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Construction of chiral nitrogen stereocenters via enantioselective C–H activation 通过对映选择性碳氢活化构建手性氮立体中心

IF 19.6 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chem

Pub Date : 2026-01-15 DOI: 10.1016/j.chempr.2025.102730

Zechen Wu , Dongsheng Yi , Junhao Tang , Fanyi Meng , Haining Zhu , Kevin Wu , Kaining Duanmu , Jin-Quan Yu , Yanghui Zhang

Enantioselective C–H activation has recently emerged as a versatile method for selectively constructing point, axial, and planar chirality. Out of the main strategies in asymmetric catalysis, desymmetrization, enantioselection, and classical kinetic resolutions have been demonstrated in C–H activation reactions. To the best of our knowledge, dynamic kinetic resolution (DKR) via enantioselective C(sp³)-H activation to set point chirality remains unrealized. While the rapid inversion of nitrogen stereocenters typically presents a challenge to their enantioselective synthesis, this phenomenon provides a unique opportunity to selectively access nitrogen stereocenters via a DKR given the appropriate system. Here, we report the DKR of nitrogen stereocenters via a Pd-catalyzed enantioselective C–H olefination yielding enantioenriched tribenzo[b,d,f]azepines and dibenzo[b,f]azepines, thus demonstrating the feasibility of constructing enantioenriched nitrogen stereocenters by harnessing nitrogen inversion. The chiral tribenzo[b,d,f]azepine products exhibit high circularly polarized luminescence (CPL) performance, representing a novel scaffold for exploration in this area.

对映选择性碳氢化合物活化最近成为一种选择性地构建点、轴和平面手性的通用方法。在不对称催化的主要策略中，去对称化、对映体选择和经典动力学分解已经在碳氢活化反应中得到证实。据我们所知，通过对映选择性C(sp3)-H活化到设定点手性的动态动力学分辨率（DKR）仍未实现。虽然氮立体中心的快速反转通常对其对映选择性合成提出了挑战，但这种现象为通过给定适当系统的DKR选择性地获得氮立体中心提供了独特的机会。本研究报道了通过pd催化的对映选择性碳氢烯化反应生成富对映三苯[b，d，f]氮卓类化合物和二苯[b，f]氮卓类化合物，从而证明了利用氮转化构建富对映氮卓类化合物的可行性。手性三苯并[b，d，f]氮卓类化合物具有较高的圆偏振发光（CPL）性能，为该领域的研究提供了新的框架。

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引用次数: 0

A protease repurposed for thiotemplated amide synthesis 一种用于硫代模板酰胺合成的蛋白酶

IF 19.6 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chem

Pub Date : 2026-01-15 DOI: 10.1016/j.chempr.2025.102915

Max Bernstein Sosa , Ikuro Abe

In this issue of Chem, Hertweck, Groll, and co-workers characterize an amide-forming ligase central to closthioamide biosynthesis: CtaG. They provide a mechanistic and structural explanation for how CtaG repurposes a protease-like active site to catalyze amide-bond formation between two carrier protein-bound substrates.

在这一期的《化学》杂志上，Hertweck、Groll和同事们描述了一种酰胺形成连接酶，这种连接酶对闭合硫代酰胺的生物合成至关重要：CtaG。它们为CtaG如何重新利用蛋白酶样活性位点来催化两个载体蛋白结合底物之间的酰胺键形成提供了机制和结构上的解释。

引用次数: 0

Long-wavelength photocatalysis enabled by an in-situ-assembled manganese platform 由原位组装的锰平台实现的长波长光催化

IF 19.6 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chem

Pub Date : 2026-01-15 DOI: 10.1016/j.chempr.2025.102916

Sejin Park , Jihwan Kim , Hyotcherl Ihee , Yoonsu Park

Advances in long-wavelength photocatalysis have drawn significant attention within organic synthesis. In this issue of Chem, Niu and co-workers describe a manganese-based long-wavelength photocatalytic platform that mediates alkene oxygenation and nitrogenation through a modular in situ assembly approach. The utility of this platform is demonstrated by its wide substrate scope, scalability, and efficient late-stage functionalization.

