本文選題：銠催化　切入點：密度泛函理論　出處：《溫州大學》2016年碩士論文　論文類型：學位論文

【摘要】：銠催化C-H活化反應是當前有機化學研究的熱點,該類反應是把不活潑的C-H鍵轉變成C-C鍵、C-X鍵的有效途徑。本論文運用密度泛函理論(DFT)對銠催化含有內(nèi)部氧化劑的苯甲酰胺衍生物C-H活化反應機理進行了理論研究。通過對各種反應路徑能量的比較,確定了反應的具體歷程,同時對實驗中的現(xiàn)象進行了解釋,本論文研究結果對今后的實驗設計和相關理論研究具有重要的理論指導意義。本論文包括以下兩方面的研究內(nèi)容:(1)銠催化苯甲酰胺衍生物與亞甲基環(huán)丙烷的C-H活化/環(huán)化反應的機理研究。通過DFT計算首先研究了N-叔戊酰氧基苯甲酰胺與亞甲基環(huán)丙烷(MCP)反應的各種反應路徑,計算結果發(fā)現(xiàn),當芳基取代基為苯基時,反應發(fā)生OPiv遷移的過程;當芳基取代基為2-呋喃基時,反應發(fā)生β-C消除的過程;但兩種反應過程均需形成Rh(V)-乃春中間體;當芳基取代基為2-噻吩基時,以上兩種反應過程均可發(fā)生。然后對N-甲氧基苯甲酰胺與亞甲基環(huán)丙烷(MCP)的反應機理進行了理論計算研究,通過計算解釋說明兩者無反應發(fā)生的原因。(2)銠催化苯甲酰胺衍生物與環(huán)丙烯的C-H活化/環(huán)化反應的機理研究。通過DFT計算研究了Wang等人發(fā)現(xiàn)的由底物調(diào)控反應化學選擇性的反應機理:反應通過C-H活化過程、烯烴插入形成七元苯并銠雜環(huán)的中間體后,當?shù)孜餅镹-叔戊酰氧基苯甲酰胺時,發(fā)現(xiàn)內(nèi)部氧化劑N-O鍵斷裂較β-C消除更容易,最終生成三環(huán)產(chǎn)物;當?shù)孜餅橐阴１桨窌r,發(fā)現(xiàn)β-C消除較內(nèi)部氧化劑N-O鍵斷裂更容易,最終生成取代的2H-吡喃產(chǎn)物。
[Abstract]:Rhodium-catalyzed C-H activation is a hot topic in organic chemistry. This kind of reaction is an effective way to transform the inert C-H bond into C-C bond C-X bond. In this paper, the mechanism of rhodium catalyzed activation of benzoamide derivative C-H with internal oxidant was studied by using density functional theory (DFT). By comparing the energy of various reaction pathways, The specific course of the reaction is determined, and the phenomena in the experiment are explained. The results of this thesis have important theoretical significance for future experimental design and related theoretical research. This thesis includes two aspects: 1) Rhodium catalyzed C-H activity of benzamide derivatives and methylene cyclopropane. The mechanism of cyclization reaction was studied by DFT calculation. Firstly, various reaction paths of N-tert-glutaryl benzoamide with methylene cyclopropane were studied. The results show that the process of OPiv migration occurs when the aryl substituents are phenyl, the 尾 -C elimination process occurs when the aryl substituents are 2-furyl, but both reaction processes need to form the intermediate RhVAV. When the aryl substituted group is 2-thiophene group, the above two reactions can occur. The mechanism of the reaction between N-methoxy benzoamide and methylene cyclopropane MCPis studied theoretically. The mechanism of C-H activation / cyclization of benzamide derivatives with cyclopropene catalyzed by rhodium was investigated by means of DFT calculations. The substrate-regulated reactions discovered by Wang et al were studied by DFT calculations. Selective reaction mechanism: reaction through C-H activation, After the alkenes were inserted into the intermediates of the 7-member benzo rhodium heterocycles, when the substrate was N-tert-glutaryl benzoamide, it was found that the N-O bond of the internal oxidant was easier to be destroyed than 尾 -C, and the tricyclic product was formed when the substrate was acetanilide. It is found that 尾 -C can eliminate the breakage of N-O bond more easily than the internal oxidant N-O bond, and finally produce the substituted 2H-pyran product.
【學位授予單位】：溫州大學
【學位級別】：碩士
【學位授予年份】：2016
【分類號】：O621.251

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