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Construction of 1,4-Dihydropyridines: The Evolution of C4 Source 1,4-二氢吡啶的构建:C4来源的演化。
IF 8.6 2区 化学 Q1 Chemistry Pub Date : 2023-09-25 DOI: 10.1007/s41061-023-00440-x
Siyu Song, Yongchao Wang, Fuchao Yu

The field of cascade cyclization for the construction of 1,4-dihydropyridines (1,4-DHPs) has been continuously expanding during the last decades because of their broad-spectrum biological and synthetic importance. To date, many methods have been developed, mainly including the Hantzsch reaction, Hantzsch-like reaction and newly developed cascade cyclization, in which various synthons have been successively developed as C4 sources of 1,4-DHPs. This review presents the cascade cyclization synthesis strategy for the construction of 1,4-DHPs according to various C4 sources from carbonyl compounds, alkenyl fragments, alcohols, aliphatic amines, glycines and other C4 sources.

在过去的几十年里,用于构建1,4-二氢吡啶(1,4-DHP)的级联环化领域由于其广谱的生物和合成重要性而不断扩大。到目前为止,已经开发了许多方法,主要包括Hantzsch反应、Hantzsch-like反应和新开发的级联环化,其中各种合成子相继被开发为1,4-DHP的C4来源。本文介绍了从羰基化合物、烯基片段、醇、脂族胺、甘氨酸和其他C4来源构建1,4-DHP的级联环化合成策略。
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引用次数: 0
C–H Bond Functionalization of N-Heteroarenes Mediated by Selectfluor 选择性荧光介导N-杂芳烃的C-H键功能化。
IF 8.6 2区 化学 Q1 Chemistry Pub Date : 2023-09-22 DOI: 10.1007/s41061-023-00437-6
Angel H. Romero

Herein, recent developments for Selectfluor-mediated C–H functionalization of N-heteroarenes are described. This type of C–H bond activation is an attractive and competitive alternative to traditional methodologies, allowing the functionalization of a variety of chemical functions. In addition, Selectfluor is a more sustainable and economically accessible oxidant compared with expensive/toxic metals or hazardous peroxides. For a practical understanding, the current review classified systematically the reported strategies in four subsections as follows: (1) carbon–carbon formation, (2) carbon–nitrogen bond formation, (3) carbon–chalcogen bond, and (4) carbon–halogen bond formation. Mechanistic aspects and reaction conditions are fully discussed to provide an understanding of the aspects that govern C–H functionalization in N-heteroarenes mediated by Selectfluor.

Graphical Abstract

本文介绍了选择性荧光介导的N-杂芳烃的C-H功能化的最新进展。这种类型的C-H键活化是传统方法的一种有吸引力和竞争力的替代方法,允许各种化学功能的功能化。此外,与昂贵/有毒的金属或危险的过氧化物相比,Selectfluor是一种更可持续、更经济的氧化剂。为了便于实际理解,本综述将所报道的策略系统地分为四个子部分,如下:(1)碳-碳形成,(2)碳-氮键形成,(3)碳-硫族键和(4)碳-卤键形成。充分讨论了机理方面和反应条件,以提供对由Selectfluor介导的N-杂芳烃中C-H官能化的控制方面的理解。
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引用次数: 1
Functionalization of BODIPY Dyes with Additional C–N Double Bonds and Their Applications 附加C-N双键的BODIPY染料的功能化及其应用。
IF 8.6 2区 化学 Q1 Chemistry Pub Date : 2023-09-07 DOI: 10.1007/s41061-023-00438-5
Huriye Ilhan, Yusuf Cakmak

BODIPY (4-bora-3a,4a-diaza-s-indacene) dyes are regarded as highly useful compounds due to their rich photophysical properties, stability, and ease of functionalization. In recent years, hot topics studied with this class of compounds are targeted photodynamic therapy, photothermal therapy, fluorescent bioimaging agents, structural modification of the BODIPY core, synthesis of BODIPY analogs, and BODIPY-based supramolecular constructs. This review covers the advances in BODIPY structures substituted with additional carbon–nitrogen double bonds, namely imines, hydrazones, oximes, and related derivatives for various applications. Works based on fluorescent indicators of anions, cations, and neutral molecules are included in this review. In addition, the use of such structures for pharmaceutical applications, photodynamic therapy, fluorescent switches, and fluorescent building blocks are also investigated. In addition to covering the major literature within the mentioned subclass, design principles, working mechanisms, and outlooks are also provided to enlighten forthcoming promising efforts. With this work, we aim to provide insights about the synthesis, photophysical properties, contribution of C=N bonds to a class of dye, and possible areas of use and stimulate researchers to present new ideas and overcome the current problems using these derivatives.