长波长光催化的研究进展在有机合成领域引起了广泛的关注。在这一期的《化学》杂志上，Niu及其同事描述了一种基于锰的长波长的光催化平台，该平台通过模块化的原位组装方法介导烯烃氧化和氮化。该平台的实用性体现在其广泛的基板范围、可扩展性和高效的后期功能化。

引用次数: 0

Catalytic enantioselective synthesis of mechanically planar chiral rotaxanes by organocatalyzed desymmetrization 机械平面手性轮烷的有机催化脱对称催化对映选择性合成

IF 19.6 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chem

Pub Date : 2026-01-15 DOI: 10.1016/j.chempr.2025.102694

Mengyao Tang (唐梦瑶) , Jinmiao Zhou (周金淼) , Wansen Xie (谢万森) , Jiayi Ren (任佳艺) , Zidan Ye (叶子旦) , Huanchao Gu (谷欢潮) , Xiaoyu Yang (杨晓瑜)

Mechanical chirality, a non-classical form of molecular chirality arising from the spatial arrangements of component parts connected by mechanical bonds, has been identified in various mechanically interlocked molecules (MIMs), notably represented by mechanically planar chiral (MPC) rotaxanes. Due to their dynamic and inherently chiral properties, MPC rotaxanes have found diverse and promising applications. Despite recent advancements in practical chiral auxiliary-directed asymmetric synthesis, the catalytic enantioselective synthesis of MPC rotaxanes remains a formidable challenge because of the complexity in discriminating mechanical planar chirality and the conformational flexibility of mechanical bonds. In this work, we present an efficient desymmetrization strategy for the catalytic enantioselective synthesis of MPC rotaxanes by integrating rotaxane preorganization through multiple noncovalent interactions and the exceptional stereodiscrimination capabilities of chiral phosphoric acid catalysis, resulting in a broad scope and high enantioselectivities. Notably, the resulting MPC rotaxane products emerge as chiral rotaxane catalysts with tunable reactivity and stereoselectivity.

机械手性是由由机械键连接的组成部分的空间排列引起的分子手性的非经典形式，已在各种机械互锁分子（mim）中被发现，特别是以机械平面手性（MPC）轮烷为代表。由于其动态和固有的手性，MPC轮烷已经发现了多种和有前途的应用。尽管近年来在实际的手性辅助定向不对称合成方面取得了进展，但由于区分机械平面手性和机械键的构象柔韧性的复杂性，催化对映选择性合成MPC轮烷仍然是一个巨大的挑战。在这项工作中，我们提出了一种有效的去对称策略，通过多种非共价相互作用整合轮烷预组织和手性磷酸催化的特殊立体辨别能力，从而实现了广泛的范围和高对映选择性的MPC轮烷催化合成。值得注意的是，所得的MPC轮烷产品是具有可调反应活性和立体选择性的手性轮烷催化剂。

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引用次数: 0

Catalytic asymmetric reductive addition reactions using carbon electrophiles 用碳亲电试剂催化不对称还原加成反应

IF 19.6 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chem

Pub Date : 2026-01-15 DOI: 10.1016/j.chempr.2025.102715

Xueli Lv , Zhuangzhi Shi

Transition metal-catalyzed asymmetric reductive addition (ARA) reactions using carbon electrophiles have emerged as a robust platform for constructing molecular complexity with high enantiocontrol. This review surveys major advancements in ARA chemistry since 2020, with a focus on sustainable catalytic systems based on earth-abundant 3d transition metals such as nickel, cobalt, and chromium. These catalysts enable the reductive coupling of aryl, vinyl, propargyl, allenyl, allyl, and alkyl electrophiles with diverse unsaturated acceptors (e.g., aldehydes, ketones, imines, α,β-unsaturated compounds, nitriles, carbon dioxide [CO₂], and sulfinylamines) under mild conditions. The methodology offers broad substrate scope and delivers enantioenriched alcohols, amines, and carboxylic acids with excellent stereo- and regiocontrol. Detailed mechanistic insights into catalytic cycles, reactive intermediates, and stereodiscrimination are discussed. Looking ahead, advances in catalyst design and exploration of new electrophilic partners are expected to further expand the synthetic utility and impact of ARA reactions in asymmetric synthesis.

