[CH2:1]=[CH:2][CH2:3][CH2:4][CH:5]=[CH:6][CH2:7][CH2:8][CH:9]=[CH:10][CH2:11][CH2:12][CH2:13][CH3:14].C([Mg]Cl)CCC.[C:21]([O:24][CH2:25][CH2:26]Br)(=[O:23])[CH3:22].Cl>[Ti](Cl)(Cl)(Cl)Cl>[CH3:14][CH2:13][CH2:12][CH2:11]/[CH:10]=[CH:9]\[CH2:8][CH2:7]/[CH:6]=[CH:5]\[CH2:4][CH2:3][CH2:2][CH2:1][CH2:26][CH2:25][O:24][C:21]([CH3:22])=[O:23]1,5,9-Tetradecatriene (10 g, 0.052 mol), n-butylmagnesium chloride (24.8 mL of 2.5M in tetrahydrofuran; 0.062 mol) and titanium tetrachloride (0.52 g, 0.0027 mol) were stirred under an inert atmosphere at about 65° C. for about 4.5 hours. The reaction mixture was then cooled to 0° C. and cuprous bromide (0.14 g, 1.0 mmol) was added. 2-Bromoethyl acetate (6.9 mL, 0.063 mol) was then added dropwise and the mixture allowed to warm slowly to room temperature and stirred for several hours at room temperature. Reaction temperature was then raised to 60° C. for 4 hours before the mixture was cooled, acidified with aqueous HCl, then extracted with hexane. The hexane extract was washed with saturated sodium bicarbonate solution, dried over MgSO4, filtered and solvent removed on the rotary evaporator. GLC analysis of this crude reaction product indicated an 11% yield of gossyplure. It should be recognized that while this reaction represents successful production of gossyplure from 1,5,9 -tetradecatriene in one reaction vessel, the reaction parameters have not been optimized. Consequently, significantly improved yields of gossyplure can be expected upon optimization of various reaction parameters.
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