【摘要】：硫基化反應(yīng)是有機(jī)合成中一種重要的化學(xué)反應(yīng),能夠有效的構(gòu)筑碳-硫鍵。近些年來(lái),化學(xué)家們對(duì)硫基化反應(yīng)研究已經(jīng)取得了顯著的成果,主要集中在有機(jī)小分子催化或過(guò)渡金屬催化構(gòu)建sp~3碳-硫鍵,而構(gòu)建sp~2碳-硫鍵大多是通過(guò)過(guò)渡金屬催化鹵代芳烴、鹵代烯烴的交叉偶聯(lián)反應(yīng)或者炔烴的加成反應(yīng)得到,但大部分過(guò)渡金屬價(jià)格昂貴、毒性較大。因此,發(fā)展綠色、經(jīng)濟(jì)、環(huán)境友好的構(gòu)建sp~2碳-硫鍵的方法有著重要意義。本論文主要包含三章內(nèi)容:第一章綜述了有機(jī)小分子催化的親電硫試劑參與構(gòu)筑碳-硫鍵的反應(yīng)研究進(jìn)展。主要包括不對(duì)稱硫基化反應(yīng)、不對(duì)稱硫胺化反應(yīng)、不對(duì)稱硫醚化反應(yīng)等,為合成高對(duì)映選擇性的有機(jī)硫化合物提供了有效途徑。第二章主要介紹了氮雜環(huán)卡賓催化α,β-不飽和醛的硫基化反應(yīng)研究。我們發(fā)展了首個(gè)氮雜環(huán)卡賓催化的α,β-不飽和醛與N-芳硫基鄰苯二甲酰亞胺的硫基化反應(yīng),有效的保留了醛基,為sp~2碳-硫鍵的形成提供了一種綠色、高效的新方法。該方法有良好的兼容性,各類底物均能達(dá)到較高的產(chǎn)率以及良好的Z/E選擇性。第三章主要研究了氮雜環(huán)卡賓催化烯酮與亞胺的環(huán)加成反應(yīng)。我們?cè)O(shè)想使用手性氮雜環(huán)卡賓催化烯酮與亞胺醌環(huán)加成再異構(gòu)化,得到手性吲哚酮類化合物。經(jīng)過(guò)初步嘗試,我們已得到了目標(biāo)產(chǎn)物,但立體選擇性控制不太理想,之后,我們將進(jìn)一步嘗試。
[Abstract]:Thiomerization is an important chemical reaction in organic synthesis, which can effectively construct carbon-sulfur bond. In recent years, chemists have made remarkable achievements in the study of sulfur reaction, mainly focusing on the construction of sp~3 carbon-sulfur bond catalyzed by small organic molecules or transition metals. The construction of sp~2 carbon-sulfur bond is mostly obtained by transition metal catalyzed halogenated aromatics, cross-coupling reaction of halogenated alkenes or addition of alkynes, but most of the transition metals are expensive and toxic. Therefore, it is of great significance to develop green, economic and environmentally friendly methods to construct sp~2 carbon-sulfur bond. The main contents of this paper are as follows: in the first chapter, the research progress of organic small molecule catalyzed electrophilic sulfur reagents in the construction of carbon-sulfur bond is reviewed. It mainly includes asymmetric thiomerization reaction, asymmetric thiamine reaction, asymmetric thioetherification reaction and so on, which provides an effective way for the synthesis of organic sulfur compounds with high enantioselectivity. In the second chapter, the thiomerization of 偽, 尾-unsaturated aldehydes catalyzed by azacyclocarbene is introduced. We have developed the first thiomerization reaction of 偽, 尾-unsaturated aldehyde with N-arylthio phthalimide catalyzed by azacyclocarbene, which effectively preserves aldehyde group and provides a new green and efficient method for the formation of carbon-sulfur bond in sp~2. This method has good compatibility, and all kinds of substrate can achieve high yield and good Z / E selectivity. In the third chapter, the cycloaddition reaction of ketene with imine catalyzed by azacyclocarbene was studied. We imagine using chiral azacyclocarbene to catalyze the addition and re-isomerization of enolones with imine quinones to obtain chiral indolones. After a preliminary attempt, we have obtained the target product, but the stereoselective control is not ideal, and then we will try further.
【學(xué)位授予單位】：西北大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O621.251

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本文編號(hào)：2508271