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Recent Advances in Ene Reactions with Carbon Enophiles 烯与亲碳亲烯试剂反应的最新进展
IF 4 2区 化学 Q2 CHEMISTRY, APPLIED Pub Date : 2025-11-28 DOI: 10.1002/adsc.70122
Thomas J. J. Müller
Ene reactions are inter‐ or intramolecular addition reactions between a four‐electron "ene" component and a two‐electron enophile functionality, in which two π‐bonds and a C–H (or metal–C) σ‐bond are rearranged into one π‐bond and two σ‐bonds. One of the newly formed σ‐bonds is a carbon–carbon bond, while the other is the rearranged a C–H (or metal–C) bond. This transformation enables the formation of structurally and functionally complex ene products in a single step. Originally, ene reactions were discovered as concerted and stepwise pericyclic elementary processes. However, increasing mechanistic insight—gained through both experimental and computational studies—along with extensive empirical methodological work, has paved the way to a plethora of ene‐type reactions involving carbon enophiles. Since 2012, the already well‐established transition metal‐catalyzed variants of ene reactions have significantly expanded. Moreover, highly reactive aryne intermediates—generated in situ either by fluoride induced elimination from ortho‐silyl aryltriflates at room temperature, or by hexadehydro‐Diels–Alder reaction of a 1,3‐diyne with an alkyne (both inter‐ and intramolecularly)—find increasing application in novel ene‐type sequences. Propargyl ene reactions also gain traction, particularly because the resulting ene‐allenes serve as highly valuable intermediates in the design of domino sequences that lead to complex polycyclic fused structures. Finally, the implementation of ene reactions in polymer chemistry for the synthesis of functionalized polymers and renewable unsaturated raw materials has emerged as a promising alternative to the use of purely petrochemistry based substrates.
烯反应是四电子“烯”组分与两个电子亲烯官能团之间的分子间或分子内加成反应,其中两个π键和一个C-H(或金属- c) σ键被重排成一个π键和两个σ键。新形成的σ-键一个是碳-碳键,另一个是重排的碳-氢(或金属-碳)键。这种转化可以在一个步骤中形成结构和功能复杂的烯产品。最初,烯反应被发现为协调的、逐步的周环基本过程。然而,通过实验和计算研究,以及广泛的经验方法工作,不断增加的机理见解,为涉及亲碳试剂的过多的烯型反应铺平了道路。自2012年以来,已经建立的过渡金属催化的烯反应变体得到了显着扩展。此外,高活性的芳基中间体——在室温下由氟诱导的邻硅基芳基三氟酯消除原位生成,或由1,3-二炔与炔(分子间和分子内)的六氢- diels - alder反应生成——在新型基因型序列中越来越多地应用。丙炔反应也获得了关注,特别是因为产生的烯-烯在设计导致复杂多环融合结构的多米诺骨牌序列中作为非常有价值的中间体。最后,在聚合物化学中实施烯反应来合成功能化聚合物和可再生的不饱和原料已经成为使用纯石化基底物的有希望的替代方法。
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引用次数: 0
Ortho‐Functionalized Diaryliodonium Salts: Synthesis and Reactivity 邻位官能化二芳基碘鎓盐:合成与反应性
IF 4 2区 化学 Q2 CHEMISTRY, APPLIED Pub Date : 2025-11-28 DOI: 10.1002/adsc.70135
Lifeng Chu , Limin Wang , Jianwei Han
Hypervalent iodine reagents have attracted considerable attention in modern organic synthesis due to their low toxicity and versatile reactivity. Among them, ortho‐functionalized diaryliodonium salts represent an important subclass, distinguished by their unique structural characteristics and reactivity. This review summarizes recent advances in the development of ortho‐functionalized diaryliodonium reagents, with particular emphasis on the role of ortho‐substituents as leaving groups or participanting moieties in reactions. Newly developed transformations are discussed alongside their mechanisms, highlighting the intramolecular interactions with the iodine(III) center.