利用碳亲电试剂催化过渡金属催化的不对称还原加成反应（ARA）已成为构建具有高对映控制力的分子复杂性的强大平台。本文综述了自2020年以来ARA化学的主要进展，重点关注基于地球上丰富的三维过渡金属（如镍、钴和铬）的可持续催化系统。这些催化剂使芳基、乙烯基、丙炔基、烯丙基、烯丙基和烷基亲电试剂能够在温和条件下与各种不饱和受体（如醛、酮、亚胺、α、β-不饱和化合物、腈、二氧化碳和亚胺）还原偶联。该方法提供了广泛的底物范围，并提供了对映体富集的醇，胺和羧酸具有良好的立体和区域控制。详细的机理见解催化循环，反应中间体，和立体识别进行了讨论。展望未来，在催化剂设计和新的亲电性伙伴的探索方面的进展有望进一步扩大ARA反应在不对称合成中的应用和影响。

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引用次数: 0

Signal processing programmed by non-equilibrium phase transition of enzyme-responsive short peptide 酶反应短肽非平衡相变编程的信号处理

IF 19.6 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chem

Pub Date : 2026-01-15 DOI: 10.1016/j.chempr.2025.102718

Xuewen Wei , Xiaohan Mei , Qingyun Zhang , Qian Zhang , Yaling Wang , Xiaoying Kang , Ji Qi , Ang Li , Nannan Xiao , Yan Zhang , Lina Zou , Deling Kong , Chunqiu Zhang

Liquid-liquid phase separation (LLPS) has gained acceptance as a ubiquitous route to membraneless organelles (known as coacervates) that are found in living cells. Emerging evidence reveals that the dynamic coacervates in response to enzymatic modulations play an indispensable role in the spatiotemporal organization of intracellular signal networks. However, the design of enzyme-responsive LLPS-competent components capable of generating biomimetic functional coacervates for signal processing remains relatively unexplored. Here, we present a non-equilibrium phase transition system in which the coacervation was induced by the dephosphorylation of LLPS-competent component precursor and dismantled in an oxidation-driven process. The dynamic control of LLPS enabled us to implement a range of logic gates, including BUFFER, AND, NOT, NAND, NOR, and INHIBIT gate, and programmable signal processing by using biochemical inputs. Our findings provide a step toward constructing an enzymatic-responsive non-equilibrium phase transition system with a single LLPS-competent component and great potential for engineering precise signal processing and bio-computation.

液-液相分离（LLPS）作为一种在活细胞中发现的无膜细胞器（称为凝聚体）的普遍途径已被接受。新出现的证据表明，响应酶调节的动态凝聚在细胞内信号网络的时空组织中起着不可或缺的作用。然而，能够产生用于信号处理的仿生功能凝聚体的酶响应LLPS-competent组件的设计仍然相对未被探索。在这里，我们提出了一个非平衡相变系统，其中凝聚是由LLPS-competent组分前体的去磷酸化引起的，并在氧化驱动的过程中被拆除。LLPS的动态控制使我们能够实现一系列逻辑门，包括缓冲器，AND， NOT， NAND， NOR和抑制门，以及使用生化输入的可编程信号处理。我们的发现为构建具有单个llps胜任成分的酶响应非平衡相变系统提供了一步，并且在工程精确信号处理和生物计算方面具有巨大潜力。

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引用次数: 0

Structure-performance relationships for catalysis-driven molecular machinery 催化驱动分子机械的结构-性能关系

