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Oscillatory adaptive catalysis: Intramolecular chain shuttling regulated by stereo-autocorrection in stereoselective polymerization of lactide 振荡自适应催化：立体选择性聚合内酯过程中由立体自校正调节的分子链内穿梭

IF 19.1 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chem

Pub Date : 2024-11-14 DOI: 10.1016/j.chempr.2024.06.031

Wuchao Zhao , Fengchao Cui , Jianghua He , Yuetao Zhang , Eugene Y.-X. Chen

In metal-mediated stereoselective polymerization of cyclic esters, racemic catalysts use their enantiomers for enantioselective roles and achieve diverse polymer stereomicrostructures through intermolecular chain exchange. Here, an intramolecular chain shuttling mechanism is achieved by the combination of cis (R,S)-dithiourea and MeOK to overcome limitations on intermolecular polymer exchange and also offer diverse polymer stereomicrostructures. This system exhibits diastereospecificity toward the polymerization of both rac-lactide (rac-LA) and meso-LA, producing highly isotactic PLA (P_m ∼ 0.96) and heterotactic PLA (P_r ∼ 0.92), respectively. Mechanistic studies reveal an “oscillatory adaptive catalysis” (OAC) phenomenon, which is key to achieving dual recognition of the chirality of both the chain end and incoming monomer by using the two switchable chiral centers in catalyst. Such OAC enables dynamic interchange between chiral recognition (that triggers chain propagation) and stereochemical autocorrection (when monomer mismatched) by multi-site cooperativity, which induces chiral-site switching and polymer-chain shuttling intramolecularly within a single catalyst molecule.

在金属介导的环酯立体选择性聚合反应中，外消旋催化剂利用其对映体发挥对映选择性作用，并通过分子间链交换实现多样化的聚合物立体结构。在这里，顺式 (R,S)- 二硫代脲和 MeOK 的组合实现了分子内链穿梭机制，从而克服了分子间聚合物交换的限制，并提供了多样化的聚合物立体结构。该体系对rac-内酯（rac-LA）和介-LA 的聚合具有非对映特异性，可分别生成高度同构聚乳酸（Pm ∼ 0.96）和异构聚乳酸（Pr ∼ 0.92）。机理研究揭示了一种 "振荡自适应催化"（OAC）现象，它是利用催化剂中的两个可切换手性中心实现对链端和进入单体的手性双重识别的关键。这种 OAC 通过多位点协同作用实现了手性识别（触发链的扩展）和立体化学自动校正（当单体不匹配时）之间的动态交换，从而在单个催化剂分子内诱导手性位点切换和聚合物链的分子内穿梭。

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引用次数: 0

Selective hydrogenation catalysis enabled by nanoscale galvanic reactions 利用纳米级电化反应实现选择性氢化催化

IF 19.1 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chem

Pub Date : 2024-11-14 DOI: 10.1016/j.chempr.2024.06.030

Mengfei Qiao , Qingyuan Wu , Ying Wang , Shanshan Gao , Ruixuan Qin , Shengjie Liu , Kehong Ding , Dongyuan Zhao , Nanfeng Zheng

By mimicking nanoscale galvanic reactions, this study focuses on optimizing catalytic hydrogenation by introducing two spatially separated sites for the activation of H₂ into proton and electron pairs and the selective reduction of –NO₂. The catalyst system is designed with the co-deposition of Pt and Fe₂O₃ nanoparticles on conductive carbon nanotubes, establishing an electron-transferring pathway. Protic solvents facilitate proton transport. Upon activation of H₂ molecules into proton and electron pairs on Pt, modified with ammonia or amines, these active species are efficiently transferred to Fe₂O₃ nanoparticles for the selective reduction of –NO₂ into amines without affecting other functional groups. Compared with Pt/CNT, which easily hydrogenates both C=C and –NO₂ groups of 4-nitrostyrene, the Pt&Fe₂O₃/CNT catalyst modified by NH₃ exhibits higher activity and selectivity for –NO₂ hydrogenation. Electrochemically, Pt functions as the anode for the hydrogen oxidation reaction, while Fe₂O₃ acts as the cathode, selectively reducing –NO₂.

