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One step at a time 一步一个脚印
IF 19.1 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-09-12 DOI: 10.1016/j.chempr.2024.08.007

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Dr. Rui Tang obtained her BSc degree in chemistry/chemical technology from a joint program between Sun Yat-Sen University and the Hong Kong Polytechnic University. She then got a MRes degree with distinction in catalysis from Imperial College London. After that, she was admitted to the joint PhD program offered by the University of Hong Kong and Southern University of Science and Technology under the supervision of Prof. Chi-Ming Che and Prof. Wei Lu. She completed her PhD degree at HKU in 2023. Now, she is a postdoctoral fellow in Prof. Che’s group at HKU.

下载:下载高清图片 (379KB)Download:下载全尺寸图片唐蕊博士在中山大学和香港理工大学的联合课程中获得化学/化学技术理学士学位。之后,她以优异成绩获得伦敦帝国理工学院催化专业的硕士学位。之后,她考取了香港大学和南方科技大学的联合博士学位课程,师从车志明教授和卢伟教授。她于 2023 年在香港大学完成博士学位。现在,她是香港大学车志明教授课题组的博士后研究员。
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引用次数: 0
Copper(I)-based metal-metal-to-ligand charge transfer excited state with halogen-atom transfer photo-reactivity and photocatalysis 基于铜(I)的金属-金属-配体电荷转移激发态与卤原子转移光活性和光催化
IF 19.1 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-09-12 DOI: 10.1016/j.chempr.2024.05.003

Metal-metal-bonded excited states of Cu(I) complexes have rarely been studied, although such excited states of d10 noble metal complexes have been well documented to cleave C–H and C–X bonds. We describe here a panel of air-stable two-coordinate binuclear Cu2(I,I) N-heterocyclic carbene complexes with short intramolecular Cu–Cu (2.75–2.88 Å) and Cu–arene (2.61–2.65 Å) distances. The triplet metal-metal-to-ligand charge transfer excited states of these Cu2(I,I) complexes are highly emissive and long-lived (Φem up to 0.67, τ 2.9–36.1 μs in solution) and can cleave strong R–X (X = Br or Cl) bonds to give mixed-valence [X–Cu1.5Cu1.5–Y]+/2+ (Y = X or solvent) species and carbon-centered radicals via an excited-state halogen-atom transfer mechanism. The spin-delocalized [X–Cu1.5Cu1.5–X]+ species (X = Br or Cl) have been characterized by single-crystal XRD, EPR spectroscopy, and density functional theory (DFT) calculations. Cu3 is an efficient photocatalyst for C–C coupling reactions with aryl/alkyl halides under 390 nm LED irradiation.

Cu(I) 复合物的金属-金属键激发态很少被研究,尽管 d10 贵金属复合物的此类激发态可裂解 C-H 和 C-X 键,这一点已得到充分证明。我们在此描述了一组具有短分子内 Cu-Cu(2.75-2.88 Å)和 Cu-烯(2.61-2.65 Å)距离的空气稳定双核 Cu2(I,I) N-杂环碳烯配合物。这些 Cu2(I,I)配合物的三重金属-金属-配体电荷转移激发态具有高辐射性和长寿命(Φem 高达 0.67,τ 在溶液中为 2.9-36.1 μs),可通过激发态卤原子转移机制裂解强 R-X(X = Br 或 Cl)键,产生混合价 [X-Cu1.5Cu1.5-Y]+/2+ (Y = X 或溶剂)物种和碳中心自由基。自旋定位的 [X-Cu1.5Cu1.5-X]+ 物种(X = Br 或 Cl)通过单晶 XRD、EPR 光谱和密度泛函理论(DFT)计算得到了表征。在 390 纳米 LED 的照射下,Cu3 是一种与芳基/烷基卤化物进行 C-C 偶联反应的高效光催化剂。
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引用次数: 0
Metal-peptidic cages—Helical oligoprolines generate highly anisotropic nanospaces with emergent isomer control 金属肽笼--螺旋状低聚果糖产生具有新兴异构体控制功能的高度各向异性纳米空间
IF 19.1 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-09-12 DOI: 10.1016/j.chempr.2024.05.002

The self-assembly of metal-organic cages enables the rapid creation of atomically defined, three-dimensional, nanoscale architectures reminiscent of proteins. However, existing metal-organic cages are almost exclusively built from rigid and flat aromatic panels, limiting binding selectivity and, often, water solubility. Herein, we disclose a new class of cages—metal-peptidic cages—which utilize water-soluble, chiral, and helical oligoproline strands of varying lengths to generate highly anisotropic nanospaces. Further, we find that the formation of the cis isomer of the cage is strongly favored and is an emergent property of using complex and chiral building blocks in the formation of defined nanospaces. We demonstrate that the use of peptidic building blocks allows us to rapidly tune the size of the nanospace formed, from c. 1 to 4 nm, and that the use of biologically relevant components enables targeted binding of therapeutic molecules, highlighting the potential of these systems for selective drug delivery.

