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Iron-Catalyzed Aminomethyloxygenative Cyclization of Hydroxy-α-diazoesters with N,O-Aminals

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Chinese Journal of Chemistry 2020年第4期38卷 389-393页

作者： Suchen Zou Tianze Zhang Siyuan Wang hanmin huang Hefei National Laboratory for Physical Sciences at the Microscale and Department of Chemistry Center for Excellence in Molecular SynthesisUniversity of Science and Technology of ChinaChinese Academy of SciencesHefeiAnhui 230026China State Key Laboratory of Applied Organic Chemistry Lanzhou UniversityLanzhouGonsu 730000China

Summary of main observation and conclusion A new and eficient cyclization reaction has bleen developed to synthesize cyclic a,a-disubstituted B-amino esters via iron-catalyzed intramolecular aminomethyloxygenative cyclization of diazo compounds with N,O-aminal under mild reaction condi-tions.A broad range of hydroxy-a diazoesters with different substituents and various N,O-aminals were compatible with this protocol,affording the corresponding a,a-disubstitutedβ-amino esters bearing a five-to eight-membered oxacycle in good yields.

关键词： esters substituted cyclization

Catalytic Benzylation Reactions: From C-H Bond Activation to C-N Bond Activation

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Chinese Journal of Chemistry 2021年第5期39卷 1070-1078页

作者： Tianxiao Jiang Hongchi Liu Haocheng Zhang hanmin huang Hefei National Laboratory for Physical Sciences at the Microscale and Department of ChemistryUniversity of Science and Technology of ChinaHefeiAnhui 230026China Center for Excellence in Molecular Synthesis of CAS HefeiAnhui 230026China

Transition-metal mediated activation of inert chemical bonds is an ongoing topic in homogeneous catalysis.In view of the abundance and accessibility of alkylarenes and benzylamines,the use of them as benzyl source in catalytic benzylation reactions via benzylic C-H and C-N bond activation is highly desirable.Indeed,compared with the traditional approaches with benzyl halide as the substrates,benzylation reactions via C-H and C-N bond cleavage provide more efficient,atom-economic strategies to access myriads of synthetically important molecules.In this account,our group's efforts on catalytic benzylation reactions via directed C-H activation,nondirected C-H activation and C-N bond activation are summarized.

关键词： Benzylation C-H activation C-N activation Radicals Catalysis

Palladium-Catalyzed Aminomethylation of Nitrodienes and Dienones via Double C-N Bond Activation

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Chinese Journal of Chemistry 2021年第3期39卷 566-570页

作者： Bangkui Yu Bao Gao Xuexia Zhang Haocheng Zhang hanmin huang Hefei National Laboratory for Physical Sciences at the Microscale and Department of Chemistry University of Science and Technology of ChinaHefeiAnhui 230026China Center for Excellence in Molecular Synthesis of CAS HefeiAnhui 230026China

Main observation and conclusion A new strategy for the generation of the active Pd-alkyl species from aminal via C-N bond activation has been established,in which the formation of zwitterionic intermediate through aza-Michael addition of aminal to nitrodienes or dienones is identified as a key step for the activation of the C-N bond.The efficient strategy has enabled a new palladium-catalyzed a-aminomethylation of nitro-dienes and dienones via double C-N bond activation.The scope and versatility of the reaction were demonstrated and a broad range of substrates bearing electron-donating and-withdrawing groups on the aromatic rings were all compatible with this reaction to furnish the desired a-aminomethylated products in moderate to good yields with excellent regioselectivities and E/Z selectivities.

关键词： Aminomethylation Nitrodienes Dienones Aminals C-N bond activation

Palladium-Catalyzed Cascade Double C--N Bond Activation： A New Strategy for Aminomethylation of 1,3-Dienes with Aminals

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Chinese Journal of Chemistry 2018年第10期36卷 929-933页

作者： Cuifang Qiao Anrong Chen Bingjian Gao Yang Liu hanmin huang Hefei National Laboratory for Physical Sciences at the Microscale and Department of Chemistry Center for Excellence in Molecular Synthesis University of Science and Technology of China Chinese Academy of Sci- ences Hefei Anhui 230026 China State Key Laboratory for Oxo Synthesis and Setective Oxidation Lanzhou institute of Chemical Physics Chinese Academy of Sciences Lanzhou Gansu 730000 China

A new palladium-catalyzed selective aminomethylation of conjugated 1,3-dienes with aminais via double C-N bond activation is described. This simple method provides an effective and rapid approach for the synthesis of linear a,13-unsaturated allylic amines with perfect regioselectivity. Mechanistic studies disclosed that one palladium catalyst cleaved two distinct C-N bond to furnish a cascade double C-N bond activation, in which an allylic 1,3-diamine and allylic 1,2-diamine were initially formed as key intermediates through the palladium-catalyzed C-N bond activation of aminal and the α,β-unsaturated allylic amine was subsequently produced via palladium-catalyzed C-N bond activation of the allylic diamines.