Graphical Abstract

BODIPY(4-硼-3a,4-二氮杂-s-茚)染料由于其丰富的光物理性质、稳定性和易于官能化而被认为是非常有用的化合物。近年来,这类化合物的研究热点是靶向光动力疗法、光热疗法、荧光生物成像剂、BODIPY核心的结构修饰、BODIPY类似物的合成以及基于BODIPY的超分子构建。本文综述了用额外的碳氮双键取代的BODIPY结构的进展,即亚胺、腙、肟和用于各种应用的相关衍生物。基于阴离子、阳离子和中性分子的荧光指示剂的工作包括在这篇综述中。此外,还研究了这种结构在药物应用、光动力治疗、荧光开关和荧光构建块中的应用。除了涵盖上述子类中的主要文献外,还提供了设计原则、工作机制和展望,以启发即将进行的有希望的工作。通过这项工作,我们旨在提供关于合成、光物理性质、C=N键对一类染料的贡献以及可能的使用领域的见解,并激励研究人员提出新的想法,使用这些衍生物克服当前的问题。
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引用次数: 0
Recent Advances in MXene Quantum Dots: A Platform with Unique Properties for General-Purpose Functional Materials with Novel Biomedical Applications MXene量子点的最新进展:一种具有独特性能的平台,用于具有新型生物医学应用的通用功能材料。
IF 8.6 2区 化学 Q1 Chemistry Pub Date : 2023-09-05 DOI: 10.1007/s41061-023-00439-4
Elham Einafshar, Nafiseh Einafshar, Majid Khazaei

Developing new, high-performance materials is a prerequisite for technological advancement. In comparison to bulk materials, quantum dots have a number of good advantages due to their small size, high surface area, and quantum dimensions. Quantum dots, two-dimensional materials with lateral dimensions less than 100 nm, can be generated by the quantum confinement effect. Mxene quantum dots (MQDs) retain some of their two-dimensional characteristics. They also exhibit novel physicochemical properties, including enhanced dispersibility in aqueous and nonaqueous phases, modification or doping capabilities, and photoluminescence. MQDs, due to their unique and diverse properties, have been receiving a great deal of attention as new members of the Mxene group and wide use for biotechnology, bioimaging, optoelectronics, catalysis, cancer therapy, etc. This review aims to provide an overview of the synthesis of MQDs, their optical properties, and their cancer therapy applications. MQDs exhibit remarkable photothermal and photodynamic features and can be suitable for bioimaging. In addition to obtaining bioimaging, photothermal therapy (PTT) and photodynamic therapy (PDT) effects simultaneously, MQDs have high biocompatibility in vitro and in vivo, providing evidence of their potential clinical utility. Herein, recent developments and future prospects concerning MQDs biomedical applications are discussed.

Graphical Abstract

开发新的高性能材料是技术进步的先决条件。与大块材料相比,量子点由于其小尺寸、高表面积和量子尺寸而具有许多良好的优势。量子点是横向尺寸小于100nm的二维材料,可以通过量子约束效应产生。Mxene量子点(MQD)保留了它们的一些二维特性。它们还表现出新的物理化学性质,包括在水相和非水相中增强的分散性、改性或掺杂能力以及光致发光。MQD由于其独特和多样的性质,作为Mxene组的新成员,以及在生物技术、生物成像、光电子、催化、癌症治疗等方面的广泛应用,受到了广泛的关注。本综述旨在概述MQD的合成、其光学性质及其癌症治疗应用。MQD表现出显著的光热和光动力特性,可适用于生物成像。除了同时获得生物成像、光热治疗(PTT)和光动力治疗(PDT)效果外,MQD在体外和体内都具有高度的生物相容性,为其潜在的临床应用提供了证据。本文讨论了MQDs生物医学应用的最新进展和未来前景。
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引用次数: 2
The Novel Organic Emitters for High-Performance Narrow-Band Deep Blue OLEDs 用于高性能窄带深蓝OLED的新型有机发光体。
IF 8.6 2区 化学 Q1 Chemistry Pub Date : 2023-08-26 DOI: 10.1007/s41061-023-00436-7
Jialu Gu, Wei Shi, Haixia Zheng, Guo Chen, Bin Wei, Wai-Yeung Wong