IF 19.6 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chem

Pub Date : 2026-01-15 DOI: 10.1016/j.chempr.2025.102742

Joaquin Baixeras Buye , James M. Gallagher , David A. Leigh

Chemically fueled molecular motors are key to life’s most fundamental processes. In recent years, theoretical and experimental insights garnered from chemistry, biology, and physics have led to an understanding of the molecular basis of catalysis-driven motor mechanisms. Unlike their biological counterparts, for which evolutionary baggage and complexity often preclude a complete untangling of the reasons behind particular aspects of their mechanisms, artificial small-molecule motors operate with mechanisms that are entirely knowable. Here, we outline how key performance indicators, such as speed, stalling force, and fuel efficiency, are related to distinct structural and mechanistic features, contextualizing the analysis with both biological and small-molecule examples. These provide rational design principles for functional chemically fueled molecular machinery and benchmarking comparisons with biomolecular machinery. We have made available as a Jupyter notebook an interactive visualization tool that highlights how the key performance indicators change and depend upon the underlying kinetics of chemical fueling: https://github.com/JoaquinBaixerasBuye/Performance-Characteristics-of-Motors.

化学燃料的分子马达是生命最基本过程的关键。近年来，从化学、生物学和物理学中获得的理论和实验见解已经导致了对催化驱动运动机制的分子基础的理解。与生物发动机不同的是，生物发动机的进化包袱和复杂性往往使我们无法完全弄清其机制特定方面背后的原因，而人工小分子发动机的运作机制是完全可知的。在这里，我们概述了关键性能指标，如速度、失速力和燃油效率，如何与不同的结构和机械特征相关，并将分析与生物和小分子示例联系起来。这为功能性化学燃料分子机械提供了合理的设计原则，并与生物分子机械进行了基准比较。我们已经提供了一个交互式可视化工具作为Jupyter笔记本，它突出显示了关键性能指标是如何变化的，并依赖于化学燃料的潜在动力学：https://github.com/JoaquinBaixerasBuye/Performance-Characteristics-of-Motors。

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引用次数: 0

In vivo antibody-selective conjugation technology for long-acting drugs 长效药物的体内抗体选择性偶联技术

IF 19.6 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chem

Pub Date : 2026-01-15 DOI: 10.1016/j.chempr.2025.102705

Katsushi Kitahara , Aurélie Rondon , Edward Miller , Howard H. Mak , Andrei Loas , Bradley L. Pentelute

Peptide-based therapeutics are currently in great demand but often suffer from rapid clearance and accumulation in off-target tissues, which continue to present barriers in their clinical translation. We report the development of an electrophilic peptide for the attachment of therapeutics to native immunoglobulin G (IgG) antibodies in vivo. This reactive scaffold enables the biorthogonal, selective covalent linkage of drugs of choice to circulating IgGs directly in live animals. Native IgG-selective conjugation with glucagon-like peptide-1 (GLP-1) results in sustained body weight loss and prolonged blood glucose management after one dose. This versatile technology has the potential to advance the next generation of long-acting peptide-based medicines.

基于肽的治疗方法目前需求量很大，但往往存在快速清除和在非靶组织中积累的问题，这在其临床转化中继续存在障碍。我们报道了一种亲电肽的发展，用于在体内将治疗药物附着于天然免疫球蛋白G （IgG）抗体。这种反应性支架使选择药物的双正交、选择性共价连锁直接在活体动物中循环igg。天然igg选择性结合胰高血糖素样肽-1 （GLP-1）可在一次剂量后持续减轻体重和延长血糖控制时间。这种多功能技术有可能推动下一代长效肽类药物的发展。

引用次数: 0

In situ cryogenic X-ray photoelectron spectroscopy unveils metastable components of the solid electrolyte interphase in Li-ion batteries 原位低温x射线光电子能谱揭示了锂离子电池中固体电解质界面的亚稳态成分

IF 23.5 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chem

Pub Date : 2025-12-16 DOI: 10.1016/j.chempr.2025.102837

Dan-Thien Nguyen, Venkateshkumar Prabhakaran, Vaithiyalingam Shutthanandan, Karl T. Mueller, Vijayakumar Murugesan

Identifying the intrinsic chemical composition of the solid electrolyte interphase (SEI) in Li-ion batteries has long been a challenging endeavor. Herein, we have developed a state-of-the-art cryogenic X-ray photoelectron spectroscopy (XPS) system integrated with residual gas analysis to capture the metastable components of the SEI. This advanced configuration enables instantaneous freezing of the cycled graphite electrode, followed by monitoring of the surface evolution and gas release as the electrode transitions from cryogenic temperature to room temperature. Our findings reveal that lithium fluorophosphate is the primary decomposition product of lithium hexafluorophosphate, which rapidly degrades into LiF and POF₃ upon transitioning out of the cryogenic state. Utilizing this experimental setup, we identified critical experimental parameters that can lead to measurement artifacts, including prolonged exposure to ultrahigh vacuum conditions, improper neutralizer control, and inadequate sample-drying protocols. Careful management of these factors will ensure reliable and reproducible XPS measurements for battery-related materials, and our findings highlight best practices for such analyses.

