【摘要】：發(fā)展新的有機(jī)合成方法能夠?yàn)獒t(yī)藥、農(nóng)藥、材料和精細(xì)化工品的研發(fā)提供簡(jiǎn)便而有效的途徑。探索廉價(jià)高效的催化劑以及溫和的反應(yīng)條件,實(shí)現(xiàn)碳-碳鍵、碳-氮鍵和其它碳-雜原子鍵的構(gòu)建,進(jìn)而完成復(fù)雜分子的合成,是有機(jī)化學(xué)的研究主題之一。本論文工作主要圍繞以下反應(yīng)進(jìn)行:1.通過(guò)缺電子烯烴和硝酮參與的不對(duì)稱1,3-偶極環(huán)加成反應(yīng)制備手性異VA唑烷類化合物;2.苯并磺內(nèi)酰亞胺和烯醇硅醚的不對(duì)稱Mukaiyama-Mannich反應(yīng)實(shí)現(xiàn)含季碳中心的苯并磺酰胺類衍生物的制備;3.探索出通過(guò)鈀催化的構(gòu)建烯基Csp2-P鍵的方式合成α,β-不飽和烯基膦化物的方法。研究了 α,β-不飽和�；人狨ズ拖跬獏⑴c的不對(duì)稱1,3-偶極環(huán)加成反應(yīng),以中等以上的收率,高非對(duì)映選擇性和對(duì)映選擇性地得到含三個(gè)相鄰手性中心的異VA唑烷類化合物。該反應(yīng)運(yùn)用了少有報(bào)道的可雙齒配位的聯(lián)羰型缺電子烯烴為親偶極體,與金屬絡(luò)合物以1,4-位配位的形式形成五元環(huán)反應(yīng)中間體,進(jìn)而降低缺電子烯烴的HOMO能量而活化底物。該部分工作進(jìn)一步豐富了 α,β-不飽和酰基羧酸酯的C=C體系所參與的反應(yīng)類型。發(fā)展了一種制備手性2,3-位芳基(烷基)取代4-位酯基取代的異VA唑烷類化合物的新方法,該反應(yīng)使用Cu(Ⅱ)-Inda-BOX為催化劑,在0℃條件下催化α,β-不飽和�；⑺狨ズ拖跬沫h(huán)加成,以良好的收率得到環(huán)化產(chǎn)物,并獲得唯一的區(qū)域選擇性、優(yōu)異的非對(duì)映選擇性和對(duì)映選擇性。該反應(yīng)在溫和的條件下得到含三個(gè)相鄰手性中心的異VA唑烷類化合物,同時(shí)膦酸酯具有易衍生化的優(yōu)點(diǎn)。研究了芳香酮衍生的烯醇硅醚和環(huán)狀N-磺�；鶃啺孵サ牟粚�(duì)稱Mukaiyama-Marmich加成反應(yīng)。在優(yōu)化的反應(yīng)條件下(2-10 mol%的Ni(ClO4)·6H2O-雙VA唑啉,在0℃或室溫條件下,CHCl3為溶劑),以高收率(89-99%)和高對(duì)映選擇性(84-99%ee)得到一系列不同取代的含手性季碳中心的苯并磺內(nèi)酰胺類化合物。該方法能夠拓展到遠(yuǎn)端的共軛體系和有空間位阻的烯醇硅醚,同樣取得了優(yōu)異的催化結(jié)果。Mannich加成產(chǎn)物可以方便地轉(zhuǎn)化為吖啶類或新骨架的多元環(huán)狀苯并磺內(nèi)酰胺類化合物。發(fā)展了鈀催化的α-位連有吸電子基團(tuán)的鹵代烯烴和二苯基膦的偶聯(lián)反應(yīng),并完成了系列新型的芳甲叉基膦氧配體的制備。該合成策略可作為構(gòu)建新型的烯基Csp2-P鍵的補(bǔ)充方案,更進(jìn)一步,可將烯基膦化物產(chǎn)物應(yīng)用到不同類型的反應(yīng)中以考察其潛在的配位作用和催化性能。
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【學(xué)位授予單位】：中國(guó)農(nóng)業(yè)大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2017
【分類號(hào)】：O621.251

【參考文獻(xiàn)】

相關(guān)期刊論文 前5條

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