基于2-溴芳基烷基酮的C—N键构建反应

C—N键的构建反应对于药物开发,天然产物合成,以及含氮化合物的代谢等都具有重要意义。本文结合作者的研究,主要介绍基于2-溴芳基烷基酮的C—N键构建反应及其在药物合成中的应用。

调控CN_x薄膜的紫外可见波段光学性能研究

采用等离子体增强化学气相沉积(PECVD)在不同衬底温度(常温、50、100、150、200℃)下制备了碳氮(CNx)薄膜,并对其形貌、结构及光学性能进行了研究。通过扫描电镜得出随着衬底温度的升高,薄膜由疏松逐渐变得致密。X射线光电子能谱分析表明:薄膜的结合健有sp^2C=C、sp^3C-C、sp^2C=N和sp^3C-N。随着衬底温度的升高,sp^2C=C的比例没有明显变化,sp3C-C比例逐渐增大(28.6%~36.4%),sp^3C-N的比例也逐渐增大(21.4%~33.4%),而sp^2C=N的比例减小(40.2%~21%)。反射光谱和吸收光谱显示:随着衬底温度的升高,薄膜在200~800 nm波段内的反射率增大(8%~40%),吸收率减小(92%~60%)。进一步推导得到薄膜的光学带隙随着衬底温度的升高而增大(2.5~3.57 e V),主要由薄膜中sp^2C=N减少导致的。本文实现了对CN_x薄膜在紫外可见波段范围内的光学带隙的调控。

Metal-Free,Site-Selective C-H Fluorination of Heteroarenes Under Visible Light

The site-selective C-H fluorination of heteroarenes is a straightforward approach to accessing valuable heteroaryl fluorides but remains a formidable challenge.Herein,we report a general strategy for visible-light-induced C-H fluorination of heteroarenes via the merger of N-F fluorinating reagents and silane.Electron paramagnetic resonance experiments provide evidence for the homolytic cleavage of the N-F bond under blue light-emitting diode irradiation,which is the key step in the process.This transformation is metal-free,photocatalysts-free,and site-selective under mild reaction conditions(ambient temperature,visible-light irradiation,tolerant to H2O).The robustness of this protocol has also been highlighted by late-stage modification of complex and medicinally relevant molecules.

无过渡金属体系下C(sp^2)—H键的自由基反应构建C—N键研究进展

C—N键广泛存在于药物分子、天然产物及功能材料中,开发简洁高效的C—N键构建方法具有重要意义.近年来,无过渡金属体系下C(sp^2)—H键的自由基反应构建C—N键取得了诸多进展.该方法反应条件相对温和,反应活性较高,为C—N键构建提供了一条新途径.根据氮源类型的不同,对近年来C(sp^2)—H键的自由基反应构建C—N键的研究进展进行简要论述.

N-doped carbon supported Pd catalysts for N-formylation of amines with CO2/H2

Using mesoporous N-doped carbons(NCs)derived from glucose and melamine as the supports,a series of Pd/NC catalysts were prepared,in which Pd nanoparticles with average size<2.0 nm were uniformly distributed on the supports.It was indicated that the resultant Pd/NC catalysts were effective for N-formylation of amines with CO_2and H_2in ethanol without any additives.Especially,the catalyst Pd/NC-800-6.9%containing quaternary N showed the best performance,affording a series of formylamides in good or even excellent yields.Further investigation reveals that the interaction between the Pd nanoparticles and quaternary nitrogen in the NC support was responsible for the good performance of the catalyst.

Synthesis of N^2-arylaminopyrimidine-5-carbonitrile derivatives via S_NAr amination reaction

An efficient and high-yielding synthesis of N~2-arylaminopyrimidine-5-carbonitrile derivatives starting from arylamines and 2-methylthio-pyrimidine-5-carbonitriIe derivatives has been developed in the presence of cesium carbonate as basic reagent.This new protocol showed high chemical tolerance for a range of functional groups,and only the methylthio substituent on C2 of the pyrimidine ring was replaced with arylamine derivatives under the reaction conditions.

2-氨基吡啶在构建五元、六元氮稠环合成中的应用

2-氨基吡啶是一类重要的合成子,具有独特的双亲核结构,可与酮、醛、酸、多官能团酯类以及卤代芳烃等化合物反应,以构建五元、六元含氮稠杂环.近年来,基于2-氨基吡啶的成环反应倍受关注.鉴于此,以底物种类为分类依据,重点综述了近5年来基于2-氨基吡啶构建咪唑并[1,2-a]吡啶、吡啶并[1,2-a]嘧啶合成方法的研究进展,总结了其在有机合成方法学、药物合成和荧光探针等领域的应用,并展望了基于2-氨基吡啶的绿色化成环及其应用的未来发展趋势.

过渡金属催化合成吡咯-2-甲酸酯的研究进展

吡咯-2-甲酸酯广泛存在于生物活性分子中,在医药领域具有十分重要的应用,因此吡咯-2-甲酸酯类化合物的合成研究受到了广泛关注.过渡金属催化的环加成反应在合成吡咯骨架方面应用广泛,具有区域选择性专一的优点.且过渡金属配体导向的C-N键构筑方法具有原子步骤经济性较高、效率高、反应条件温和以及选择性高等优点.按照过渡金属催化剂分类,对吡咯-2-甲酸酯的[3+2]、[4+1]与[2+2+1]等成环反应的合成方法进行综述,介绍了过渡金属催化吡咯-2-甲酸酯化合物的机理及其应用,并对吡咯-2-甲酸酯的合成进行了展望.

铜催化芳烃胺化反应研究

含氮芳香类化合物在天然产物、药物化学和材料科学等领域得到广泛应用,因此,通过金属催化C–N键偶联反应构建含氮芳香化合物的新方法一直是合成化学家关注的研究课题.铜作为芳烃C–N偶联胺化反应的催化剂,由于其氧化态的多样性表现出了独特的催化性能.本文综述了近年来铜催化芳香类化合物C(sp^(2))–N构建方法的研究进展,也简要描述了代表性胺类反应的反应机理.