本研究通过模仿纳米级电偶反应，重点优化催化加氢反应，引入两个空间上分离的位点，将 H2 活化为质子和电子对，并选择性还原 -NO2。催化剂系统的设计是在导电碳纳米管上共沉积铂和铁氧体纳米粒子，从而建立电子传递途径。质子溶剂有利于质子传输。用氨或胺修饰的铂上的 H2 分子活化成质子和电子对后，这些活性物质会有效地转移到 Fe2O3 纳米粒子上，从而选择性地将 -NO2 还原成胺，而不会影响其他官能团。与易于氢化 4-硝基苯乙烯的 C=C 和 -NO2 基团的 Pt/CNT 催化剂相比，经 NH3 修饰的 Pt&Fe2O3/CNT 催化剂在 -NO2 氢化方面表现出更高的活性和选择性。在电化学上，铂是氢氧化反应的阳极，而 Fe2O3 则是阴极，可选择性地还原 -NO2。

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引用次数: 0

In situ energy dispersive X-ray diffraction achieved in twin screw extrusion 在双螺杆挤压中实现原位能量色散 X 射线衍射

IF 19.1 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chem

Pub Date : 2024-11-14 DOI: 10.1016/j.chempr.2024.10.011

Edward J. Broker Jr. , Kathleen Floyd , James D. Batteas

In the current issue of Chem, Gugin et al. are showcasing the power of energy-dispersive X-ray diffraction to track kinetics and chemical phenomena in situ during twin screw extrusion. This technique holds great promise for industrial scale-up of green chemical syntheses.

在本期《化学》杂志上，Gugin 等人展示了能量色散 X 射线衍射在双螺杆挤压过程中现场跟踪动力学和化学现象的能力。这项技术为绿色化学合成的工业放大带来了巨大希望。

引用次数: 0

Enhancing multi-resonance thermally activated delayed fluorescence emission via through-space heavy-atom effect 通过穿透空间重原子效应增强多共振热激活延迟荧光发射

IF 23.5 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chem

Pub Date : 2024-11-14 DOI: 10.1016/j.chempr.2024.10.020

Qi Zheng, Yang-Kun Qu, Peng Zuo, Hai-Tian Yuan, Yue-Jian Yang, Yu-Chen Qiu, Liang-Sheng Liao, Dong-Ying Zhou, Zuo-Quan Jiang

Recent research has focused on the heavy-atom effect in organic luminescent materials, especially in multi-resonance thermally activated delayed fluorescence (MR-TADF) emitters. Traditional strategies involve directly conjugating heavy atoms to the chromophore, which often broadens the emission spectrum. This study explores an unconventional approach using the through-space heavy-atom effect, positioning heavy-atom moieties with nonconjugated short-range interaction with the chromophore. This method successfully demonstrates the “intramolecular external heavy-atom effect” proposed in the 1970s in cutting-edge high-efficiency emissive materials. Comparative analysis of these emitters confirms the spatial heavy-atom effect, maintaining the spectroscopic properties of MR chromophore while significantly improving external quantum efficiency in organic light-emitting diodes (OLEDs). These emitters also mitigate efficiency roll-off, showcasing the potential of spatial interactions to enhance MR-TADF materials for OLED applications.

近期研究的重点是有机发光材料中的重原子效应，尤其是多共振热激活延迟荧光（MR-TADF）发射器中的重原子效应。传统的策略是将重原子直接与发色团共轭，这往往会扩大发射光谱。本研究探索了一种非常规方法，即利用穿透空间重原子效应，定位与发色团具有非共轭短程相互作用的重原子分子。这种方法成功地将 20 世纪 70 年代提出的 "分子内外部重原子效应 "应用到了最先进的高效发射材料中。对这些发射器的比较分析证实了空间重原子效应，在保持 MR 发色团光谱特性的同时，显著提高了有机发光二极管（OLED）的外部量子效率。这些发射器还减轻了效率衰减，展示了空间相互作用在增强 MR-TADF 材料在有机发光二极管应用中的潜力。

引用次数: 0

Enantioselective desymmetrization and parallel kinetic resolution of cyclopropanes via C–C activation: Synthesis of chiral β-lactams 通过 C-C 活化实现环丙烷的对映选择性去对称化和平行动力学解析：手性 β-内酰胺的合成

IF 19.1 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chem

Pub Date : 2024-11-14 DOI: 10.1016/j.chempr.2024.08.005

Hao Wu , Yiyao Wang , Shiyuan Sui , Gongming Chen , Lei Wang , Jiaxin Yang , Junbiao Chang , Dachang Bai

β-Lactams are privileged and appealing motifs in medicinal chemistry. Herein, we report enantioselective desymmetrization and parallel kinetic resolution of aminocyclopropanes for the synthesis of chiral β-lactams through Rh(I)-catalyzed asymmetric C–C bond activation. The chiral Rh(I) catalyzed C–C bond cleavage of aminocyclopropanes first and then underwent β-hydride elimination to generate π-allylic hydridorhodium(III) intermediates, which could be trapped by tethered alkyne units, and gave various strained chiral β-lactams with excellent regio- and enantioselectivity (90%–99% ee). Moreover, parallel kinetic resolution was realized when using unsymmetrical aminocyclopropanes with pre-existing C2-stereocenters through C–C bond activation, delivering two types of β-lactams in one pot with excellent enantiomeric excesses. Notably, these systems achieve complete atom and step economy. The obtained enantioenriched β-lactams exhibit the capability to undergo a variety of stereospecific transformations. Theoretical calculations reveal the origin of enantioselectivity and support the alkyne unit insertion to allylic Rh(III) –C bond mechanisms.

