有机膦及金属催化的原位生成的两性离子与1,3-偶极子的环加成反应
发布时间：2018-09-01 08:15
【摘要】：含氮杂环化合物在农药、医药、材料以及其他精细化工领域中占有重要地位。探索绿色、经济、高效的合成方法,用以构建含氮杂环化合物显得尤为重要。1,3-偶极环加成反应作为构建杂环化合物的重要手段之一,也因此受到了越来越多的关注。本文发展了有机膦及金属催化的原位生成的两性离子与1,3-偶极子的环加成反应,构建了一系列多元含氮杂环化合物,以期望筛选出农药新品种。本文发展了有机膦催化的酞嗪衍生的甲亚胺叶立德与联烯酸酯的新型[3+2]环加成反应,在温和的条件下,以91%-99%的产率构建了一系列酞嗪并四氢吡咯类衍生物,此外还分别以88%产率得到异喹啉并四氢吡咯以及79%产率得到哒嗪并二氢吡咯类化合物,当反应扩大至克级规模时,仍然可以保持98%产率。此反应丰富了有机膦催化领域的[3+2]环加成反应,为合成新型吡咯类杂环化合物提供借鉴参考。本文发展了首例手性膦催化的不对称[4+3]环加成反应。在Kwon手性膦催化下,联烯酸酯与喹唑啉衍生的偶氮次甲基亚胺发生不对称[4+3]环加成反应,可以高达98%产率,33:1 dr的非对映选择性以及96%ee的对映选择性得到喹唑啉并四氢二氮杂卓类化合物,此外,[4+3]环加成产物经氧化开环,可在保持手性的情况下,以高产率得到了系列单环的四氢二氮杂卓类化合物。本文发展了铜催化1,3-偶极子对1,3-偶极子的不对称[3+3]环加成反应。在四氟化硼(四乙腈)铜与手性二茂铁配体催化下,酞嗪衍生的甲亚胺叶立德与亚胺乙酸酯衍生的甲亚胺叶立德可以高达99%产率,20:1 dr的非对映选择性以及99%ee的对映选择性,构建系列酞嗪并哌嗪类环状化合物。此外,将反应放大至克级规模时,仍然可以保持95%产率,20:1 dr的非对映选择性以及94%ee的对映选择性。此反应为手性哌嗪环的合成提供了新的方法依据。本文报道了钯催化的乙烯基碳酸乙烯酯作为五元合成子与偶氮次甲基亚胺的[5+3]环加成反应,在温和的反应条件下,以高达98%产率以及99:1的化学选择性,构建了喹唑啉以及异喹啉并八元环状化合物,发展了一锅法合成中环化合物。
[Abstract]:Nitrogen heterocyclic compounds play an important role in pesticide, medicine, materials and other fine chemicals. It is very important to explore green, economical and efficient synthesis methods to construct nitrogen-containing heterocyclic compounds. As one of the important means of constructing heterocyclic compounds, it is becoming more and more important to construct nitrogen-containing heterocyclic compounds. In this paper, a series of heterocyclic compounds containing nitrogen were constructed by the cycloaddition reaction of organophosphine and metal-catalyzed in situ amphoteric ions with 1 ~ (3) -dipole, in order to screen out new pesticide varieties. In this paper, a new [32] cycloaddition reaction of dienoate with metimide ylide derived from phthalazine catalyzed by organic phosphine was developed. Under mild conditions, a series of phthalazine and tetrahydropyrrole derivatives were constructed in a yield of 91- 99%. In addition, isoquinoline tetrahydropyrrole and pyridazinopyrrole compounds were obtained in 88% yield and 79% yield, respectively. The yield of pyridazinopyrrole compounds remained 98% when the reaction was extended to gram order. This reaction enriches the [32] cycloaddition reaction in the field of organic phosphine catalysis and provides a reference for the synthesis of new pyrrole heterocyclic compounds. The first asymmetric [43] cycloaddition reaction catalyzed by chiral phosphine has been developed. Under the catalysis of Kwon chiral phosphine, [43] cycloaddition reaction of [43] cycloaddition of azomethimide derived from quinazoline was observed. The enantioselectivity of 33: 1 dr and 96% enantioselectivity of quinazoline and tetrahydrodiazepines can be obtained by up to 98% yield. In addition, the [43] cycloaddition product can be oxidized and the chiral property can be maintained. A series of monocyclic tetrahydrodiazepines were obtained in high yield. In this paper, the asymmetric [33] cycloaddition reaction of 1 ~ (3) -dipole catalyzed by copper has been developed. Under the catalysis of copper tetrafluoride (tetraacetonitrile) and chiral ferrocene ligands, the enantioselectivity and enantioselectivity of methyl imine ylide derived from phthalazine and imine acetate can reach up to 99%, 20: 1 dr and 99%, respectively. A series of phthalazine and piperazine ring compounds were constructed. In addition, the enantioselectivity of 95% yield of 20: 1 dr and 94% of enantioselectivity can be maintained when the reaction is enlarged to g order. This reaction provides a new method for the synthesis of chiral piperazine ring. The palladium catalyzed [53] cycloaddition reaction of vinylidene carbonate with azomethimide as a quaternary synthesizer was reported in this paper. Under mild reaction conditions, the yield of vinyl carbonate was as high as 98% and the chemical selectivity of 99:1 was obtained. Quinazoline and isoquinoline octa-ring compounds were synthesized by one-pot method.
