(E)-1-iodooct-1-ene

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of oct-1-yne (56.2 mg, 0.5 mmol) and Cp2ZrCl2 (206.7 mg, 1.4 mmol, 1.4 eq.) in THF (2.5 mL) at RT was rapidly added a 1 M THF solution of LiAlH(Ot-Bu)3 (0.7 mL, 1.4 mmol, 1.4 eq.). A resulting dark red solution was stirred at RT for 15 min. At that time, dry ZnBr2 (157.7 mg, 1.4 mmol, 1.4 eq., Aldrich) and THF (1 mL) were added at RT. After 30 min., 1-iodo-4-methoxybenzene (165.5 mg, 1.4 mmol, 1.4 eq., Aldrich), Pd(PPh3)4 (11.6 mg, 0.001 mmol, 0.02 eq.) and DMF (1 mL) were added. The resultant mixture was stirred at RT for 5 h and then quenched with 1 N HCl, and extracted with EtOAc (4×5 mL). Organic extracts were combined and washed with H2O and brine, dried over MgSO4 and concentrated via evaporation under reduced pressure. Purification of the residue was performed using a silica gel column (silica gel 60, 230-400 mesh) with CH2Cl2/hexanes as eluent. (E)-1-iodooct-1-ene (41.3 mg, 38% yield) was obtained as a colorless oil. 1H NMR (400 MHz, CDCl3) δ ppm: 7.27 (d, J=8.62 Hz, 21-1), 6.83 (d, J=8.64 Hz, 2H), 6.31 (d, J=15.79 Hz, 1H), 6.08 (dt, J=14.23, 6.89 Hz, 1H), 3.79 (s, 3H), 2.17 (td, J=7.14, 7.07 Hz, 2H), 1.50-1.40 (m, 2H), 1.38-1.27 (m, 6H), 0.89 (t, J=6.31 Hz, 3H) 13C NMR (101 MHz, CDCl3) δ ppm: 158.59, 130.84, 129.09, 128.99, 126.93 (2C), 113.89 (2C), 55.27, 33.02, 31.77, 29.50, 28.91, 22.63, 14.09. Physical and spectral data were consistent with those previously reported (see Nakao, Y.; Imanaka, H.; Sahoo, A. K.; Yada, A.; Hiyama, T. J. Am. Chem. Soc. 2005, 127, 6952-6953.) After 30 min. quenched with 1 N HCl extracted with EtOAc (4×5 mL) washed with H2O and brine dried over MgSO4 concentrated via evaporation under reduced pressure Purification of the residue

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of oct-1-yne (113 mg, 1 mmol, available from Lancaster, Pelham, N.H., USA) and Cp2ZrCl2 (413 mg, 1.4 mmol, 1.4 eq.) in THF (4 mL) at RT was rapidly added a 1 M THF solution of LiAlH(Ot-Bu)3 (1.4 mL, 1.4 mmol, 1.4 eq.). A resulting dark red solution was stirred at RT for 15 min. Then, a solution of iodine (355 mg, 1.4 mmol, 1.4 eq., Aldrich) in THF (2 mL) was added. After additional stirring at RT for 15 min., the reaction mixture was quenched with 1 N HCl, and extracted with diethyl ether (3×10 mL). The organic extracts were combined and washed successively with saturated Na2SO3, H2O, and brine. The organic residue was then dried over MgSO4 and concentrated via evaporation under reduced pressure. Purification of the residue was performed using a short silica gel column (silica gel 60, 230-400 mesh) with EtOAc/hexanes as eluent. (E)-1-iodooct-1-ene (217 mg, 91% yield) was obtained as a light yellow oil. 1H NMR (400 MHz, CDCl3) δ ppm: 6.51 (dt, J=14.30, 7.12 Hz, 1H), 5.97 (d, J=14.31 Hz, 1H), 2.05 (dt, J=7.01, 6.96 Hz, 2H), 1.45-1.34 (m, 2H), 1.33-1.18 (m, 6H), 0.88 (t, J=6.66 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ ppm: 146.78, 74.21, 36.03, 31.56, 28.58, 28.32, 22.54, 14.04. The physical and spectral data are consistent with those previously reported (see Ren, H.; Krasovskiy, A.; Knochel, P. Org. Lett. 2004, 6, 4215-4217). After additional stirring at RT for 15 min. the reaction mixture was quenched with 1 N HCl extracted with diethyl ether (3×10 mL) washed successively with saturated Na2SO3, H2O, and brine The organic residue was then dried over MgSO4 concentrated via evaporation under reduced pressure Purification of the residue

Conditions: temp:-35.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 5.99 ml of a pentane solution of 9.34 mmols of t-butyl lithium was added to 1.11 g (4.67 mmols) of trans-1-iodo-1-octene, 15 ml ether solution in an atmosphere of argon at -78° C. and stirred at the same temperature for 2 hours. 400 mg (2.10 mmols) of copper iodide was added to the reaction solution, after which it was heated up to -35° C. and stirred at the same temperature for 45 minutes. 941 mg (5.25 mmols) of hexamethylphosphorus triamide was added to the solution and stirred at -35° C. for 10 minutes, to which 10 ml of a tetrahydrofuran solution of 628 mg (1.75 mmols) of 2-iodomethyl-3-methyl-4 acetoxy-6-fluoroquinoline was added, followed by stirring at the same temperature for 30 minutes. The reaction solution was added to a solution of 2 ml of 1N hydrochloric acid and 100 ml of water, followed by filtration through Celite. The resultant filtrate was extracted with chloroform, washed with water and dried with anhydrous sodium sulfate. The solvent was distilled off under the reduced pressure and the residue was purified by silica gel column chromatography (solvent: n-hexane : ethyl acetate=15:1) to obtain 120 mg (yield 20 %) of 2-(trans-2-nonenyl)-3-methyl-4-acetoxy-6-fluoroquinoline. stirred at the same temperature for 45 minutes was added by stirring at the same temperature for 30 minutes followed by filtration through Celite The resultant filtrate was extracted with chloroform washed with water dried with anhydrous sodium sulfate The solvent was distilled off under the reduced pressure the residue was purified by silica gel column chromatography (solvent: n-hexane : ethyl acetate=15:1)

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The modified procedure was used to convert phenylacetylene and (E)-1-iodooctene to the title product. Purification by flash chromatography (light petroleum ether as eluent) afforded a clear oil (418 mg, 98% yield). The proton spectra obtained matches that of the analytically pure compound previously isolated (see Table 3, entry 5). 1H NMR (400 MHz, CDCl3) δ 7.42 (m, 2H), 7.28 (m, 3H), 6.24 (m, 1H), 5.66 (d, J=15.85, 1H), 2.15 (q, 2H), 1.42-1.29 (m, 8H), 0.89 (t, 3H).

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The general procedure was used to convert phenylacetylene and (E)-1-iodooctene to the title product in 24 hours. Purification by flash chromatography (light petroleum ether as eluent) gave the analytically pure product as a clear oil (423 mg, 99% yield). 1H NMR (400 MHz, CDCl3) δ 7.40 (m, 2H), 7.28 (m, 3H), 6.24 (m, 1H), 5.68 (d, J=15.84, 1H), 2.15 (q, 2H), 1.41-1.28 (m, 8H), 0.89 (t, 3H). 13C NMR (100 MHz, CDCl3) δ 145.08, 131.24, 128.07, 127.67, 123.49, 109.32, 88.23, 87.68, 33.08, 31.52, 28.66, 28.59, 22.45, 13.94. Anal. Calc'd. for C16H20: C, 90.51; H, 9.49; Found C, 90.65; H, 9.58.