1,2,3-三氮唑衍生物选择性碳氢活化研究
发布时间：2018-09-04 14:26
【摘要】：和传统构建碳-碳键及碳-杂键的方法相比,过渡金属催化的碳-氢活化反应具有底物易得、操作简单、副产物少等优点,符合原子经济性要求,是当前研究的热点之一。实现该类反应区域选择性的重要策略,是利用导向基团的辅助功能。本论文主要研究了在1,2,3-三唑环导向下的芳烃碳-氢键的选择性芳基化、硝基化及酰氧基化反应。整个论文主要内容如下:论文第一章综述了近些年碳-氢活化反应进展。主要介绍了在吡啶、偶氮、噻唑、酰胺等基团导向下的钯、铜、钌催化的碳-氢键直接官能团化反应,包含碳-碳、碳-氮及碳-氧键的形成情况。论文第二章研究了 1-苄基-4-芳基-1,2,3-三氮唑与碘代芳烃的反应。以1-苄基-4-苯基-1,2,3-三氮唑与对甲基碘苯的反应为模型,通过条件筛选获得最优反应条件:1-苄基-4-苯基-1,2,3-三氮唑(0.3 mmol),对甲基碘苯(0.75 mmol),Pd(OAc)2(10 mol%),AgOAc(2 eq.),TFA(2 mL),在 110℃下反应 18 小时。在最优条件下,区域选择性的实现了三氮唑环的4号位芳基邻位C-H键直接芳基化反应。当底物1,2,3-三氮唑4号位芳基的间位或邻位含有取代基时会得到单芳基化产物,反之得到双芳基化产物。同位素竞争实验表明,碳-氢键活化不是本反应的决速步骤。论文第三章研究了钯催化的芳烃碳-氢键直接硝基化反应。以1-对甲苯基-4-苯基-1,2,3-三氮唑的反应为模型,通过条件的筛选获得最优条件:1-对甲苯基-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℃下反应18小时。在最优条件下,1,4-二芳基-1,2,3-三氮唑可选择性实现其4号位芳基的邻位碳-氢键的硝化反应,合成了一系列带有硝基的1,4-二芳基-1,2,3-三氮唑衍生物。本方法具有收率高、成本低的优点。该碳-氢键活化过程可能是Pd(Ⅱ)/Pd(Ⅳ)催化循环,按自由基机理进行。论文第四章主要研究了钯催化1,4-二芳基-1,2,3-三氮唑乙酰氧基化反应。以1-对甲苯基-4-苯基-1,2,3-三氮唑的反应作为模型反应,通过条件筛选获得最优反应条件:1-对甲苯基-4-苯基-1,2,3-三氮唑(0.3 mmol),Pd(OAc)2(10 mol%),K2S2O8(2eq.),在混合溶剂(DCE:AcOH=1:1)中,100℃下反应18小时。在最优条件下,实现了三氮唑底物4号位芳基邻位碳-氢键的选择性氧化,且只生成单乙酰氧基化产物,选择性好、收率高,得到了一系列带有乙酰氧基的1,4-二芳基-1,2,3-三氮唑衍生物。同位素竞争实验表明,碳-氢键活化是本反应的决速步骤。
[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，
本文编号：2222425
[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，
本文编号：2222425
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