β-内酰胺是药物化学中极具吸引力的特异主题。在此，我们报告了通过 Rh(I) 催化的不对称 C-C 键活化，对氨基环丙烷进行对映体选择性去对称化和平行动力学解析，以合成手性 β-内酰胺。手性 Rh(I) 首先催化氨基环丙烷的 C-C 键裂解，然后进行 β-酸酐消除，生成π-烯丙基氢化铑(III)中间体，该中间体可被系链炔烃单元捕获，并以优异的区域和对映体选择性（90%-99% ee）得到各种手性β-内酰胺。此外，通过 C-C 键活化，使用带有预先存在的 C2-stereocenters 的不对称氨基环丙烷时，实现了平行动力学解析，在一锅中制备出两种类型的 β-内酰胺，对映体过量率极高。值得注意的是，这些系统实现了完全的原子和步骤经济性。获得的对映体富集的 β-内酰胺具有进行多种立体特异性转化的能力。理论计算揭示了对映体选择性的来源，并支持炔烃单元插入烯丙基 Rh(III) -C 键的机制。

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引用次数: 0

Quantifying zinc and manganese reduction potentials in organic solvents 量化锌和锰在有机溶剂中的还原电位

IF 19.1 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chem

Pub Date : 2024-11-14 DOI: 10.1016/j.chempr.2024.10.015

Sagnik Chakrabarti , Liviu M. Mirica

Zinc and manganese are the reductants of choice for nickel-catalyzed cross-electrophile coupling (XEC), but their exact redox potentials are unknown in organic solvents. In a recent report from Stahl and colleagues in Nature Chemistry, these potentials have been measured for the first time and their implications on model XEC reactions have been discussed.

锌和锰是镍催化交叉亲电偶联（XEC）的首选还原剂，但它们在有机溶剂中的确切氧化还原电位尚不清楚。Stahl 及其同事最近在《自然-化学》（Nature Chemistry）杂志上发表的一篇报告首次测量了这些氧化还原电位，并讨论了它们对模型 XEC 反应的影响。

引用次数: 0

Inherently chiral resorcinarene cavitands through ionic catalyst-controlled cross-coupling 通过离子催化剂控制的交叉偶联获得固有手性的间苯二酚空穴剂

IF 19.1 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chem

Pub Date : 2024-11-14 DOI: 10.1016/j.chempr.2024.06.012

Mingfeng Li , Clement Kim Soon Ho , Ivan Keng Wee On , Vincent Gandon , Ye Zhu

Cavitands have emerged as privileged architectures in supramolecular chemistry. Nonetheless, achieving structural diversity and tunability through heterofunctionalization along the rims of macrocycles has remained a formidable challenge. As a rudimental example, stepwise conversion of C_4v-symmetric scaffolds to inherently chiral ABCD patterns is synthetically impractical owing to the low theoretical yields (0.8%) and the need for chromatographic enantioseparation.

Herein, we report a catalytic desymmetrization strategy to access inherently chiral cavitands. Through engineering ionic chiral palladium catalysts, diverse functionalities, including aryl, alkenyl, alkynyl, and amino groups, can be installed on the large rims with high site- and stereoselectivity. An adaptable stepwise protocol has been established to furnish designer ABCD-type cavitands in accordance with the choreography of coupling partners. Experimental and computational studies reveal synergistic electrostatic steering and electrostatic catalysis by the ionic catalyst–substrate interactions.