Narrow-band deep-blue organic light-emitting diodes (OLEDs) have played a key role in the field of high-quality full-color displays. However, because of the considerable challenges of inherent band gaps, unbalanced carrier injection and the lack of molecular structures, narrow-band deep-blue emitters develop slowly compared with red- and green-emitting materials. Encouragingly, with the continuous efforts of scientists in recent years, great progress has been made in the molecule design and material synthesis of highly efficient narrow-band deep-blue emitters. The typical deep-blue emitters which exhibit narrow emission with a full width at half maximum of < 50 nm are summarized in this article. They are divided into the three categories: fluorescence, phosphorescence and thermally activated delayed fluorescence. The methods of molecular design for realizing narrow-band deep-blue emission are described in detail and future research directions are also discussed in this article.

窄带深蓝色有机发光二极管(OLED)在高质量全色显示器领域发挥了关键作用。然而,由于固有带隙、不平衡载流子注入和分子结构的缺乏等诸多挑战,与红色和绿色发射材料相比,窄带深蓝色发射体发展缓慢。令人鼓舞的是,近年来,在科学家的不断努力下,高效窄带深蓝发射体的分子设计和材料合成取得了巨大进展。本文总结了典型的深蓝色发射体,它们表现出窄发射,半峰全宽<50nm。它们分为三类:荧光、磷光和热激活延迟荧光。本文详细介绍了实现窄带深蓝色发射的分子设计方法,并对未来的研究方向进行了讨论。
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引用次数: 0
Recent Progress on Nitrogen-Rich Energetic Materials Based on Tetrazole Skeleton 基于四唑骨架的富氮含能材料研究进展。
IF 8.6 2区 化学 Q1 Chemistry Pub Date : 2023-08-23 DOI: 10.1007/s41061-023-00435-8
Bihai Chen, Han Lu, Jiayi Chen, Zhaoxu Chen, Shuang-Feng Yin, Lifen Peng, Renhua Qiu

Development of nitrogen-rich energetic materials has gained much attention because of their remarkable properties including large nitrogen content and energy density, good thermal stability, low sensitivity, good energetic performance, environmental friendliness and so on. Tetrazole has the highest nitrogen and highest energy contents among the stable azoles. The incorporation of diverse explosophoric groups or substituents into the tetrazole skeleton is beneficial to obtain high-nitrogen energetic materials having excellent energetic performance and suitable sensitivity. In this review, the development of high-nitrogen energetic materials based on tetrazole skeleton is highlighted. Initially, the property and utilization of nitrogen-rich energetic materials are presented. After showing the advantage of the tetrazole skeleton, the high-nitrogen energetic materials based on tetrazole are classified and introduced in detail. Based on different types of energetic materials (EMs), the synthesis and properties of nitrogen-rich energetic materials based on mono-, di-, tri- and tetra-tetrazole are summarized in detail.

Graphical Abstract

富氮含能材料因其氮含量和能量密度大、热稳定性好、灵敏度低、高能性能好、环境友好等显著性能而备受关注。在四唑骨架中掺入不同的爆炸基团或取代基有利于获得具有优异能量性能和合适灵敏度的高氮含能材料。综述了基于四唑骨架的高氮含能材料的研究进展。首先介绍了富氮含能材料的性质及其利用。在展示了四唑骨架的优点后,对基于四唑的高氮含能材料进行了详细的分类和介绍。基于不同类型的含能材料,详细总结了基于单、二、三和四唑的富氮含能材料的合成和性能。
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引用次数: 1
Performance Regulation of Single-Atom Catalyst by Modulating the Microenvironment of Metal Sites 通过调节金属位点的微环境来调节单原子催化剂的性能。
IF 8.6 2区 化学 Q1 Chemistry Pub Date : 2023-07-22 DOI: 10.1007/s41061-023-00434-9
Hanyu Hu, Yanyan Zhao, Yue Zhang, Jiangbo Xi, Jian Xiao, Sufeng Cao