通过金属有机笼的自组装,可以快速创建原子定义的三维纳米级结构,让人联想到蛋白质。然而,现有的金属有机笼几乎都是由刚性和扁平的芳香族面板构建而成,从而限制了结合的选择性,通常也限制了水溶性。在这里,我们揭示了一类新的笼子--金属肽笼,它利用水溶性、手性和长度不等的螺旋状低聚脯氨酸链来产生高度各向异性的纳米空间。此外,我们还发现,笼子的顺式异构体的形成非常有利,这是使用复杂的手性构建模块形成确定的纳米空间的一个新特性。我们证明,使用肽构建模块可以快速调整所形成的纳米空间的大小(从约 1 纳米到 4 纳米),而且使用生物相关成分可以有针对性地结合治疗分子,从而凸显了这些系统在选择性给药方面的潜力。
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引用次数: 0
Pyridine-boryl radical-catalyzed [3π + 2σ] cycloaddition for the synthesis of pyridine isosteres 吡啶-硼氢基催化 [3π + 2σ] 环加成法合成吡啶异甾烷
IF 23.5 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-09-12 DOI: 10.1016/j.chempr.2024.08.010
Yuan Liu, Shuang Lin, Zhengwei Ding, Yin Li, Ya-Jie Tang, Jiang-Hao Xue, Qingjiang Li, Pengfei Li, Honggen Wang

The pursuit of C(sp3)-enriched three-dimensional (3D) scaffolds as isosteric analogs for planar aromatic compounds is an area of increasing interest. In this report, we report a pyridine-boryl radical-catalyzed [3π + 2σ] cycloaddition reaction between vinyl azides and bicyclo[1.1.0]butanes (BCBs). The reaction leads to the synthesis of semisaturated bridged 2-azabicyclo[3.1.1]heptenes, a structural framework previously inaccessible. The semisaturation characteristic of these scaffolds results in an effective reproduction of the geometry of 1,3,5-substituted pyridine, with the imine group exhibiting comparable basicity to pyridine rings. Synthetic manipulation of these products reveals valuable synthetic handles, enabling a modular approach to the synthesis of potential pyridine isosteres.

将富含 C(sp3)的三维(3D)支架作为平面芳香化合物的同位类似物是一个越来越受关注的领域。在本报告中,我们报告了乙烯基叠氮化物与双环[1.1.0]丁烷(BCBs)之间的吡啶-硼自由基催化[3π + 2σ] 环加成反应。该反应导致了半饱和桥接 2-氮杂双环[3.1.1]庚烯的合成,这是一种以前无法获得的结构框架。这些支架的半饱和特性有效地再现了 1,3,5-取代吡啶的几何结构,亚胺基团表现出与吡啶环相当的碱性。对这些产品的合成操作揭示了有价值的合成途径,使潜在吡啶异构体的合成采用模块化方法成为可能。
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引用次数: 0
A selectivity switch for CO2 electroreduction by continuously tuned semi-coherent interface 通过连续调谐半相干界面实现二氧化碳电还原的选择性开关
IF 19.1 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-09-12 DOI: 10.1016/j.chempr.2024.04.009

Mass production of Au–Cu-based catalysts with tailored selectivity is a complex and challenging task. We report a semi-affinity strategy to realize the synthesis of Au–Cu Janus nanocrystals with continuously tuned interfaces (from dimer, Janus, acorn-like Janus, to core-shell) based on Au nanosphere seeds. We highlight the role of interfacial strain due to a large lattice mismatch in growth control. The systematic electrochemical evaluation shows that the interfacial Cu oxide state, ∗CO coverage, and intermediate adsorption configuration can be well tuned by tailoring the Janus nanostructure. Optimized Au–Cu Janus catalyst reaches an efficiency of up to 80.0% for C2+ product with a partial current density of 466.1 mA cm−2. The reaction products can be selectively switched from methanol (dimer) to ethanol (Janus) and further to ethylene (acorn-like Janus) by increasing the interface area of the Au–Cu heterostructures. The catalytic mechanisms are unraveled by operando surface-enhanced Raman spectroscopy (SERS) analysis and density functional theory calculations.

