本文選題：可見光催化 + 氧氣活化　； 參考：《華中師范大學(xué)》2017年博士論文

【摘要】：氧氣因其豐富、綠色、廉價(jià)及環(huán)境友好等自身優(yōu)點(diǎn),而被視為有機(jī)合成中最理想的氧化劑�；鶓B(tài)的氧氣分子一般以三線態(tài)的形式(3O2)存在,并且通常表現(xiàn)出較低的反應(yīng)活性,而無法被直接應(yīng)用到許多有機(jī)轉(zhuǎn)化中。因此,對(duì)氧氣的活化已經(jīng)成為有機(jī)合成化學(xué)中的一個(gè)重要研究領(lǐng)域。近年來,可見光誘導(dǎo)的反應(yīng)體系作為一種新型的策略已經(jīng)被廣泛應(yīng)用于氧氣活化中,并成功實(shí)現(xiàn)了一系列氧氣參與的氧合反應(yīng)。本論文對(duì)該領(lǐng)域的最新研究進(jìn)展進(jìn)行了詳細(xì)的介紹,并圍繞可見光催化的需氧氧合反應(yīng)開展了相關(guān)研究工作。首先,我們利用可見光誘導(dǎo)的光氧化還原催化體系將氧氣轉(zhuǎn)化為超氧自由基負(fù)離子中間體,并將其應(yīng)用于2,3-二取代吲哚的氧氣氧化/半頻哪醇重排串聯(lián)反應(yīng)中,在溫和的反應(yīng)條件下,高效、綠色地合成了一系列結(jié)構(gòu)多樣的2,2-二取代吲哚-3-酮類化合物。同時(shí),我們通過O-18標(biāo)記實(shí)驗(yàn)、熒光淬滅實(shí)驗(yàn)及反應(yīng)中間體檢測(cè)實(shí)驗(yàn)詳細(xì)地研究了該串聯(lián)反應(yīng)的機(jī)理,并且我們還利用可見光催化一手性磷酸序列催化實(shí)現(xiàn)了該反應(yīng)的不對(duì)稱過程。隨后,基于“優(yōu)勢(shì)骨架合理組合”的設(shè)計(jì)理念,我們將手性雙VA唑啉骨架與光敏劑噻噸酮片段相結(jié)合,設(shè)計(jì)并合成了一類新型可見光響應(yīng)的手性VA唑啉配體。并且,我們還將這類手性配體應(yīng)用于可見光催化的不對(duì)稱氧化輕基化反應(yīng)中,以優(yōu)異的產(chǎn)率和對(duì)映選擇性合成了 一系列α-輕基-β酮酸酯類化合物。通過簡(jiǎn)單的合成轉(zhuǎn)化,該產(chǎn)物可以用于合成高價(jià)值的手性1,2-二醇和1,2-氨基醇類化合物。同時(shí),我們通過一系列實(shí)驗(yàn)對(duì)該轉(zhuǎn)化的反應(yīng)機(jī)理和立體誘導(dǎo)的模式進(jìn)行了研究。另外,我們使用甲基肼與氧氣原位產(chǎn)生雙氧水的策略,實(shí)現(xiàn)了無金屬參與的芳基硼酸的氧化輕基化反應(yīng),并以空氣作為最終的氧化劑。該反應(yīng)以較高的效率合成了一系列苯酚類化合物,并且表現(xiàn)出了較寬的底物及官能團(tuán)適用范圍,操作簡(jiǎn)單(室溫敞口反應(yīng))等優(yōu)點(diǎn)。同時(shí),該反應(yīng)還可以安全的擴(kuò)大到克量級(jí),并且反應(yīng)的效率沒有受到影響。最后,基于課題組的前期工作,我們發(fā)展了可見光催化的胺與醛/酮的自由基交叉偶聯(lián)反應(yīng)。該反應(yīng)以廉價(jià)易得的胺和羰基類化合物為原料,高效、綠色及高原子經(jīng)濟(jì)性地合成了一系列結(jié)構(gòu)多樣的1,2-氨基醇類化合物。同時(shí),該反應(yīng)還可以擴(kuò)大到克量級(jí),或者直接使用太陽(yáng)光作為光源,而反應(yīng)的產(chǎn)率并未受到影響。
[Abstract]:Oxygen is regarded as the most ideal oxidant in organic synthesis because of its advantages such as rich, green, cheap and environmentally friendly.Oxygen molecules in the ground state usually exist in the form of triplet state and usually exhibit low reaction activity and can not be directly used in many organic transformations.Therefore, the activation of oxygen has become an important research field in organic synthesis chemistry.In recent years, the visible light-induced reaction system, as a new strategy, has been widely used in oxygen activation, and a series of oxygenation reactions have been successfully realized.In this paper, the latest research progress in this field is introduced in detail, and the related research work is carried out around the aerobic reaction catalyzed by visible light.Firstly, the oxygen was transformed into superoxide radical anion intermediate by visible light-induced photoredox catalytic system, and it was applied to the series reaction of oxygen oxidation / half-frequency alcohol rearrangement of 2o 3-disubstituted indoles.A series of 2-disubstituted indole-3-ketones with various structures were synthesized efficiently and green under mild reaction conditions.At the same time, the mechanism of the series reaction was studied in detail by O-18 labeling experiment, fluorescence quenching experiment and reaction intermediate detection experiment.Moreover, the asymmetric process of this reaction was realized by using visible light to catalyze the chiral phosphoric acid sequence.Then, based on the design concept of "reasonable combination of dominant skeletons", a novel visible-light responsive chiral VAZoline ligands were designed and synthesized by combining the chiral bis-VA azoline framework with the fragment of Guang Min.Moreover, the chiral ligands were used in the visible photocatalytic asymmetric oxidative light reaction, and a series of 偽-light-尾-ketoacid esters were synthesized with excellent yield and enantioselectivity.By simple synthesis and conversion, the product can be used to synthesize high value chiral 1o 2 diol and 1 o 2 amino alcohol compounds.At the same time, a series of experiments were carried out to study the reaction mechanism and stereoscopic induction model of the transformation.In addition, we use methylhydrazine and oxygen to produce hydrogen peroxide in situ to realize the oxidation of aryl boric acid without metal participation, with air as the final oxidant.A series of phenol compounds were synthesized with high efficiency and showed the advantages of wide application range of substrates and functional groups, simple operation (room temperature exposure reaction) and so on.At the same time, the reaction can be safely extended to the gram order of magnitude, and the efficiency of the reaction is not affected.Finally, based on our previous work, we developed a visible photocatalytic cross-coupling reaction of amine with aldehydes / ketones.In this reaction, a series of 2-amino alcohols with various structures were synthesized by using cheap and easily available amines and carbonyl compounds as raw materials, high efficiency, green and high atomic economy.At the same time, the reaction can be extended to the order of gram, or the direct use of solar light as a light source, and the yield of the reaction has not been affected.
【學(xué)位授予單位】：華中師范大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2017
【分類號(hào)】：O621.251
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本文編號(hào)：1747219