高价碘试剂因其低毒性和多用途反应性在现代有机合成中引起了广泛的关注。其中,正官能化二芳基碘鎓盐是一类重要的亚类,以其独特的结构特征和反应性而著称。本文综述了邻位功能化二芳基碘鎓试剂的最新进展,重点介绍了邻位取代基在反应中作为离开基团或参与基团的作用。讨论了新发展的转化及其机制,重点介绍了与碘(III)中心的分子内相互作用。
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引用次数: 0
N‐Containing Carbon Materials in Metal‐Free and Non‐Noble Metal Liquid Phase Heterogenous Catalysis 含氮碳材料在无金属和非贵金属液相多相催化中的应用
IF 4 2区 化学 Q2 CHEMISTRY, APPLIED Pub Date : 2025-11-28 DOI: 10.1002/adsc.70134
Fulvio Varamo , Anna Katharina Beine
Non‐noble metal and metal‐free catalysts can be of great benefit for the development of economically and environmentally sustainable chemical processes. In this context, N‐containing carbon materials serve both as effective catalyst supports and standalone catalysts, offering enhanced stability by mitigating deactivation mechanisms such as metal leaching and sintering. The review is primarily organized by non‐noble metal, systematically covering each case in which their use as an active phase on N‐containing carbon materials has been reported in literature. In parallel, cross‐cutting aspects are examined throughout, including the role of different N‐functionalities (graphitic, pyridinic, pyrrolic, and pyridinic‐N‐oxide) in active‐phase stabilization mechanisms. Structurally diverse carbon materials—such as amorphous carbon, carbon nanotubes, carbon spheres, carbon nanofibers, and graphene—are also considered. Furthermore, the influence of preparation methods, including template‐free, hard‐templating and soft‐templating techniques, is analyzed with emphasis on their role in tuning textural properties. Despite significant progress, uncertainties remain regarding the precise stabilization mechanisms and the relative contributions of different N‐functionalities to catalytic activity and surface acid–base properties. Addressing these knowledge gaps will be essential for optimization of N‐containing carbon materials and to drive the transition towards greener and more sustainable catalytic technologies.
非贵金属和无金属催化剂对经济上和环境上可持续的化工过程的发展具有重要的意义。在这种情况下,含n碳材料既可以作为有效的催化剂载体,也可以作为独立的催化剂,通过减轻金属浸出和烧结等失活机制,提高了稳定性。这篇综述主要是由非贵金属组织的,系统地涵盖了它们在含氮碳材料上作为活性相使用的每一种情况。同时,横切方面的研究贯穿始终,包括不同的n官能团(石墨、吡啶、吡咯烷和吡啶- n -氧化物)在活性相稳定机制中的作用。结构多样的碳材料-如无定形碳,碳纳米管,碳球,碳纳米纤维,石墨烯-也被考虑。此外,分析了制备方法的影响,包括无模板、硬模板和软模板技术,重点分析了它们在调整纹理性能方面的作用。尽管取得了重大进展,但关于精确的稳定机制以及不同n官能团对催化活性和表面酸碱性质的相对贡献仍然存在不确定性。解决这些知识差距对于优化含氮碳材料以及推动向更环保、更可持续的催化技术过渡至关重要。
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引用次数: 0
Charge Controlled Engineering: Constructing Built‐in Electric Fields at CoCu‐ZIF/Cu3P‐GDY Interfaces for Enhanced Photocatalytic Hydrogen Evolution 电荷控制工程:在CoCu-ZIF/Cu3P-GDY界面上构建增强光催化析氢的内置电场
IF 4 2区 化学 Q2 CHEMISTRY, APPLIED Pub Date : 2025-11-28 DOI: 10.1002/adsc.70126
Jieyuan Du , Yuyu Wang , Guoping Jiang , Fei Jin , Zhiliang Jin
Rational design of interfacial electric fields in nanostructures for accelerated photogenerated carrier transfer and separation. First, Cu+‐mediated self‐assembly engineering narrows the bandgap of ZIF‐67 while extending the light absorption range of CoCu‐ZIF. Furthermore, hierarchical architecture is constructed to incorporate the cocatalyst Cu3P‐GDY. The staggered energy levels in the resulting CoCu‐ZIF/Cu3P‐GDY composite generate a strong driving force. Comprehensive characterization, including density functional theory calculations and Mott–Schottky analysis, confirm the formation of an S‐scheme heterojunction between GDY and CoCu‐ZIF. Cu3P acts as an electron bridge to promote the directional transfer of photogenerated carriers driven by interfacial electric fields. Differential surface photovoltage signals demonstrate that the robust interfacial electric field enables efficient carrier separation in the CoCu‐ZIF/Cu3P‐GDY composite. This work establishes a new paradigm for enhancing catalytic performance through broadened light absorption and rationally engineered interfacial electric fields.
