【作者】 王芳；

【导师】 郭胜海；

【作者基本信息】 河南师范大学 ， 化学， 2018， 硕士

【摘要】 本论文以2-(2-酰胺基芳基)-1H-吲哚或NH-异喹啉酮衍生物为主要原料,基于铜催化氧化反应和分子内环化反应或钯催化氧化环羰化反应,研究并建立了3H-吲哚-3-酮、吲哚[1,2-c]喹唑啉及异吲哚[2,1-b]异喹啉-5,7-二酮的高效合成新方法。主要研究内容如下:一、在盐酸存在下,通过铜催化的2-(2-酰胺基芳基)-1H-吲哚衍生物的C3-氧化以及N1-环化反应,可以顺利实现3H-吲哚-3-酮和吲哚[1,2-c]喹唑啉衍生物的高选择性合成。研究结果表明:该反应的选择性取决于所使用的溶剂。当选用N,N-二甲基甲酰胺(DMF)为反应溶剂时,空气中的氧气可以将吲哚底物选择性地氧化为3H-吲哚-3-酮;而当反应溶剂为1,4-二氧六环时,该底物经由分子内的N1-环化反应,则可以选择性地生成吲哚[1,2-c]喹唑啉衍生物。二、在常压一氧化碳氛围下,基于钯催化的NH-异喹啉酮类化合物的C-H键活化及后续的环羰化反应,建立了一种高效合成异吲哚[2,1-b]异喹啉-5,7-二酮的新方法。氘标记实验结果表明:芳基C(sp~2)-H键的活化可能是该反应的决速步骤。更有趣的是,在一氧化碳的存在下,通过铑/钯接力催化,上述异吲哚[2,1-b]异喹啉-5,7-二酮类化合物还可以直接通过NH-异喹啉酮的前体—N-甲氧基苯甲酰胺和非末端炔烃来制备。更多还原

【Abstract】 In this thesis,several highly efficient and novel methods for the preparation of 3H-indol-3-ones and indolo[1,2-c]quinazolines or isoindolo[2,1-b]isoquinoline-5,7-diones have been achieved through copper-catalyzed indolyl C3-oxygenation and N1-cyclization reactions of 2-(2-amidoaryl)-1H-indoles or palladium-catalyzed oxidative cyclocarbonylation reaction of NH isoquinolone derivatives with CO(1 atm).The main results are as follows:Firstly,a simple and practical procedure for the selective preparation of 3H-indol-3-one and indolo[1,2-c]quinazoline derivatives through copper-catalyzed aerobic oxygenation and intramolecular cyclization reactions of 2-(2-amidoaryl)-1H-indoles in the presence of acid has been developed.Interestingly,the reaction outcomes are exclusively dependent on the reaction medium employed.With DMF as the solvent,the amide moiety of indole substrates could act as an auxiliary to enable the indole’s oxygenation reaction with molecular oxygen from air as the oxidant to give 3H-indol-3-one derivatives in a highly selective manner.On the other hand,when the reactions were performed in 1,4-dioxane,the amide moiety switched to participate in an intramolecular indolyl N1-cyclization to afford indolo[1,2-c]quinazolines as the predominating products.Secondly,an efficient and practical synthesis of isoindolo[2,1-b]isoquinoline-5,7-diones through Pd-catalyzed C-H activation/carbonylative annulation of NH isoquinolones with CO(1 atm)is presented.Deuterium-labeling experiments revealed that the aryl C(sp~2)-H bond activation might be the rate-determining step.More interestingly,the title compounds could also be prepared directly from the the precursors of NH isoquinolones,N-methoxy benzamides and internal alkynes,under an atmospheric pressure of carbon monoxide through a Rh/Pd relay catalysis.更多还原