空穴带已成为超分子化学中的重要结构。然而，通过大环边缘的异功能化实现结构多样性和可调性仍然是一项艰巨的挑战。举个简单的例子，将 C4v 对称支架逐步转化为固有手性 ABCD 模式在合成上并不可行，因为理论产率低（0.8%），而且需要进行色谱对映体分离。通过对离子手性钯催化剂进行工程化，可以在大边缘上安装包括芳基、烯基、炔基和氨基在内的多种官能团，并具有很高的位点选择性和立体选择性。根据偶联伙伴的编排，我们建立了一个可调整的步骤协议，以提供设计的 ABCD 型空穴剂。实验和计算研究揭示了离子催化剂与底物相互作用所产生的协同静电引导和静电催化作用。

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引用次数: 0

On the road to isolable geminal carbodications 通往可分离的宝石碳化物之路

IF 19.1 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chem

Pub Date : 2024-11-14 DOI: 10.1016/j.chempr.2024.09.008

Yiwei Gong , Jan Langwald , Florian F. Mulks

Recent advances in the isolation of masked gem-carbodications have shown that such species may be more accessible than we thought. This perspective article summarizes the milestones of the last 140 years of research and aims to point the way toward the isolation of species containing true four-valence-electron carbon. Currently, strong mesomeric donation or coordination by donor ligands is used to stabilize such dications. Achieving true localization of both charges on a single atom will require smart combinations of inductive donation, hyperconjugation, and steric hindrance.

最近在分离掩蔽宝石碳化物方面取得的进展表明，这类物种可能比我们想象的更容易获得。这篇观点性文章总结了过去 140 年研究的里程碑，旨在为分离含有真正四价电子碳的物种指明方向。目前，供体配体的强中间体捐赠或配位被用来稳定此类阳离子。要在单个原子上实现两种电荷的真正定位，需要巧妙地结合感应捐献、超共轭和立体阻碍。

引用次数: 0

New light on proton transfer: Spectral and kinetic signature of a transient Eigen complex 质子转移的新发现：瞬态特征复合体的光谱和动力学特征

IF 19.1 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chem

Pub Date : 2024-11-14 DOI: 10.1016/j.chempr.2024.10.017

Niklas Sülzner

Despite the long-lasting research on proton transfer as a fundamental chemical reaction, not all details regarding its precise mechanism have been revealed. Particularly, a complete spectroscopic and kinetic characterization of all intermediates remains challenging. In the September issue of Cell Reports Physical Science, Lee et al. identify a transient Eigen complex and determine the molecularity of each elementary step.

尽管对质子转移这一基本化学反应的研究持续了很长时间，但有关其精确机理的所有细节仍未得到揭示。特别是，对所有中间产物进行完整的光谱和动力学表征仍然具有挑战性。在 9 月份的《细胞报告-物理科学》（Cell Reports Physical Science）杂志上，Lee 等人确定了一个瞬态 Eigen 复合物，并确定了每个基本步骤的分子性。

引用次数: 0

Self-activated energy release cascade from anthracene-based solid-state molecular solar thermal energy storage systems 蒽基固态分子太阳能热储存系统的自激活能量释放级联

IF 19.1 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chem

Pub Date : 2024-11-14 DOI: 10.1016/j.chempr.2024.06.033

Subhayan Chakraborty , Han P.Q. Nguyen , Junichi Usuba , Ji Yong Choi , Zhenhuan Sun , Cijil Raju , Gustavo Sigelmann , Qianfeng Qiu , Sungwon Cho , Stephanie M. Tenney , Katherine E. Shulenberger , Klaus Schmidt-Rohr , Jihye Park , Grace G.D. Han

We introduce donor-acceptor substituted anthracenes as effective molecular solar thermal energy storage compounds that operate exclusively in the solid state. The donor-acceptor anthracenes undergo a visible light-induced [4+4] cycloaddition reaction, producing metastable cycloadducts—dianthracenes with quaternary carbons—and storing photon energy. The triggered cycloreversion of dianthracenes to anthracenes discharges the stored energy as heat in the order of 100 kJ/mol (200 J/g). The series of compounds displays remarkable self-heating, or cascading heat release, upon the initial triggering. Such self-activated energy release is enabled by the large energy storage in dianthracenes, low activation energy for their thermal reversion, and effective heat transfer to unreacted molecules in the solid state. This process mirroring the self-ignition of fossil fuels opens up opportunities to use dianthracenes as effective and renewable solid-state fuels that can release energy rapidly and completely upon initial activation.

我们将供体-受体取代的蒽作为有效的分子太阳能热能储存化合物介绍给大家，这种化合物只在固态下工作。供体-受体蒽发生可见光诱导的[4+4]环加成反应，生成具有季碳的可转移环加成物--二蒽，并储存光子能量。二蒽与蒽的触发环化反应将储存的能量以热量的形式释放出来，热量约为 100 kJ/mol（200 J/g）。这一系列化合物在最初触发时显示出显著的自加热或级联热释放。这种自激活能量释放得益于二蒽的巨大能量储存、其热还原的低活化能以及固态中未反应分子的有效热传导。这一过程与化石燃料的自燃过程如出一辙，为将二蒽用作有效的可再生固态燃料提供了机会，这种燃料在初始活化时就能快速、完全地释放能量。

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