加速光生载流子转移和分离的纳米结构界面电场的合理设计。首先,Cu+介导的自组装工程缩小了ZIF-67的带隙,同时扩大了CoCu-ZIF的光吸收范围。此外,还构建了含Cu3P-GDY共催化剂的分层结构。CoCu-ZIF/Cu3P-GDY复合材料的交错能级产生了强大的驱动力。综合表征,包括密度泛函理论计算和Mott-Schottky分析,证实了GDY和CoCu-ZIF之间形成了s型异质结。Cu3P作为电子桥,在界面电场的驱动下促进光生载流子的定向转移。差分表面光电压信号表明,强大的界面电场使CoCu-ZIF/Cu3P-GDY复合材料中的载流子有效分离。本研究建立了一种通过扩大光吸收和合理设计界面电场来提高催化性能的新范式。
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引用次数: 0
Photoinduced Copper‐Catalyzed Radical Ring‐Opening Azidation of Cyclic Oxime Esters 光诱导铜催化环肟酯自由基开环叠氮化反应
IF 4 2区 化学 Q2 CHEMISTRY, APPLIED Pub Date : 2025-11-28 DOI: 10.1002/adsc.70133
Li‐Bo Yang , Jia Hu , Tian‐Tian Zou , Xin‐Song Zhou , Jing Li , Yuan Qu , Ya‐Min Li
A photoinduced copper‐catalyzed radical ring‐opening azidation of cyclic oxime esters has been developed for the synthesis of valuable γ‐azido alkylnitriles. Furthermore, a one‐pot sequential strategy integrating this ring‐opening azidation with copper‐catalyzed azide–alkyne cycloaddition is successfully implemented, enabling the direct construction of 1,2,3‐triazole derivatives in a single operation.
采用光诱导铜催化环肟酯自由基开环叠氮化反应,合成了有价γ-叠氮基烷基腈。此外,成功地实现了一锅序贯策略,将开环叠氮化与铜催化叠氮化-炔环加成相结合,实现了在一次操作中直接构建1,2,3-三唑衍生物。
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引用次数: 0
Thioether Synthesis via the Nickel‐Catalyzed Electrochemical Cross Electrophile Coupling of Aryl/Alkyl Disulfides and Aryl/Alkyl Halides 镍催化芳基/烷基二硫化物和芳基/烷基卤化物电化学交叉亲电偶联合成硫醚
IF 4 2区 化学 Q2 CHEMISTRY, APPLIED Pub Date : 2025-11-28 DOI: 10.1002/adsc.70116
Jona Queder , Gerhard Hilt
A formal cross‐electrophile coupling approach enables the base‐free synthesis of (un)symmetric (hetero)aryl and alkyl sulfides from organic halides and disulfides. This water and air‐tolerant process utilizes the addition of electrochemically generated thiolate to an in situ‐generated reactive nickel species.
