ammonium chloride in tetrahydrofuran; methanol; water To a stirred soln. of Me3SnCu*Me2S in THF (Ar, -78°C) was added sequentially a THF soln. of the 1-alkyne and CH3OH. The mixt. was stirred(10 min) and then at -63°C (12 h). Satd. aq. NH4Cl and ether were added; allowed to warm to room temp.; Aq. phase was extd. (ether). The org. exts. were washed (satd. aq. NH4Cl) and dried (MgSO4). Removal of the solvent; flash chromy. on silica gel followed by distillation. (E)-1-trimethylstannyl-1-alkene not isolated, detected by gas-liq. chromy..;

toluene-4-sulfonic acid in toluene 144 h;

(i) Li, liq. NH3, (ii) /BRN= 1733136/; Multistep reaction;

1: 1.) LiNH2, liq. NH3, HMPA / 1.) -33 deg C, 2 h, 2.) THF, -33 deg C, 6 h 2: 90 percent / PTSA / methanol; H2O / 12 h / Ambient temperature 3: 88.8 percent / DMAP / pyridine / 8 h / Ambient temperature 4: 85 percent / H2, quinoline / Lindlar catalyst / ethanol View Scheme

1.1: bis(cyclopentadienyl)zirconium chloride hydride / tetrahydrofuran / 2 h / 20 °C 1.2: iodine / tetrahydrofuran / 1 h / 20 °C 1.3: 81 percent / HCl / methanol / 5 h 2.1: pyridine / 0 - 20 °C 3.1: 1.15 g / NaI / acetone / 6 h View Scheme

1.1: zirconocene chloride hydride / benzene / 6 h / 20 °C 1.2: 71 percent / I2 / benzene 2.1: Pd(PPh3)4 / benzene / 0.25 h / 20 °C 2.2: 70 percent / benzene / 20 °C 3.1: 80 percent / PPTs / methanol / 24 h / 20 °C 4.1: 82 percent / pyridine / 12 h / 20 °C View Scheme

N,N,N',N',N'',N''-hexamethylphosphoric triamide; lithium amide; ammonia 1.) -33 deg C, 2 h, 2.) THF, -33 deg C, 6 h; Yield given. Multistep reaction;

1: 1.) n-BuLi, 2.) HMPA / 1.) THF, hexane, from -78 deg C to RT, 1 h, 2.) THF, hexane, form -78 deg C to RT, 4 h 2: 68 percent / methanolic para-toluenesulfonic acid / toluene / 144 h 3: 88 percent / H2 / 10percent Pd/C / diethyl ether / 16 h 4: 44 percent / molecular sieves 4 A, pyridinum dichromate / dimethylformamide / 120 h / Ambient temperature 5: 94 percent / 10percent aq. tetrabutylammonium hydroxide / CH2Cl2 / 16 h View Scheme

1.1: zirconocene chloride hydride / benzene / 6 h / 20 °C 1.2: 71 percent / I2 / benzene 2.1: Pd(PPh3)4 / benzene / 0.25 h / 20 °C 2.2: 70 percent / benzene / 20 °C 3.1: 80 percent / PPTs / methanol / 24 h / 20 °C View Scheme

1: 1.) EtMgBr, 2.) CuI 2: 83 percent / Ph3P, Br2 / CCl4 / 3 h 3: 1.) Mg / 1.) THF, from 45 deg C to 50 deg C, 2.) THF, RT, 0.5 h 4: tetrahydrofuran / 1 h / Ambient temperature 5: O3 / cyclohexane; acetic acid / 5 °C 6: aq. H2CrO4 / cyclohexane; acetic acid / 4 h / 20 °C 7: 94 percent / K2CO3 / methanol / 2 h / 50 °C View Scheme