关键词： aminomethylation 1,3-diene amine C-N bond activation allyic compounds synthetic methods

阿托伐他汀治疗的心肌梗死患者应用人性化护理的干预效果

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中国医药指南 2024年第11期22卷 90-93页

作者：黄小燕朱晓平黄翰民江西上犹县人民医院赣州341200

目的探析阿托伐他汀治疗的心肌梗死患者应用人性化护理的临床干预效果。方法纳入2021年1月至2022年11月60例在本院接受PCI治疗的心肌梗死患者,纳入患者以随机数字表原则分为对照组、观察组,在阿托伐他汀治疗期间分别给予常规护理、人性... 详细信息

目的探析阿托伐他汀治疗的心肌梗死患者应用人性化护理的临床干预效果。方法纳入2021年1月至2022年11月60例在本院接受PCI治疗的心肌梗死患者,纳入患者以随机数字表原则分为对照组、观察组,在阿托伐他汀治疗期间分别给予常规护理、人性化护理干预,对两组患者的自我管理、生活质量、对护理的满意度评价进行比较。结果关于自我管理评价,在自我概念、自我管理技能、健康知识掌握、自我管理责任感方面,干预后观察组患者评价高于对照组(P<0.05)。关于生活质量评价,干预后两组患者项目评分均提升,观察组患者分数高于对照组(P<0.05)。对护理的满意度,观察组患者评价分数高于对照组(P<0.05)。结论PCI术后的心肌梗死患者在阿托伐他汀治疗期间应用人性化护理干,有利于提高患者对自我管理的认识,提高生活质量,改善预后。

关键词：人性化护理阿托伐他汀心肌梗死自我管理生活质量

Creating Multiple Stereocenters via Rational Design Chiral Ligands and Reactions

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Creating Multiple Stereocenters via Rational Design Chiral L...

Oxidative Strategy for Catalytic C-N Bond Activation

中国化学会第六届全国分子手性学术研讨会

作者： hanmin huang State key laboratory for Oxo Synthesis and Selective Oxidation Lanzhou Institute of Chemical PhysicsChinese Academy of Sciences

Organic motifs with multiple stereocenters exist in numerous natural and unnatural products that exhibit important biological activity.Highly selective synthesis of these chiral compounds from simple starting materials is a challenge.The designing efficient chiral catalysts as well as developing new strategies for controlling the stereoselectivity are critical in this research area.In the past several years,huang and co-workers mainly focused on exploration of efficient enantioselectivity-controlling strategies and designing new catalysts for construction of efficient reactions toward creating multiple stereocenters.Some new chiral diamine ligands and efficient strategies have been developed by rational design,which led to establishing a series of new asymmetric reactions1"7.In this presentation,he will demonstrate some progress on this subject.

关键词： asymmetric catalysis tandem reaction chiral ligands multiple stereocenters

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Oxidative Strategy for Catalytic C-N Bond Activation

Exploring Versatile Metal-Complexes for Catalytic Transformation of C-N Bond

中国化学会第十四届全国有机合成化学学术研讨会

作者： hanmin huang Department of Chemistry University of Science and Technology of China

Transition-metal-catalyzed C-N bond formation reaction has been extensively studied and widely applied in synthetic organic chemistry. Mechanistically, the formation of metal-amide species is crucial for successful realization of such a kind of reaction. Although the primary amines and secondary amines have been commonly employed as amino-sources in these reactions, the easy formation of Werner-type complexes due to their higher affinity to transition metal generally rendered the lower conversion. In comparison, tertiary amines possessing lower affinity to transition metal, which can avoid to formation the Werner-type complex, might be an alternative amino-sources for C-N bond formation reactions. However, the the formidable challenge of activation of simple C-N bonds has largely restrained the development. In this context, we developed three kinds oxidative strategy for activation of the C-N bond and established a series of C-C and C-N bond formation reactions.

关键词： C-N bond activation oxidative strategy transition metal C-N formation

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Exploring Versatile Metal-Complexes for Catalytic Transforma...

中国化学会第九届全国有机化学学术会议

作者： hanmin huang State Key Laboratory for Oxo Synthesis and Selective Oxidation Lanzhou Institute of Chemical physics Chineses Academy of Sciences

＜正＞The transition-metal-catalyzed reactions have emerged as powerful strategy for construction of the diverse organic molecules starting from simple raw materials.In this context,the direct transformation of inert chemical bonds such as C-H,C-C and C-N bond constitutes a conceptually attractive methodology since it avoids the otherwise necessary prefunctionalization of simple starting materials.Mechanistically,the discovery and development new and structure-defined

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碳-杂原子键复分解反应的研究进展

有机化学 2022年第8期42卷 2376-2389页

作者：于帮魁黄汉民中国科学技术大学化学系合肥230026

复分解反应作为一种重要的化学键重组反应,被认为是构建常规路径无法获得的复杂分子的重要方法,极大地推动了合成化学的发展.然而,目前已知的复分解反应大多局限于多重键的重组反应,碳-杂原子键的复分解反应由于其键能比较高,不容易被切... 详细信息

复分解反应作为一种重要的化学键重组反应,被认为是构建常规路径无法获得的复杂分子的重要方法,极大地推动了合成化学的发展.然而,目前已知的复分解反应大多局限于多重键的重组反应,碳-杂原子键的复分解反应由于其键能比较高,不容易被切断,面临着诸多机遇和挑战.根据成键类型进行划分,总结了近十年来过渡金属及氢键催化的C—Si、C—P、C—S、C—I、C—O和C—N键复分解反应的研究进展.

关键词：化学键重组碳-杂原子键复分解杂环化合物