确定锂离子电池固体电解质界面（SEI）的固有化学成分一直是一个具有挑战性的工作。在此，我们开发了一种最先进的低温x射线光电子能谱（XPS）系统，集成了残余气体分析，以捕获SEI的亚稳成分。这种先进的配置可以使循环石墨电极瞬间冻结，然后在电极从低温过渡到室温时监测表面演变和气体释放。我们的研究结果表明，氟磷酸锂是六氟磷酸锂的主要分解产物，在脱离低温状态后迅速降解为LiF和POF3。利用该实验装置，我们确定了可能导致测量伪影的关键实验参数，包括长时间暴露在超高真空条件下、不适当的中和剂控制和不适当的样品干燥方案。仔细管理这些因素将确保对电池相关材料进行可靠和可重复的XPS测量，我们的研究结果突出了此类分析的最佳实践。

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引用次数: 0

Synthesis of single-crystalline carbon nanothreads from 1-naphthoic acid with high anisotropic thermal conductivity 高各向异性导热系数的1-萘酸单晶碳纳米线的合成

IF 23.5 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chem

Pub Date : 2025-12-15 DOI: 10.1016/j.chempr.2025.102836

Xin Yang, Qingchao Zeng, Yizhe Liu, Bo Sun, Ruyue Shi, Xingyu Tang, Guangwei Che, Peijie Zhang, Haiyan Zheng, Yajie Wang, Aijiao Guan, Junfeng Xiang, Dexiang Gao, Xuan Wang, Yida Wang, Yongjin Chen, Xiao Dong, George D. Cody, Ho-kwang Mao, Kuo Li

Carbon nanothreads (CNThs) are one-dimensional diamondoid nanomaterials. They are predicted to combine diamonds’ high strength and thermal conductivity with enhanced flexibility, but current synthesis methods struggle to produce high-quality single-crystalline CNThs. Here, we report the synthesis of a 100-μm-scale CNTh single crystal via a single-crystal-to-single-crystal transformation by compressing 1-naphthoic acid at 20 GPa and 573 K. Structurally, the CNTh resembles a hexagonal diamond. The intrathread bonding is governed by a sequential regioselective Diels-Alder reaction, and hydrogen bonds control the interthread ordering. The large, high-quality crystal allowed the experimental demonstration of the highly anisotropic compressibility and thermal conductivity. The thermal conductivity was 11.2 W m⁻¹ K⁻¹ along the thread, 84 times greater than across it, and a near-zero compressibility along the thread, in contrast to 0.013 GPa⁻¹ across the thread. CNThs are therefore demonstrated as anisotropic thermal conductive materials with excellent mechanical properties.

碳纳米线是一种一维金刚石纳米材料。预计它们将结合钻石的高强度、导热性和增强的柔韧性，但目前的合成方法很难生产出高质量的单晶cnth。本文报道了1-萘酸在20gpa和573 K下通过单晶到单晶的转变合成了100 μm尺度的CNTh单晶。在结构上，CNTh类似于六边形钻石。螺纹内键由连续的区域选择性Diels-Alder反应控制，氢键控制螺纹间的顺序。大而高质量的晶体使实验证明了高各向异性的可压缩性和导热性。沿螺纹的导热系数为11.2 W m−1 K−1，是沿螺纹的84倍，沿螺纹的可压缩性接近于零，而沿螺纹的可压缩性为0.013 GPa−1。因此，碳纳米管被证明是具有优异机械性能的各向异性导热材料。

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引用次数: 0

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