / CH2Cl2 / 20 °C 2.1: 86.1 percent / dimethylsulfoxide / 20 °C 3.1: 72.4 percent / cateholborane / 36 h / 20 °C 4.1: 95.4 percent / I2; aq. NaOH / diethyl ether / 0.33 h / 20 °C 5.1: BuLi / tetrahydrofuran; hexane / 1 h / -78 °C 5.2: MeCuCNLi / tetrahydrofuran; hexane; diethyl ether / 1 h / -78 °C 5.3: 92.6 percent / tetrahydrofuran; hexane; diethyl ether / 1 h / -78 °C 6.1: 131 mg / (S)-2-methyl-CBS-oxazaborolidine; BH3*Me2S / tetrahydrofuran; toluene / 0.25 h / 0 °C 7.1: 96.4 percent / diethyl ether / 1 h / 0 °C 8.1: 72 percent / Li-naphthalene / tetrahydrofuran / -25 °C 9.1: MnO2 / CH2Cl2 / 3 h / Heating 10.1: 33.6 mg / NaH2PO4; 2-methyl-2-butene; NaClO2 / 2-methyl-propan-2-ol; H2O / 20 °C 11.1: NEt3; 2,4,6-trichlorobenzoyl chloride / tetrahydrofuran / 6 h 11.2: 81 percent / DMAP / tetrahydrofuran; toluene / Heating 12.1: 91 percent / aq. HCl / tetrahydrofuran; H2O / 48 h / 20 °C View Scheme

1.1: 72.4 percent / cateholborane / 36 h / 20 °C 2.1: 95.4 percent / I2; aq. NaOH / diethyl ether / 0.33 h / 20 °C 3.1: BuLi / tetrahydrofuran; hexane / 1 h / -78 °C 3.2: MeCuCNLi / tetrahydrofuran; hexane; diethyl ether / 1 h / -78 °C 3.3: 92.6 percent / tetrahydrofuran; hexane; diethyl ether / 1 h / -78 °C 4.1: 131 mg / (S)-2-methyl-CBS-oxazaborolidine; BH3*Me2S / tetrahydrofuran; toluene / 0.25 h / 0 °C 5.1: 96.4 percent / diethyl ether / 1 h / 0 °C 6.1: 72 percent / Li-naphthalene / tetrahydrofuran / -25 °C 7.1: MnO2 / CH2Cl2 / 3 h / Heating 8.1: 33.6 mg / NaH2PO4; 2-methyl-2-butene; NaClO2 / 2-methyl-propan-2-ol; H2O / 20 °C 9.1: NEt3; 2,4,6-trichlorobenzoyl chloride / tetrahydrofuran / 6 h 9.2: 81 percent / DMAP / tetrahydrofuran; toluene / Heating 10.1: 91 percent / aq. HCl / tetrahydrofuran; H2O / 48 h / 20 °C View Scheme

1.1: BuLi / tetrahydrofuran; hexane / 1 h / -78 °C 1.2: MeCuCNLi / tetrahydrofuran; hexane; diethyl ether / 1 h / -78 °C 1.3: 92.6 percent / tetrahydrofuran; hexane; diethyl ether / 1 h / -78 °C 2.1: 131 mg / (S)-2-methyl-CBS-oxazaborolidine; BH3*Me2S / tetrahydrofuran; toluene / 0.25 h / 0 °C 3.1: 96.4 percent / diethyl ether / 1 h / 0 °C 4.1: 72 percent / Li-naphthalene / tetrahydrofuran / -25 °C 5.1: MnO2 / CH2Cl2 / 3 h / Heating 6.1: 33.6 mg / NaH2PO4; 2-methyl-2-butene; NaClO2 / 2-methyl-propan-2-ol; H2O / 20 °C 7.1: NEt3; 2,4,6-trichlorobenzoyl chloride / tetrahydrofuran / 6 h 7.2: 81 percent / DMAP / tetrahydrofuran; toluene / Heating 8.1: 91 percent / aq. HCl / tetrahydrofuran; H2O / 48 h / 20 °C View Scheme

1.1: 95.4 percent / I2; aq. NaOH / diethyl ether / 0.33 h / 20 °C 2.1: BuLi / tetrahydrofuran; hexane / 1 h / -78 °C 2.2: MeCuCNLi / tetrahydrofuran; hexane; diethyl ether / 1 h / -78 °C 2.3: 92.6 percent / tetrahydrofuran; hexane; diethyl ether / 1 h / -78 °C 3.1: 131 mg / (S)-2-methyl-CBS-oxazaborolidine; BH3*Me2S / tetrahydrofuran; toluene / 0.25 h / 0 °C 4.1: 96.4 percent / diethyl ether / 1 h / 0 °C 5.1: 72 percent / Li-naphthalene / tetrahydrofuran / -25 °C 6.1: MnO2 / CH2Cl2 / 3 h / Heating 7.1: 33.6 mg / NaH2PO4; 2-methyl-2-butene; NaClO2 / 2-methyl-propan-2-ol; H2O / 20 °C 8.1: NEt3; 2,4,6-trichlorobenzoyl chloride / tetrahydrofuran / 6 h 8.2: 81 percent / DMAP / tetrahydrofuran; toluene / Heating 9.1: 91 percent / aq. HCl / tetrahydrofuran; H2O / 48 h / 20 °C View Scheme

