本論文以合成具長碳鏈 (Z)-烯烴類的昆蟲性費洛蒙為目標。首先以丁基格里納試劑與 DHP 進行鎳催化開環偶合反應,再經由溴化反應形成溴化物4。溴化物4 與另一溴化物7,交互作為反應物或製備相對應之格里納試劑,進行銅催化交叉偶聯反應合成順式烯醇化合物 (Z)-十四碳-9-烯-1-醇(2)。 其中銅催化偶合反應的探討,共利用3 種不同組合的銅催化劑與配體 CuI, 2,2’-bipyridine、CuI, 1-phenyl-1-propyne 及Li2CuCl4, NMP)進行測試。實驗結果顯示3% Li2CuCl4 為最適當的銅催化劑及其用量。此外,最佳的偶合反應物組合為採用溴化物7 作為反應物,而將溴化物4 製備成格里納試劑,在室溫下搭配NMP,或在 –5 °C 下無需添加NMP 進行反應,可得到相同的反應產率(55%),整體合成之總產率為28%。
The target of this thesis is to synthesize insect sex pheromone containing long-chain (Z)-alkenyl hydrocarbon. The synthesis began with Ni-catalyzed ring-opening cross-coupling reaction of n-butyl Grignard reagent and DHP. The successive bromination yielded the corresponding bromo compound 4. Bromo compounds 4 and 7 can be used either as starting material or for the preparation of the orresponding Grignard reagent, in order to underwent Cu-catalyzed cross-coupling reaction to furnish (Z)-alkenol compound, i.e.(Z)-9-tetradecenol (2). Regarding to the examination of Cu-catalyzed cross-coupling reaction, three different catalyst and ligand combinations, e.g. CuI/2,2’-bipyridine, CuI/1-phenyl-1-propyne, and Li2CuCl4/NMP, were investigated. The results showed that 3 mol% Li2CuCl4 to be the best copper catalyst and its loading. Moreover, the best substrates combination were using bromo compound 7 as the starting material and bromo compound 4 for the preparation of Grignard reagent. The Cu-catalyzed cross-coupling, performed either with NMP at rt, or without NMP at –5 °C, gave the same yield (55%), and the overall yield for the synthesis was 28%.