1,2,3-三氮唑衍生物選擇性碳?xì)浠罨芯?/H1>
發(fā)布時間：2018-09-04 14:26
【摘要】：和傳統(tǒng)構(gòu)建碳-碳鍵及碳-雜鍵的方法相比,過渡金屬催化的碳-氫活化反應(yīng)具有底物易得、操作簡單、副產(chǎn)物少等優(yōu)點,符合原子經(jīng)濟(jì)性要求,是當(dāng)前研究的熱點之一。實現(xiàn)該類反應(yīng)區(qū)域選擇性的重要策略,是利用導(dǎo)向基團(tuán)的輔助功能。本論文主要研究了在1,2,3-三唑環(huán)導(dǎo)向下的芳烴碳-氫鍵的選擇性芳基化、硝基化及酰氧基化反應(yīng)。整個論文主要內(nèi)容如下:論文第一章綜述了近些年碳-氫活化反應(yīng)進(jìn)展。主要介紹了在吡啶、偶氮、噻唑、酰胺等基團(tuán)導(dǎo)向下的鈀、銅、釕催化的碳-氫鍵直接官能團(tuán)化反應(yīng),包含碳-碳、碳-氮及碳-氧鍵的形成情況。論文第二章研究了 1-芐基-4-芳基-1,2,3-三氮唑與碘代芳烴的反應(yīng)。以1-芐基-4-苯基-1,2,3-三氮唑與對甲基碘苯的反應(yīng)為模型,通過條件篩選獲得最優(yōu)反應(yīng)條件:1-芐基-4-苯基-1,2,3-三氮唑(0.3 mmol),對甲基碘苯(0.75 mmol),Pd(OAc)2(10 mol%),AgOAc(2 eq.),TFA(2 mL),在 110℃下反應(yīng) 18 小時。在最優(yōu)條件下,區(qū)域選擇性的實現(xiàn)了三氮唑環(huán)的4號位芳基鄰位C-H鍵直接芳基化反應(yīng)。當(dāng)?shù)孜?,2,3-三氮唑4號位芳基的間位或鄰位含有取代基時會得到單芳基化產(chǎn)物,反之得到雙芳基化產(chǎn)物。同位素競爭實驗表明,碳-氫鍵活化不是本反應(yīng)的決速步驟。論文第三章研究了鈀催化的芳烴碳-氫鍵直接硝基化反應(yīng)。以1-對甲苯基-4-苯基-1,2,3-三氮唑的反應(yīng)為模型,通過條件的篩選獲得最優(yōu)條件:1-對甲苯基-4-苯基-1,2,3-三氮唑(0.2 mmol),Pd(OAc)2(10 mol%),NaNO2(1.5eq.),K2S208(2.0eq),DMSO(1.5mL),120℃下反應(yīng)18小時。在最優(yōu)條件下,1,4-二芳基-1,2,3-三氮唑可選擇性實現(xiàn)其4號位芳基的鄰位碳-氫鍵的硝化反應(yīng),合成了一系列帶有硝基的1,4-二芳基-1,2,3-三氮唑衍生物。本方法具有收率高、成本低的優(yōu)點。該碳-氫鍵活化過程可能是Pd(Ⅱ)/Pd(Ⅳ)催化循環(huán),按自由基機理進(jìn)行。論文第四章主要研究了鈀催化1,4-二芳基-1,2,3-三氮唑乙酰氧基化反應(yīng)。以1-對甲苯基-4-苯基-1,2,3-三氮唑的反應(yīng)作為模型反應(yīng),通過條件篩選獲得最優(yōu)反應(yīng)條件:1-對甲苯基-4-苯基-1,2,3-三氮唑(0.3 mmol),Pd(OAc)2(10 mol%),K2S2O8(2eq.),在混合溶劑(DCE:AcOH=1:1)中,100℃下反應(yīng)18小時。在最優(yōu)條件下,實現(xiàn)了三氮唑底物4號位芳基鄰位碳-氫鍵的選擇性氧化,且只生成單乙酰氧基化產(chǎn)物,選擇性好、收率高,得到了一系列帶有乙酰氧基的1,4-二芳基-1,2,3-三氮唑衍生物。同位素競爭實驗表明,碳-氫鍵活化是本反應(yīng)的決速步驟。
[Abstract]:Compared with the traditional methods of constructing carbon-carbon bond and carbon-hetero-bond, the carbon-hydrogen activation reaction catalyzed by transition metals has the advantages of easy to obtain substrate, simple operation, less by-products, and meets the requirements of atom economy. It is one of the hot spots in current research. An important strategy for realizing regioselectivity of this kind of reaction is to utilize the auxiliary function of the guided group. In this paper, the selective aromatization, nitration and acyloxylation of aromatics under the guidance of 1 ~ (2) C ~ (2 +) -triazole ring were studied. The main contents of the thesis are as follows: in chapter 1, the recent progress of carbon-hydrogen activation reaction is reviewed. The direct functionalization of carbon-hydrogen bond catalyzed by pyridine, azo, thiazolium and amide was introduced, including the formation of carbon-carbon, carbon-nitrogen and carbon-oxygen bonds. In chapter 2, the reaction of 1-benzyl-4-aryl-2-triazolium with iodinated aromatics is studied. The reaction of 1-benzyl-4-phenyl-2-triazolium with p-methyliobenzene was used as a model. The optimum reaction conditions were obtained by screening the optimum reaction conditions: 1: 1-benzyl-4-phenyl-2-triazole (0.3 mmol), p-methyliobenzene (0.75 mmol) PD (OAc) 2 (10 mol%) AgOAc (2 eq.) TFA (2 mL),) reacted at 110 鈩，
本文編號：2222425
本文鏈接：http://sikaile.net/kejilunwen/huaxue/2222425.html
[Abstract]:Compared with the traditional methods of constructing carbon-carbon bond and carbon-hetero-bond, the carbon-hydrogen activation reaction catalyzed by transition metals has the advantages of easy to obtain substrate, simple operation, less by-products, and meets the requirements of atom economy. It is one of the hot spots in current research. An important strategy for realizing regioselectivity of this kind of reaction is to utilize the auxiliary function of the guided group. In this paper, the selective aromatization, nitration and acyloxylation of aromatics under the guidance of 1 ~ (2) C ~ (2 +) -triazole ring were studied. The main contents of the thesis are as follows: in chapter 1, the recent progress of carbon-hydrogen activation reaction is reviewed. The direct functionalization of carbon-hydrogen bond catalyzed by pyridine, azo, thiazolium and amide was introduced, including the formation of carbon-carbon, carbon-nitrogen and carbon-oxygen bonds. In chapter 2, the reaction of 1-benzyl-4-aryl-2-triazolium with iodinated aromatics is studied. The reaction of 1-benzyl-4-phenyl-2-triazolium with p-methyliobenzene was used as a model. The optimum reaction conditions were obtained by screening the optimum reaction conditions: 1: 1-benzyl-4-phenyl-2-triazole (0.3 mmol), p-methyliobenzene (0.75 mmol) PD (OAc) 2 (10 mol%) AgOAc (2 eq.) TFA (2 mL),) reacted at 110 鈩，
本文編號：2222425
本文鏈接：http://sikaile.net/kejilunwen/huaxue/2222425.html
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