本文選題：脫羧偶聯(lián) + 光催化　； 參考：《中國(guó)科學(xué)技術(shù)大學(xué)》2017年博士論文

【摘要】：脫羧偶聯(lián)反應(yīng)為碳-碳鍵和碳-雜鍵的構(gòu)建提供了強(qiáng)有力的方法。本論文在第一章綜述了脫羧偶聯(lián)反應(yīng)的發(fā)展歷史和現(xiàn)狀,主要包括過(guò)渡金屬催化的脫羧偶聯(lián)反應(yīng)以及可見(jiàn)光促進(jìn)的光催化脫羧偶聯(lián)反應(yīng)。傳統(tǒng)過(guò)渡金屬催化的脫羧偶聯(lián)經(jīng)過(guò)近15年的發(fā)展,已經(jīng)建立了 Pd、Cu、Ag、Au、Rh等單金屬催化體系以及Pd/Cu、Pd/Ag等雙金屬催化體系,實(shí)現(xiàn)了脫羧構(gòu)建C-C鍵、C-N鍵、C-S鍵以及C-P鍵等。然而該類型反應(yīng)的條件相對(duì)苛刻,常需要很高的反應(yīng)溫度來(lái)滿足脫羧所需要的能量,例如Pd催化的脫羧偶聯(lián)反應(yīng)溫度一般在120攝氏度以上,這阻礙了脫羧偶聯(lián)反應(yīng)的發(fā)展和應(yīng)用。且反應(yīng)主要集中在活化的芳基羧酸、烯基羧酸、炔基羧酸等非脂肪類羧酸上,而對(duì)于來(lái)源廣泛的脂肪類羧酸的研究相對(duì)較少。因此急需發(fā)展新的催化體系來(lái)解決這些問(wèn)題。近年來(lái)發(fā)展的可見(jiàn)光促進(jìn)的脫羧偶聯(lián)反應(yīng)條件十分溫和,反應(yīng)利用光照下激發(fā)態(tài)的光催化劑與羧酸負(fù)離子的單電子轉(zhuǎn)移成功實(shí)現(xiàn)了自由基脫羧。將光催化引入脫羧偶聯(lián)將會(huì)為脫羧偶聯(lián)反應(yīng)的發(fā)展提供新的機(jī)遇。光催化的脫羧偶聯(lián)反應(yīng)不僅條件溫和、兼容性強(qiáng),還可以通過(guò)和過(guò)渡金屬催化相結(jié)合解決此前難以解決的問(wèn)題。在第二章中,我們將光催化引入Pd催化的脫羧偶聯(lián)反應(yīng)中,通過(guò)利用光催化和Pd催化相結(jié)合的雙催化體系在溫和條件下實(shí)現(xiàn)了 α-羰基羧酸脫羧芳基化。反應(yīng)既利用了光催化的脫羧能力,又結(jié)合了 Pd催化的成鍵能力。反應(yīng)解決了傳統(tǒng)的Pd催化脫羧偶聯(lián)需要高溫的問(wèn)題。反應(yīng)具有很好的兼容性,能夠?yàn)橥王０奉惢衔锏暮铣商峁┯行Х椒�。N-雜環(huán)芳烴的C-H活化烷基化是N-雜環(huán)芳烴衍生化的重要手段。傳統(tǒng)的Minisci反應(yīng)可以實(shí)現(xiàn)這一過(guò)程,然而傳統(tǒng)的Minisci反應(yīng)依賴于強(qiáng)氧化體系來(lái)實(shí)現(xiàn)脫羧,反應(yīng)兼容性差,且會(huì)誘發(fā)自由基副反應(yīng)。在第三章中,我們結(jié)合光催化利用烷基羧酸作為親電試劑在氧化還原中性條件下實(shí)現(xiàn)了脫羧Minisci反應(yīng),反應(yīng)為N-雜環(huán)芳烴的C-H活化烷基化提供了溫和的有效策略。反應(yīng)通過(guò)光催化實(shí)現(xiàn)自由基脫羧,不需要外加氧化劑。反應(yīng)條件溫和,可以兼容醛基、硫醚、烯烴等易被氧化的官能團(tuán)。傳統(tǒng)的Minisci反應(yīng)難以實(shí)現(xiàn)N-雜環(huán)芳烴C-H活化α-氨基烷基化。因?yàn)閺?qiáng)氧化性條件下脫羧形成的α-氨基烷基自由基很容易被過(guò)渡氧化,形成亞胺正離子,從而失去親核性。第四章中,我們利用氨基酸或多肽的活性羧酸酯作為α-氨基烷基化試劑,結(jié)合光催化和有機(jī)磷酸催化成功實(shí)現(xiàn)了 N-雜環(huán)芳烴C-H活化α-氨基烷基化。反應(yīng)能夠兼容各種天然和非天然氨基酸,多肽也是該反應(yīng)合適的底物類型。同時(shí)溫和的反應(yīng)條件能夠?qū)崿F(xiàn)各類復(fù)雜N-雜環(huán)芳烴的衍生化。我們通過(guò)結(jié)合光催化部分解決了脫羧偶聯(lián)反應(yīng)中的難點(diǎn)問(wèn)題,豐富了脫羧偶聯(lián)反應(yīng)類型,推動(dòng)了光催化在脫羧偶聯(lián)反應(yīng)中的應(yīng)用。當(dāng)然,一些難題依然存在,比如更豐富的脫羧轉(zhuǎn)化類型。這些問(wèn)題將是我們需要繼續(xù)研究和克服的難點(diǎn)。
[Abstract]:Decarboxylation coupling provides a powerful method for the construction of carbon carbon and carbon heteroatom bond. In this paper, the first chapter summarizes the decarboxylation reaction development history and current situation, including the decarboxylation coupling reaction catalyzed by transition metal and visible light to promote the photocatalytic decarboxylation coupling reaction. The traditional transition metal catalyzed decarboxylative coupling after nearly 15 years of development, has established the Pd, Cu, Ag, Au, Rh and Pd/Cu single metal catalysts, Pd/Ag bimetallic catalyst system, realized the decarboxylative C-C bond, C-N bond, C-S bond and C-P bond. However, this type of reaction relatively harsh conditions, often require high reaction temperature to meet the decarboxylation of the energy needed, such as temperature decarboxylation coupling reaction catalyzed by Pd is generally more than 120 degrees Celsius, which hinders the development and application of the decarboxylation reaction. The reaction is mainly concentrated in the aryl carboxylic acid activation, ene Carboxylate alkynyl carboxylic acid, non fatty carboxylic acid, and for the study of fatty carboxylic acid extensive source is relatively small. An urgent need for the development of new catalytic systems to solve these problems. In recent years the development of