量产具有定制选择性的金-铜基催化剂是一项复杂而具有挑战性的任务。我们报告了一种半亲和性策略,以金纳米球种子为基础,实现了具有不断调整的界面(从二聚体、Janus、橡树果状 Janus 到核壳状)的金-铜 Janus 纳米晶体的合成。我们强调了大晶格失配导致的界面应变在生长控制中的作用。系统电化学评估表明,通过定制 Janus 纳米结构,可以很好地调整界面氧化铜状态、∗CO 覆盖率和中间吸附构型。优化后的 Au-Cu Janus 催化剂在部分电流密度为 466.1 mA cm-2 的情况下,C2+ 产物的效率高达 80.0%。通过增大金-铜异质结构的界面面积,反应产物可选择性地从甲醇(二聚体)转化为乙醇(Janus),并进一步转化为乙烯(橡树醛样 Janus)。通过操作表面增强拉曼光谱(SERS)分析和密度泛函理论计算,揭示了催化机理。
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引用次数: 0
B(C6F5)3-catalyzed selective C–H chalcogenation of arenes and heteroarenes B(C6F5)3催化的炔类和杂环烯类选择性 C-H钙化反应
IF 19.1 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-09-12 DOI: 10.1016/j.chempr.2024.05.025

The synthesis of organochalcogenides remains a valuable area of research due to their widespread biological applications, particularly in pharmaceuticals. Herein, our study details the B(C6F5)3-catalyzed Csp2–H functionalization of diverse arenes, heteroarenes, and pharmacophores with thiosuccinimides or selenosuccinimides, providing selective access to chalcogenated products. This protocol enables the selective late-stage chalcogenation of drug molecules such as the anti-inflammatory drug naproxen, the estrogen steroid hormone estradiol derivatives, and the industrially relevant trifluoromethylthiolation reaction. Furthermore, this C–S coupling methodology provides a facile and metal-free route to synthesize vortioxetine, an antidepressant drug, and a plethora of significant organic motifs. Detailed NMR, EPR analyses, and density functional theory (DFT) computational studies indicate that the elongation of the thiosuccinimide N–S bond is assisted by a boron-centered adduct, which then leads to a stable ion pair with an arene. The EPR analysis shows that a transient radical pair, potentially an off-cycle species, is not directly involved in the catalytic process.

由于有机钙苷在生物学上的广泛应用,尤其是在医药方面的应用,因此有机钙苷的合成仍然是一个有价值的研究领域。在本文中,我们的研究详细介绍了 B(C6F5)3 催化的 Csp2-H 功能化技术,该技术可将多种烯烃、杂环烯烃和药用烯烃与硫代琥珀酰亚胺或硒代琥珀酰亚胺进行官能化,从而有选择性地获得瑀化产物。通过这种方法,可以对药物分子(如消炎药萘普生、雌激素类固醇雌二醇衍生物)进行选择性后期钙化,并实现与工业相关的三氟甲基硫代反应。此外,这种 C-S 偶联方法还为合成抗抑郁药物伏替西汀和大量重要的有机基团提供了一条简便的无金属路线。详细的 NMR、EPR 分析和密度泛函理论 (DFT) 计算研究表明,硫代丁二酰亚胺 N-S 键的伸长得到了硼中心加合物的帮助,然后导致与炔烃形成稳定的离子对。EPR 分析表明,瞬时自由基对(可能是一种非循环物种)并没有直接参与催化过程。
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引用次数: 0
New trends for transition metal-catalyzed ortho/ipso difunctionalizations of arenes 过渡金属催化的炔烃正/反二官能化新趋势
IF 19.1 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-09-12 DOI: 10.1016/j.chempr.2024.07.003

Direct access to polyfunctionalized compounds by regioselective vicinal difunctionalizations of arenes is a challenging synthetic task that inspired the scientific community for years. The discovery of the Catellani reaction in 1997, a palladium-catalyzed vicinal difunctionalization reaction, was a real game-changer. This new paradigm offered various possibilities to access ortho/ipso-difunctionalized arenes and garnered attention over the years. From this pioneering work, innovative strategies have emerged. This perspective provides an overview of recent advances made in the field of catalytic vicinal arene difunctionalizations. It highlights current challenges and discusses future perspectives and opportunities.

通过烷的区域选择性邻接双官能化反应直接获得多官能化化合物是一项极具挑战性的合成任务,多年来一直激励着科学界。1997 年发现的 Catellani 反应--一种钯催化的邻位双官能化反应--真正改变了游戏规则。这一新范例为获得正/反双官能化的烯烃提供了多种可能性,多年来备受关注。在这一开创性工作的基础上,创新战略应运而生。本视角概述了催化沧醛炔双官能化领域的最新进展。它强调了当前面临的挑战,并讨论了未来的前景和机遇。
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引用次数: 0
Synthesis of polyethylene-polyacrylate block copolymers in continuous flow 在连续流中合成聚乙烯-聚丙烯酸酯嵌段共聚物
IF 19.1 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-09-12 DOI: 10.1016/j.chempr.2024.05.016

Continuous flow reactions for the synthesis of block copolymers are a useful synthetic strategy because they provide better control over the polymerization reactions with easy scaling-up ability. Herein, a continuous flow system has been designed to combine two adverse polymerization processes, coordination-insertion using gaseous ethylene and free radical polymerization utilizing monomers of the acrylate family, to form polar polyethylene block copolymers. We demonstrate that a gas-liquid heterogeneous droplet flow system can lead to a successful living ethylene polymerization in which the gaseous component contains the reactive monomer. The addition of acrylates switches the reaction location to the liquid phase through the formation of a macroinitiator for the radical pathway and retarding the ethylene polymerization. We demonstrate that block copolymer segments can engage all phases of the droplet flow system and enable the synthesis of polar polyolefin block copolymers employing a single catalyst.

