本文選題：三氟甲硫基化　切入點(diǎn)：串聯(lián)環(huán)化　出處：《蘭州大學(xué)》2017年博士論文

【摘要】：本論文對(duì)AgSCF3促進(jìn)的三氟甲硫基化-串聯(lián)環(huán)化反應(yīng)和酸催化或親電試劑促進(jìn)炔的丙醇(酮)串聯(lián)環(huán)化反應(yīng)進(jìn)行了系統(tǒng)研究,主要包括以下六個(gè)章節(jié):第一章在第一章中,我們主要介紹三氟甲硫基化反應(yīng)的發(fā)展歷程,根據(jù)所用試劑的性質(zhì)可將三氟甲硫基化反應(yīng)分為:自由基型、親電型、親核型、過(guò)渡金屬催化的偶聯(lián)或C-H活化以及多組分參與的三氟甲硫基化反應(yīng)等。自由基三氟甲硫基化反應(yīng)主要是利用AgSCF3與過(guò)硫酸鹽產(chǎn)生的?SCF3自由基引發(fā)的反應(yīng)。親電三氟甲硫基化反應(yīng)主要是一些N-SCF3和O-SCF3試劑參與的反應(yīng),包括對(duì)硼酸、末端炔烴、烯烴、β-酮酯和羧酸等進(jìn)行的三氟甲硫基化反應(yīng)。親核三氟甲硫基化試劑主要包括一些含SCF3陰離子的鹽,它們?cè)贚ewis的催化下可將三氟甲硫基引入到目標(biāo)分子中。在過(guò)渡金屬的催化下,許多親核的三氟甲硫基化試劑可與鹵代芳烴發(fā)生偶聯(lián)反應(yīng),或者在導(dǎo)向基團(tuán)誘導(dǎo)下通過(guò)C-H活化而引入三氟甲硫基。三氟甲硫基中的硫和氟也可以由單質(zhì)硫和TMSCF3分別提供,即多組分參與的三氟甲硫基化反應(yīng)。第二章在自由基反應(yīng)中,烯烴較炔烴更容易捕獲自由基從而生成烷基自由基,因此由炔烴引發(fā)的自由基反應(yīng)會(huì)更加困難,產(chǎn)率通常也會(huì)大幅降低。由于1,6-烯炔具有多個(gè)反應(yīng)位點(diǎn),因此我們?cè)O(shè)想將1,6-烯炔底物中的烯烴部分與位阻基團(tuán)相連,強(qiáng)迫三氟甲硫基自由基從叁鍵引發(fā)反應(yīng)。在本章中,我們?cè)谝粋�(gè)反應(yīng)歷程中成功構(gòu)建了一個(gè)C-SCF3鍵和兩個(gè)C-C鍵,合成了一系列三氟甲硫基取代的芴衍生物,這也是從碳碳叁鍵引發(fā)的三氟甲硫基化-自由基串聯(lián)環(huán)化反應(yīng)的首例報(bào)道。第三章在第三章中,我們利用AgSCF3中的三氟甲硫基負(fù)離子直接參與反應(yīng),發(fā)展了BF3·OEt2?AgSCF3促進(jìn)的炔丙醇的三氟甲硫基化-串聯(lián)環(huán)化反應(yīng)。在一步反應(yīng)中構(gòu)建了一個(gè)C-SCF3鍵和一個(gè)C-O/N鍵,得到了許多三氟甲硫基取代的2H-色烯和1,2-二氫喹啉衍生物。第四章在第四章中,我們對(duì)各種酸催化和親電試劑促進(jìn)的炔丙醇(酮)參與的串聯(lián)環(huán)化反應(yīng)進(jìn)行了簡(jiǎn)單歸納。首先介紹了Meyer-Schuster重排反應(yīng)和基于Meyer-Schuster重排反應(yīng)的串聯(lián)環(huán)化反應(yīng)設(shè)計(jì)。炔丙醇的串聯(lián)環(huán)化反應(yīng)主要?dú)v程包括:(i)炔丙醇的羥基在酸或者親電試劑作用下離去生成炔丙基碳正離子中間體,(ii)上述中間體緊接著會(huì)重排為聯(lián)烯碳正離子中間體,(iii)體系中親核性比水強(qiáng)的親核試劑會(huì)進(jìn)攻該聯(lián)烯碳正離子中間體得到聯(lián)烯中間體,(iv)最后在酸或親電試劑作用下,體系中其他親核基團(tuán)進(jìn)攻原聯(lián)烯碳原子后成環(huán)。炔丙酮中的炔鍵可在酸或親電試劑活化下與親核試劑參與反應(yīng)。根據(jù)親核試劑的不同,我們主要介紹碳親核試劑(富電子芳烴、烯烴等)和含雜原子官能團(tuán)的親核試劑(氧、硫、氮原子)參與的串聯(lián)環(huán)化反應(yīng)。第五章在第五章中,我們從同一個(gè)二炔酮底物出發(fā),發(fā)展了在布朗斯特酸催化下合成4-吡喃酮的反應(yīng)以及NIS促進(jìn)的選擇性合成4-吡啶酮和3-吡咯酮的反應(yīng)。這三種產(chǎn)物的分子結(jié)構(gòu)都是某些具有藥物活性的天然產(chǎn)物分子的關(guān)鍵骨架。第六章2H-色烯和4-色滿酮作為重要的類黃酮骨架結(jié)構(gòu),其合成方法歷來(lái)受到有機(jī)化學(xué)家的廣泛關(guān)注。在第六章中,我們?cè)趦煞N反應(yīng)體系中發(fā)展了同一炔丙醇底物的兩種環(huán)化方式,分別構(gòu)筑了2H-色烯和4-色滿酮分子的骨架結(jié)構(gòu)。所得碘代4-色滿酮產(chǎn)物還可通過(guò)鈀催化的交叉偶聯(lián)反應(yīng)實(shí)現(xiàn)進(jìn)一步衍生。
[Abstract]:In this paper, three fluorine methylthiolation - AgSCF3 promotes tandem cyclization and acid catalyzed electrophilic reagents or promoting alkyne propyl alcohol (ketone) studied tandem cyclization reaction, mainly includes the following six chapters: the first chapter in the first chapter, we mainly introduce the development process of three fluorine methylthio the reaction, according to the nature of the reagent can be three fluorine methylthiolation divided into: free radical, electrophilic type, pro karyotype, transition metal catalyzed coupling or C-H activation and multiple components involved in three fluorine methylthiolation. Three fluorine free radical methylthiolation reaction with persulfate is mainly produced by AgSCF3? SCF3 free radical reactions. Three electrophilic fluorine methylthiolation is mainly involved in the N-SCF3 and O-SCF3 reagent, including boric acid, terminal alkynes, alkenes, three fluorine methylthiolation beta keto ester and carboxylic acid and so on three fluorine nucleophilic. Methylthiolation reagent mainly includes some SCF3 containing anionic salts, which under the catalysis of Lewis can be three fluorine methylthio into target molecules. In the transition metal catalyzed by many nucleophilic three fluorine methylthiolation reagent reaction with halogenated aromatic hydrocarbons, or in the guide to group induced by C-H activation and the introduction