visible light and promote conditions carboxyl coupling reaction was mild, the reaction using single electron transfer light photocatalyst with the anion of carboxylic acid under the excitation of the successful implementation of the free carboxyl based photocatalytic decarboxylation. The coupling will provide new opportunities for the development of the decarboxylation reaction. The photocatalytic decarboxylation coupling not only mild conditions, good compatibility, can also solve the previous problem difficult to solve by transition metal catalysis combined. In the second chapter, we will introduce the photocatalytic Pd catalyzed decarboxylation coupling, dual catalyst system by utilizing photocatalytic and Pd catalytic phase realized a-Oxo decarboxylation under mild conditions Acid decarboxylation arylation reaction. Both the use of sodium removal capability of photocatalysis, and the combination of the bonding ability of Pd. To solve the Pd catalytic reaction catalyzed decarboxylation coupling to traditional high temperature. The reaction has good compatibility, can ketone and amide compounds to provide an effective method for.N- synthesis of heterocyclic the activation of C-H alkylation of aromatic heterocyclic aromatics is an important means of N- derivatization. Traditional Minisci reaction can be achieved in this process, however, the traditional Minisci reaction depends on the strong oxidation system to achieve the decarboxylation reaction, poor compatibility, and will induce free radical reactions. In the third chapter, we combine photocatalysis using alkyl carboxylic acids as electrophiles in redox neutral conditions the decarboxylation reaction of Minisci reaction, provides an effective strategy for mild N- heterocyclic aromatic C-H alkylation reaction activation. The photocatalytic achieve radical decarboxylation, Do not need additional oxidant. The reaction condition is mild, can be compatible with aldehyde, ether, olefin and other easily oxidized functional groups. The traditional Minisci reaction is difficult to achieve N- C-H activation of alpha amino heterocyclic aromatic alkylation. Because of strong oxidizing conditions the decarboxylation of alpha amino alkyl radicals can easily be oxidized transition and the formation of an imine positive ions, thus losing the nucleophilicity. In the fourth chapter, we use the activity of carboxylic acid esters of amino acids or peptides as alpha amino alkylation reagent combined with photocatalysis and organic phosphoric acid catalyst for the successful implementation of the N- activation of C-H alpha amino heterocyclic aromatic alkylation reaction. Compatible with a variety of natural and non natural amino acids. The reaction peptides are also suitable substrate types. At the same time the mild reaction conditions to realize all kinds of complicated N- heterocyclic aromatic derivative. We combined photocatalysis partly solves the difficulties and questions in the coupling reaction of carboxyl The problem has enriched the type of decarboxylation coupling reaction, and promoted the application of photocatalysis in decarboxylation coupling reactions. Of course, some problems still exist, such as richer decarboxylation conversion types. These problems will be difficult for us to continue to study and overcome.

【學(xué)位授予單位】：中國(guó)科學(xué)技術(shù)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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