【学位授予单位】：中国农业大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：O621.251
本文编号：2216613
[Abstract]:Nitrogen heterocyclic compounds play an important role in pesticide, medicine, materials and other fine chemicals. It is very important to explore green, economical and efficient synthesis methods to construct nitrogen-containing heterocyclic compounds. As one of the important means of constructing heterocyclic compounds, it is becoming more and more important to construct nitrogen-containing heterocyclic compounds. In this paper, a series of heterocyclic compounds containing nitrogen were constructed by the cycloaddition reaction of organophosphine and metal-catalyzed in situ amphoteric ions with 1 ~ (3) -dipole, in order to screen out new pesticide varieties. In this paper, a new [32] cycloaddition reaction of dienoate with metimide ylide derived from phthalazine catalyzed by organic phosphine was developed. Under mild conditions, a series of phthalazine and tetrahydropyrrole derivatives were constructed in a yield of 91- 99%. In addition, isoquinoline tetrahydropyrrole and pyridazinopyrrole compounds were obtained in 88% yield and 79% yield, respectively. The yield of pyridazinopyrrole compounds remained 98% when the reaction was extended to gram order. This reaction enriches the [32] cycloaddition reaction in the field of organic phosphine catalysis and provides a reference for the synthesis of new pyrrole heterocyclic compounds. The first asymmetric [43] cycloaddition reaction catalyzed by chiral phosphine has been developed. Under the catalysis of Kwon chiral phosphine, [43] cycloaddition reaction of [43] cycloaddition of azomethimide derived from quinazoline was observed. The enantioselectivity of 33: 1 dr and 96% enantioselectivity of quinazoline and tetrahydrodiazepines can be obtained by up to 98% yield. In addition, the [43] cycloaddition product can be oxidized and the chiral property can be maintained. A series of monocyclic tetrahydrodiazepines were obtained in high yield. In this paper, the asymmetric [33] cycloaddition reaction of 1 ~ (3) -dipole catalyzed by copper has been developed. Under the catalysis of copper tetrafluoride (tetraacetonitrile) and chiral ferrocene ligands, the enantioselectivity and enantioselectivity of methyl imine ylide derived from phthalazine and imine acetate can reach up to 99%, 20: 1 dr and 99%, respectively. A series of phthalazine and piperazine ring compounds were constructed. In addition, the enantioselectivity of 95% yield of 20: 1 dr and 94% of enantioselectivity can be maintained when the reaction is enlarged to g order. This reaction provides a new method for the synthesis of chiral piperazine ring. The palladium catalyzed [53] cycloaddition reaction of vinylidene carbonate with azomethimide as a quaternary synthesizer was reported in this paper. Under mild reaction conditions, the yield of vinyl carbonate was as high as 98% and the chemical selectivity of 99:1 was obtained. Quinazoline and isoquinoline octa-ring compounds were synthesized by one-pot method.
【学位授予单位】：中国农业大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：O621.251
【参考文献】
相关期刊论文 前2条
1 张芝平;吡咯类杀虫剂的构效关系和作用机理研究[J];世界农药;1999年06期
2 屠豫钦;天然源农药的研究利用—机遇与问题[J];世界农药;1999年04期
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