1.1: BuLi / tetrahydrofuran; hexane / 1 h / -78 °C 1.2: MeCuCNLi / tetrahydrofuran; hexane; diethyl ether / 1 h / -78 °C 1.3: 92.6 percent / tetrahydrofuran; hexane; diethyl ether / 1 h / -78 °C 2.1: 131 mg / (S)-2-methyl-CBS-oxazaborolidine; BH3*Me2S / tetrahydrofuran; toluene / 0.25 h / 0 °C 3.1: 96.4 percent / diethyl ether / 1 h / 0 °C 4.1: 72 percent / Li-naphthalene / tetrahydrofuran / -25 °C 5.1: MnO2 / CH2Cl2 / 3 h / Heating 6.1: 33.6 mg / NaH2PO4; 2-methyl-2-butene; NaClO2 / 2-methyl-propan-2-ol; H2O / 20 °C 7.1: NEt3; 2,4,6-trichlorobenzoyl chloride / tetrahydrofuran / 6 h 7.2: 81 percent / DMAP / tetrahydrofuran; toluene / Heating 8.1: 91 percent / aq. HCl / tetrahydrofuran; H2O / 48 h / 20 °C View Scheme

1.1: LDA / tetrahydrofuran; hexane / 1 h / -78 °C 1.2: tetrahydrofuran; hexane / -78 - 20 °C 2.1: 2.25 g / TiCl4 / CH2Cl2 / 1 h / -78 °C 3.1: 97 percent / DBU / methanol / 1 h / 0 °C 4.1: BuLi / tetrahydrofuran; hexane / 1 h / -78 °C 4.2: MeCuCNLi / tetrahydrofuran; hexane; diethyl ether / 1 h / -78 °C 4.3: 92.6 percent / tetrahydrofuran; hexane; diethyl ether / 1 h / -78 °C 5.1: 131 mg / (S)-2-methyl-CBS-oxazaborolidine; BH3*Me2S / tetrahydrofuran; toluene / 0.25 h / 0 °C 6.1: 96.4 percent / diethyl ether / 1 h / 0 °C 7.1: 72 percent / Li-naphthalene / tetrahydrofuran / -25 °C 8.1: MnO2 / CH2Cl2 / 3 h / Heating 9.1: 33.6 mg / NaH2PO4; 2-methyl-2-butene; NaClO2 / 2-methyl-propan-2-ol; H2O / 20 °C 10.1: NEt3; 2,4,6-trichlorobenzoyl chloride / tetrahydrofuran / 6 h 10.2: 81 percent / DMAP / tetrahydrofuran; toluene / Heating 11.1: 91 percent / aq. HCl / tetrahydrofuran; H2O / 48 h / 20 °C View Scheme

1.1: 97 percent / DBU / methanol / 1 h / 0 °C 2.1: BuLi / tetrahydrofuran; hexane / 1 h / -78 °C 2.2: MeCuCNLi / tetrahydrofuran; hexane; diethyl ether / 1 h / -78 °C 2.3: 92.6 percent / tetrahydrofuran; hexane; diethyl ether / 1 h / -78 °C 3.1: 131 mg / (S)-2-methyl-CBS-oxazaborolidine; BH3*Me2S / tetrahydrofuran; toluene / 0.25 h / 0 °C 4.1: 96.4 percent / diethyl ether / 1 h / 0 °C 5.1: 72 percent / Li-naphthalene / tetrahydrofuran / -25 °C 6.1: MnO2 / CH2Cl2 / 3 h / Heating 7.1: 33.6 mg / NaH2PO4; 2-methyl-2-butene; NaClO2 / 2-methyl-propan-2-ol; H2O / 20 °C 8.1: NEt3; 2,4,6-trichlorobenzoyl chloride / tetrahydrofuran / 6 h 8.2: 81 percent / DMAP / tetrahydrofuran; toluene / Heating 9.1: 91 percent / aq. HCl / tetrahydrofuran; H2O / 48 h / 20 °C View Scheme

1.1: 89.4 percent / NaHCO3; I2 / acetone; H2O / 0.25 h / 0 °C 2.1: LDA / tetrahydrofuran; hexane / 1 h / -78 °C 2.2: tetrahydrofuran; hexane / -78 - 20 °C 3.1: 2.25 g / TiCl4 / CH2Cl2 / 1 h / -78 °C 4.1: 97 percent / DBU / methanol / 1 h / 0 °C 5.1: BuLi / tetrahydrofuran; hexane / 1 h / -78 °C 5.2: MeCuCNLi / tetrahydrofuran; hexane; diethyl ether / 1 h / -78 °C 5.3: 92.6 percent / tetrahydrofuran; hexane; diethyl ether / 1 h / -78 °C 6.1: 131 mg / (S)-2-methyl-CBS-oxazaborolidine; BH3*Me2S / tetrahydrofuran; toluene / 0.25 h / 0 °C 7.1: 96.4 percent / diethyl ether / 1 h / 0 °C 8.1: 72 percent / Li-naphthalene / tetrahydrofuran / -25 °C 9.1: MnO2 / CH2Cl2 / 3 h / Heating 10.1: 33.6 mg / NaH2PO4; 2-methyl-2-butene; NaClO2 / 2-methyl-propan-2-ol; H2O / 20 °C 11.1: NEt3; 2,4,6-trichlorobenzoyl chloride / tetrahydrofuran / 6 h 11.2: 81 percent / DMAP / tetrahydrofuran; toluene / Heating 12.1: 91 percent / aq. HCl / tetrahydrofuran; H2O / 48 h / 20 °C View Scheme