1: trimethylaluminum; (5E,9E,13E,17E,21E)-6,10,14,18,22,26-Hexamethyl-heptacosa-5,9,13,17,21,25-hexaen-1-yne With zirconocene dichloride in hexane; 1,2-dichloro-ethane Metallation; 2: 2-chloromethyl-5,6-dimethoxy-3-methyl-[1,4]benzoquinone With NiCl2((PPh3)P)2; n-butyllithium in tetrahydrofuran; hexane Alkylation;

1.1: 94 percent / NaBH4 / tetrahydrofuran / 0.5 h / -20 °C 2.1: POCl3 3.1: dimethylformamide / 20 °C 4.1: TsOH / methanol / 12 h / 20 °C 5.1: 65 percent / n-BuLi 6.1: 100 percent / LiBHEt3; Pd(dppp)Cl2 / tetrahydrofuran / 3 h / 0 °C 7.1: N-chlorosuccinimide; Me2S / CH2Cl2 / 2.5 h / 0 °C 8.1: n-BuLi 8.2: -78 - 20 °C 9.1: LiBHEt3; Pd(dppp)Cl2 / tetrahydrofuran 10.1: TBAF / tetrahydrofuran / 1 h 11.1: Cp2ZrCl2 / 1,2-dichloro-ethane; hexane 11.2: 83 percent / NiCl2(PPh3)2; n-BuLi / tetrahydrofuran; hexane View Scheme

1.1: CuCl2; NaCl; conc. aq. HCl / benzene / 5 h / 50 °C 2.1: 94 percent / NaBH4 / tetrahydrofuran / 0.5 h / -20 °C 3.1: POCl3 4.1: dimethylformamide / 20 °C 5.1: TsOH / methanol / 12 h / 20 °C 6.1: 65 percent / n-BuLi 7.1: 100 percent / LiBHEt3; Pd(dppp)Cl2 / tetrahydrofuran / 3 h / 0 °C 8.1: N-chlorosuccinimide; Me2S / CH2Cl2 / 2.5 h / 0 °C 9.1: n-BuLi 9.2: -78 - 20 °C 10.1: LiBHEt3; Pd(dppp)Cl2 / tetrahydrofuran 11.1: TBAF / tetrahydrofuran / 1 h 12.1: Cp2ZrCl2 / 1,2-dichloro-ethane; hexane 12.2: 83 percent / NiCl2(PPh3)2; n-BuLi / tetrahydrofuran; hexane View Scheme

1.1: POCl3 2.1: dimethylformamide / 20 °C 3.1: TsOH / methanol / 12 h / 20 °C 4.1: 65 percent / n-BuLi 5.1: 100 percent / LiBHEt3; Pd(dppp)Cl2 / tetrahydrofuran / 3 h / 0 °C 6.1: N-chlorosuccinimide; Me2S / CH2Cl2 / 2.5 h / 0 °C 7.1: n-BuLi 7.2: -78 - 20 °C 8.1: LiBHEt3; Pd(dppp)Cl2 / tetrahydrofuran 9.1: TBAF / tetrahydrofuran / 1 h 10.1: Cp2ZrCl2 / 1,2-dichloro-ethane; hexane 10.2: 83 percent / NiCl2(PPh3)2; n-BuLi / tetrahydrofuran; hexane View Scheme

2.1: 88 percent / DCC; DMSO; 85 percent H3PO4 / benzene / 135 h 3.1: 96 percent / NaBH4 / tetrahydrofuran / 1 h / -20 °C 4.1: 98 percent / N-chlorosiccinimide; Me2S / CH2Cl2 / 2.5 h / 0 °C 5.1: 65 percent / n-BuLi 6.1: 100 percent / LiBHEt3; Pd(dppp)Cl2 / tetrahydrofuran / 3 h / 0 °C 7.1: N-chlorosuccinimide; Me2S / CH2Cl2 / 2.5 h / 0 °C 8.1: n-BuLi 8.2: -78 - 20 °C 9.1: LiBHEt3; Pd(dppp)Cl2 / tetrahydrofuran 10.1: TBAF / tetrahydrofuran / 1 h 11.1: Cp2ZrCl2 / 1,2-dichloro-ethane; hexane 11.2: 83 percent / NiCl2(PPh3)2; n-BuLi / tetrahydrofuran; hexane View Scheme

1.1: dimethylformamide / 20 °C 2.1: n-BuLi 2.2: -78 - 20 °C 3.1: LiBHEt3; Pd(dppp)Cl2 / tetrahydrofuran 4.1: TBAF / tetrahydrofuran / 1 h 5.1: Cp2ZrCl2 / 1,2-dichloro-ethane; hexane 5.2: 83 percent / NiCl2(PPh3)2; n-BuLi / tetrahydrofuran; hexane View Scheme

1.1: n-BuLi 1.2: -78 - 20 °C 2.1: LiBHEt3; Pd(dppp)Cl2 / tetrahydrofuran 3.1: TBAF / tetrahydrofuran / 1 h 4.1: Cp2ZrCl2 / 1,2-dichloro-ethane; hexane 4.2: 83 percent / NiCl2(PPh3)2; n-BuLi / tetrahydrofuran; hexane View Scheme

1.1: 96 percent / NaBH4 / tetrahydrofuran / 1 h / -20 °C 2.1: 98 percent / N-chlorosiccinimide; Me2S / CH2Cl2 / 2.5 h / 0 °C 3.1: 65 percent / n-BuLi 4.1: 100 percent / LiBHEt3; Pd(dppp)Cl2 / tetrahydrofuran / 3 h / 0 °C 5.1: N-chlorosuccinimide; Me2S / CH2Cl2 / 2.5 h / 0 °C 6.1: n-BuLi 6.2: -78 - 20 °C 7.1: LiBHEt3; Pd(dppp)Cl2 / tetrahydrofuran 8.1: TBAF / tetrahydrofuran / 1 h 9.1: Cp2ZrCl2 / 1,2-dichloro-ethane; hexane 9.2: 83 percent / NiCl2(PPh3)2; n-BuLi / tetrahydrofuran; hexane View Scheme

1.1: 65 percent / n-BuLi 2.1: 100 percent / LiBHEt3; Pd(dppp)Cl2 / tetrahydrofuran / 3 h / 0 °C 3.1: N-chlorosuccinimide; Me2S / CH2Cl2 / 2.5 h / 0 °C 4.1: n-BuLi 4.2: -78 - 20 °C 5.1: LiBHEt3; Pd(dppp)Cl2 / tetrahydrofuran 6.1: TBAF / tetrahydrofuran / 1 h 7.1: Cp2ZrCl2 / 1,2-dichloro-ethane; hexane 7.2: 83 percent / NiCl2(PPh3)2; n-BuLi / tetrahydrofuran; hexane View Scheme

1.1: 88 percent / DCC; DMSO; 85 percent H3PO4 / benzene / 135 h 2.1: 96 percent / NaBH4 / tetrahydrofuran / 1 h / -20 °C 3.1: 98 percent / N-chlorosiccinimide; Me2S / CH2Cl2 / 2.5 h / 0 °C 4.1: 65 percent / n-BuLi 5.1: 100 percent / LiBHEt3; Pd(dppp)Cl2 / tetrahydrofuran / 3 h / 0 °C 6.1: N-chlorosuccinimide; Me2S / CH2Cl2 / 2.5 h / 0 °C 7.1: n-BuLi 7.2: -78 - 20 °C 8.1: LiBHEt3; Pd(dppp)Cl2 / tetrahydrofuran 9.1: TBAF / tetrahydrofuran / 1 h 10.1: Cp2ZrCl2 / 1,2-dichloro-ethane; hexane 10.2: 83 percent / NiCl2(PPh3)2; n-BuLi / tetrahydrofuran; hexane View Scheme