用于合成嵌段共聚物的连续流反应是一种有用的合成策略,因为它能更好地控制聚合反应,而且易于放大。在此,我们设计了一种连续流系统,将两种不利的聚合过程(使用气态乙烯的配位插入和使用丙烯酸酯类单体的自由基聚合)结合起来,形成极性聚乙烯嵌段共聚物。我们证明,气液异质液滴流动系统可成功实现活乙烯聚合,其中气态成分包含活性单体。丙烯酸酯的加入通过形成自由基途径的大引发剂和延缓乙烯聚合反应,将反应位置切换到液相。我们证明了嵌段共聚物片段可参与液滴流动系统的所有阶段,并可使用单一催化剂合成极性聚烯烃嵌段共聚物。
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引用次数: 0
Trapping highly reactive photoinduced charge-transfer complex between amine and imide by light 用光诱捕胺和亚胺之间的高活性光诱导电荷转移复合物
IF 19.1 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-09-12 DOI: 10.1016/j.chempr.2024.05.005

Complexation between two organic molecules can occur either for strong electron donor-acceptor pairs in the ground state, known as charge-transfer complexes (CTCs), or for pairs of lesser strength in the excited state, such as excimers and exciplexes. However, the characterization of chemically distinct CTCs in solution remains elusive. Here, we report a light-induced, solution-persistent 1:1 CTC between an amine and an imide. The pair is not associated in the ground state at room temperature prior to light exposure. The presence and exact molecular compositions of the CTCs could be directly obtained from high-resolution mass spectrometry. Additional spectroscopic and computational evidence reveal that a kinetically trapped ground-state pair is formed following an exciplex-like process between the amine and the imide after photoexcitation. We show that such a photoinduced complex can be used to conduct photochemistry and store photon energy for producing otherwise photochromic products in the dark.

两个有机分子之间的络合既可能发生在基态的强电子供体-受体对上,即电荷转移络合物(CTC),也可能发生在激发态的强度较低的对上,如激发子和赋形剂。然而,对溶液中化学性质截然不同的 CTC 的表征仍然难以捉摸。在这里,我们报告了一种光诱导的、溶液中持久存在的 1:1 四氯化碳,它介于胺和亚胺之间。在室温下,这对化合物在光照前的基态中并不存在关联。四氯化碳的存在和确切的分子组成可以直接从高分辨率质谱中获得。其他光谱学和计算证据表明,在光激发后,胺和亚胺之间发生了类似于赋形剂的过程,从而形成了动力学捕获的基态对。我们的研究表明,这种光诱导复合物可用于进行光化学反应并储存光子能量,从而在黑暗中产生光致变色产物。
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引用次数: 0
Reaction: A future where all bonds click 反应:所有债券都能点击的未来
IF 19.1 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-09-12 DOI: 10.1016/j.chempr.2024.07.022

Tim Cernak is an associate professor of Medicinal Chemistry at the University of Michigan. He holds appointments in the University of Michigan Department of Chemistry, Program in Chemical Biology, Center for Global Health Equity, and Michigan Institute for Data Science. Tim’s research interests include chemical synthesis, catalysis, total synthesis, cheminformatics, ecology, data science, automation, natural products, medicinal chemistry, agrichemistry, sustainability, cell imaging, mass spectrometry, conservation, robotics, extinction, and drug discovery. Tim has served on the advisory board of the University of Dundee’s Drug Discovery Unit, the Open Reaction Database, and Scorpion Therapeutics. He is a co-founder of Iambic Therapeutics.

Tim Cernak 是密歇根大学药物化学副教授。他在密歇根大学化学系、化学生物学项目、全球健康公平中心和密歇根数据科学研究所任职。蒂姆的研究兴趣包括化学合成、催化、全合成、化学信息学、生态学、数据科学、自动化、天然产品、药物化学、农业化学、可持续发展、细胞成像、质谱分析、环境保护、机器人技术、物种灭绝和药物发现。蒂姆曾担任邓迪大学药物发现部门、开放反应数据库和天蝎疗法顾问委员会成员。他还是 Iambic Therapeutics 公司的共同创始人。
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引用次数: 0
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