of three fluorine methylthio sulfur and fluorine fluorine. Three methylthio in can also be provided by sulfur and TMSCF3, namely multi components involved in three fluorine methylthiolation. In the second chapter, free radical reaction, is more likely to capture the alkene alkyne free radical the formation of alkyl radicals, so radical reactions caused by alkyne will be more difficult, the yield is usually significantly reduced. Because of 1,6- enyne with multiple reaction sites, so we will assume part of 1,6- olefin enyne in the substrate is connected with the chromophore, forcing three fluorine methylmercapto Free radicals from the triple bond reaction. In this chapter, we successfully constructed a C-SCF3 bonds and two C-C bonds in a reaction process, a series of Fluorene Derivatives and three fluorine methylmercapto substituted were synthesized, which is triggered from a carbon carbon triple bond cyclization tandem three fluorine methyl sulfide base - free radical first report. The third chapter in the third chapter, we use three fluorine methylthio negative ions in AgSCF3 is directly involved in the reaction, the development of BF3 - OEt2? Cyclization of three fluorine series methylthiolation - AgSCF3 promoted propargyl alcohol. In one step reaction in a building a C-SCF3 key and a C-O/N key, 2H- chromen and 1,2- two hydrogen quinoline derivatives many three fluorine methylmercapto substituted is obtained. The fourth chapter in the fourth chapter, we analyze several acid catalyzed electrophilic reagents promoted propargyl alcohol (ketone) tandem cyclization reactions involved are outlined. Firstly Meyer-Schuster Rearrangement and tandem cyclization of Meyer-Schuster rearrangement reaction. Based on the design including the main course of tandem cyclization reaction of propargyl alcohol (I): propargyl alcohol hydroxyl in acid or electrophiles generated under the action of left propargyl carbonium ion (II), the intermediate tight then rearranged into allenes carbonium ion intermediate (III) system in the nucleophilic water than strong nucleophile will attack the allenic carbocation intermediate allene intermediates (IV) in acid or electrophiles under the system of other nucleophiles attack the original allenic carbon atom ring. Alkyne alkyne acetone in the acid or electrophiles and nucleophiles in the activation reaction. According to the different nucleophiles, we introduce carbon nucleophiles (electron rich aromatics, alkenes etc.) and heteroatom containing functional groups of nucleophiles (oxygen, sulfur and nitrogen atoms in the ring series) The reaction. The fifth chapter in the fifth chapter, we start from the same two ynones substrate, development in catalytic synthesis of Bronsted acid 4- pyrone reaction and NIS promote the selective synthesis of 4- pyridone and 3- pyrrolidone reaction. The molecular structure of these three kinds of products are the key frame of natural products some molecules having pharmacological activity. In the sixth chapter, 2H- and 4- chromen chromanone as an important flavonoid skeleton structure, the synthesis method has been widely concerned by organic chemists. In the sixth chapter, we in the two reaction system developed with a propargyl alcohol substrate two cyclization, respectively. To build a framework of 2H- and 4- chromen chromanone. The molecular iodine 4- chromanone products but also through palladium catalyzed cross coupling reactions to achieve further derivatization.

【學(xué)位授予單位】：蘭州大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2017
【分類號(hào)】：O621.25
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本文編號(hào)：1673983