Metal-based catalysts, encompassing both homogeneous and heterogeneous types, play a vital role in the modern chemical industry. Heterogeneous metal-based catalysts usually possess more varied catalytically active centers than homogeneous catalysts, making it challenging to regulate their catalytic performance. In contrast, homogeneous catalysts have defined active-site structures, and their performance can be easily adjusted by modifying the ligand. These characteristics lead to remarkable conceptual and technical differences between homogeneous and heterogeneous catalysts. As a recently emerging class of catalytic material, single-atom catalysts (SACs) have become one of the most active new frontiers in the catalysis field and show great potential to bridge homogeneous and heterogeneous catalytic processes. This review documents a brief introduction to SACs and their role in a range of reactions involving single-atom catalysis. To fully understand process-structure-property relationships of single-atom catalysis in chemical reactions, active sites or coordination structure and performance regulation strategies (e.g., tuning chemical and physical environment of single atoms) of SACs are comprehensively summarized. Furthermore, we discuss the application limitations, development trends and future challenges of single-atom catalysis and present a perspective on further constructing a highly efficient (e.g., activity, selectivity and stability), single-atom catalytic system for a broader scope of reactions.

Graphical Abstract

金属基催化剂包括均相和非均相催化剂,在现代化学工业中发挥着至关重要的作用。非均相金属基催化剂通常比均相催化剂具有更多变化的催化活性中心,这使得调节其催化性能具有挑战性。相反,均相催化剂具有明确的活性位点结构,并且可以通过修饰配体来容易地调节它们的性能。这些特征导致均相催化剂和非均相催化剂之间存在显著的概念和技术差异。单原子催化剂(SACs)作为一种新兴的催化材料,已成为催化领域最活跃的新前沿之一,在连接均相和非均相催化过程方面显示出巨大的潜力。这篇综述简要介绍了SAC及其在涉及单原子催化的一系列反应中的作用。为了充分理解化学反应中单原子催化的过程-结构-性质关系,全面总结了SAC的活性位点或配位结构和性能调节策略(如调节单原子的化学和物理环境)。此外,我们还讨论了单原子催化的应用局限性、发展趋势和未来挑战,并对进一步构建高效(如活性、选择性和稳定性)的单原子催化体系以用于更广泛的反应提出了展望。
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引用次数: 1
Recent Progress in NiH-Catalyzed Linear or Branch Hydrofunctionalization of Terminal or Internal Alkenes NiH催化末端或内部烯烃的线性或支链加氢官能化的最新进展。
IF 8.6 2区 化学 Q1 Chemistry Pub Date : 2023-07-20 DOI: 10.1007/s41061-023-00433-w
Huimin Yang, Yang Ye

The construction of C–C and C–X (X = N, O, Si, etc.) bonds is an important field in organic synthesis and methodology. In recent decades, studies on transition metal-catalyzed functionalization of alkenes have been on the rise. The individual properties of different transition metals determine the type of reaction that can be applied. Generally, post-transition metals with a large number of electrons in the d-orbit such as Mn, Fe, Co, Ni, Cu and Zn, etc., can be applied to more reaction types than pre-transition metals with a small number of electrons (e.g., Ti, Zr, etc.). Alkyl nickel intermediates formed by oxidative addition could couple with various of nucleophiles or electrophiles. Moreover, nickel has several oxidation valence states, which can flexibly realize a variety of catalytic cycles. These characteristics make nickel favored by researchers in the field of functionalization of alkenes, especially for the hydrofunctionalization of alkenes. Both terminal and internal alkenes could be converted, and the strategies of synthesizing linear and branched compounds have been expanded. Moreover, the guiding groups in alkenes played an almost decisive role in the regional selectivity, and the ligand or temperature also had regulating effects. Herein, we will give a comprehensive and timely overview of the works about the Ni-catalyzed hydrofunctionalization of alkenes and some insights on regional selectivity.

Graphic Abstract

C-C和C-X(X = N、 O、Si等)键是有机合成和方法学中的一个重要领域。近几十年来,过渡金属催化烯烃官能化的研究呈上升趋势。不同过渡金属的单独性质决定了可以应用的反应类型。通常,在d轨道上具有大量电子的后过渡金属,如Mn、Fe、Co、Ni、Cu和Zn等,可以应用于比具有少量电子的前过渡金属(如Ti、Zr等)更多的反应类型。通过氧化加成形成的烷基镍中间体可以与各种亲核试剂或亲电试剂偶联。此外,镍具有多种氧化价态,可以灵活地实现多种催化循环。这些特性使镍在烯烃官能化领域受到研究人员的青睐,尤其是在烯烃的加氢官能化方面。末端烯烃和内部烯烃都可以转化,合成直链和支链化合物的策略也得到了扩展。此外,烯烃中的引导基团对区域选择性起着几乎决定性的作用,配体或温度也有调节作用。在此,我们将全面、及时地综述镍催化烯烃加氢官能化的工作,并对区域选择性进行一些见解。
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引用次数: 0
Structure-Based Drug Design of RdRp Inhibitors against SARS-CoV-2 基于结构的抗SARS-CoV-2 RdRp抑制剂药物设计
IF 8.6 2区 化学 Q1 Chemistry Pub Date : 2023-06-15 DOI: 10.1007/s41061-023-00432-x
Kiran Shehzadi, Afsheen Saba, Mingjia Yu, Jianhua Liang

The severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) has caused a worldwide pandemic since 2019, spreading rapidly and posing a significant threat to human health and life. With over 6 billion confirmed cases of the virus, the need for effective therapeutic drugs has become more urgent than ever before. RNA-dependent RNA polymerase (RdRp) is crucial in viral replication and transcription, catalysing viral RNA synthesis and serving as a promising therapeutic target for developing antiviral drugs. In this article, we explore the inhibition of RdRp as a potential treatment for viral diseases, analysing the structural information of RdRp in virus proliferation and summarizing the reported inhibitors’ pharmacophore features and structure–activity relationship profiles. We hope that the information provided by this review will aid in structure-based drug design and aid in the global fight against SARS-CoV-2 infection.

Graphical Abstract

2019年以来,严重急性呼吸综合征冠状病毒2型(SARS-CoV-2)在全球范围内大流行,传播迅速,对人类健康和生命构成重大威胁。由于该病毒确诊病例超过60亿,对有效治疗药物的需求比以往任何时候都更加迫切。RNA依赖性RNA聚合酶(RdRp)在病毒复制和转录中起着至关重要的作用,催化病毒RNA合成,是开发抗病毒药物的一个有希望的治疗靶点。在本文中,我们探讨了抑制RdRp作为一种潜在的病毒性疾病的治疗方法,分析了RdRp在病毒增殖中的结构信息,总结了已报道的抑制剂的药效团特征和构效关系。我们希望本综述提供的信息将有助于基于结构的药物设计,并有助于全球抗击SARS-CoV-2感染。图形抽象
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引用次数: 2
Synthetic Approaches, Biological Activities, and Structure–Activity Relationship of Pyrazolines and Related Derivatives 吡唑啉类及其衍生物的合成方法、生物活性及构效关系
IF 8.6 2区 化学 Q1 Chemistry Pub Date : 2023-04-08 DOI: 10.1007/s41061-023-00422-z
Rajnish Kumar, Himanshu Singh, Avijit Mazumder,  Salahuddin, Ranjeet Kumar Yadav

It has been established that pyrazolines and their analogs are pharmacologically active scaffolds. The pyrazoline moiety is present in several marketed molecules with a wide range of uses, which has established its importance in pharmaceutical and agricultural sectors, as well as in industry. Due to its broad-spectrum utility, scientists are continuously captivated by pyrazolines and their derivatives to study their chemistry. Pyrazolines or their analogs can be prepared by several synthesis strategies, and the focus will always be on new greener and more economical ways for their synthesis. Among these methods, chalcones, hydrazines, diazo compounds, and hydrazones are most commonly applied under different reaction conditions for the synthesis of pyrazoline and its analogs. However, there is scope for other molecules such as Huisgen zwitterions, different metal catalysts, and nitrile imine to be used as starting reagents. The present article consists of recently reported synthetic protocols, pharmacological activities, and the structure–activity relationship of pyrazoline and its derivatives, which will be very useful to researchers.

Graphical Abstract

吡唑啉及其类似物是具有药理活性的支架。吡唑啉部分存在于几种市场上的分子中,具有广泛的用途,这在制药和农业部门以及工业中已经确立了它的重要性。由于它的广谱效用,科学家们不断地被吡唑啉及其衍生物所吸引,研究它们的化学性质。吡唑啉或其类似物可以通过几种合成策略来制备,并且重点将始终放在新的更环保和更经济的合成方法上。在这些方法中,查尔酮、肼、重氮化合物和腙是在不同的反应条件下最常用的合成吡唑啉及其类似物的方法。然而,其他分子如惠斯根两性离子、不同的金属催化剂和腈亚胺也可以作为起始试剂。本文综述了吡唑啉及其衍生物的合成方法、药理活性、构效关系等方面的最新报道,对研究吡唑啉及其衍生物有一定的参考价值。图形抽象
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引用次数: 0
期刊
Topics in Current Chemistry
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