正式的交叉亲电偶联方法使有机卤化物和二硫化物的(非)对称(杂)芳基和烷基硫化物的无碱合成成为可能。这种耐水和耐空气的工艺利用了将电化学生成的硫酸盐添加到原位生成的活性镍中。
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引用次数: 0
Chemodivergent Higher‐Order Annulation of Azaheptafulvenes with Enals Through N‐Heterocyclic Carbene Catalysis 氮杂环碳催化氮杂七富尔烯与烯醛的高阶化学发散环化
IF 4 2区 化学 Q2 CHEMISTRY, APPLIED Pub Date : 2025-11-28 DOI: 10.1002/adsc.70127
Yiwen Zhang , Yangjie Yu , Min Xia , Zhen Wang , Manman Sun , Weijun Yao
A base‐directed, chemodivergent, higher‐order annulation between azaheptafulvenes and enals has been developed through N‐heterocyclic carbene catalysis. In the presence of an N‐heterocyclic carbene organocatalyst, DBU promotes an [8 + 3] annulation with excellent chemo‐ and diastereoselectivities, whereas the reaction proceeds via an [8 + 2] annulation when potassium carbonate is used as the base. In addition, the reaction can be carried out on a gram scale, and the products are efficiently converted into bicyclic derivatives.
通过n -杂环碳催化,在氮杂环呋喃和烯醛之间形成了碱基定向、化学发散、高阶的环。在n -杂环羰基有机催化剂的存在下,DBU以优异的化学选择性和非对映选择性促进[8 + 3]环化,而当碳酸钾作为碱时,反应通过[8 + 2]环化进行。此外,该反应可以在克尺度上进行,产物可以有效地转化为双环衍生物。
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引用次数: 0
Gold‐Catalyzed Enantioselective Synthesis of Axially Chiral Compounds 金催化轴向手性化合物的对映选择性合成
IF 4 2区 化学 Q2 CHEMISTRY, APPLIED Pub Date : 2025-11-28 DOI: 10.1002/adsc.70139
Yirong Dong , Tao Wang
This review provides an overview of the advances in gold‐catalyzed synthesis of axially chiral compounds. The published results to date on this topic are categorized by the type of chiral axis, highlighting the structure of ligands, the reaction scope, and mechanistic insights. The challenges and the future directions of this field are also discussed.
本文综述了金催化合成轴向手性化合物的研究进展。迄今为止发表的关于该主题的结果按手性轴的类型分类,突出了配体的结构,反应范围和机理见解。讨论了该领域面临的挑战和未来的发展方向。
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引用次数: 0
Cu(I) Catalyzed Germyl S‐Phosphorothiolation of Electron‐Deficient Alkene 铜(I)催化缺电子烯烃的Germyl S -磷硫基化
IF 4 2区 化学 Q2 CHEMISTRY, APPLIED Pub Date : 2025-11-28 DOI: 10.1002/adsc.70147
Asim Kumar Ghosh , Alakananda Hajra
A copper‐catalyzed three‐component radical relay protocol is demonstrated for difunctionalization of electron‐withdrawing alkenes using germanium hydride and S‐phosphorothiol to afford the germylphosphorothiolated product. This transformation reveals excellent tolerance for functional groups and occurs under mild reaction conditions, exhibiting a high level of regioselectivity. Control experiments suggest the involvement of germyl radicals in these transformations.
采用铜催化的三组分自由基接力反应方案,利用氢化锗和硫代磷得到了缩电子烯烃的二官能化产物。这种转化显示出对官能团的良好耐受性,并且在温和的反应条件下发生,表现出高水平的区域选择性。对照实验表明胚芽基参与了这些转化。
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引用次数: 0
Direct Access to Aminocyclopentenones through Rh‐Catalyzed Cascade Wolff Rearrangement and Decarbonylative Amination 通过Rh催化级联Wolff重排和脱羰胺化直接获得氨基环戊烯酮
IF 4 2区 化学 Q2 CHEMISTRY, APPLIED Pub Date : 2025-11-28 DOI: 10.1002/adsc.70110
Lvlv Gao , