in tetrahydrofuran T=-78 - -23°C;

1: 1.) HMPA, 2.) iodine-silver trifluoracetate / 1.) THF, 2.) CH2Cl2, -78 deg C 3: 1.)disiamylborane, 2.) HOAc / 1.) THF, -40 deg C, 2 h , - 20 deg C, 4 h, 0 deg C, 1 h, 2.) 25 deg C, 4 h 4: 1.) t-BuLi, 2.) CuI*Me2s / ether/THF 5: 100 percent / LiOH / tetrahydrofuran; H2O / 14 h / 25 °C View Scheme

in tetrahydrofuran T=-90 - 25°C; 12 h;

ammonia

1: tetrahydrofuran; hexamethylphosphoric acid triamide / 2.5 h / 65 °C 2: tetrahydrofuran; hexamethylphosphoric acid triamide / 16.5 h / 65 °C 3: 100 percent / H2 / Lindlar catalyst / benzene 4: (CH2SH)2, TSOH / CHCl3 / 3 h / 60 °C 5: Pb(OAc)4 / benzene / 1 h / Ambient temperature 6: 60 percent / benzene / 6 h / 80 °C 7: 65 percent / DBU, LiCl / acetonitrile / 1 h / Ambient temperature 8: AlH3 / tetrahydrofuran / 2.5 h / 0 °C 9: CBr4, DIPHOS / CH2Cl2 / 2.5 h / -35 °C 10: acetonitrile / 2.5 h / Ambient temperature 11: 1.) BuLi 2.) HMPT / 1.) THF, -100 deg C, 2 min; 2.) -100 deg C to RT 12: nBu4NF / tetrahydrofuran 13: K2CO3 / methanol; H2O View Scheme

1: 2) NH4Cl / 1) THF, -78 deg C 2: 88 percent / Et3N / CH2Cl2 / 14 h / Ambient temperature 3: 1) NaOEt, 2) 10percent HCl / 1) ethanol, 2 h, reflux, 2) 0.5 h, RT 4: 60 percent / NaH / tetrahydrofuran / 12 h / Ambient temperature View Scheme

tert-butylamine hydrobromide in tetrahydrofuran 0 deg C, 1 h, r.t., overnight;

in ammonia with NH3, H2O and n-amylbromide formation of di-n-amylacetylene;;

1: 70 percent / HMPT / tetrahydrofuran / -5 °C 2: 82 percent / hydrogen / P-2 Ni / ethanol 3: trifluoroacetic acid, water / CHCl3 / 1 h View Scheme

1: 70 percent / HMPT / tetrahydrofuran / -5 °C 2: 82 percent / hydrogen / P-2 Ni / ethanol 3: trifluoroacetic acid, water / CHCl3 / 1 h 4: tetrahydrofuran / 1 h / -78 to 20 deg C View Scheme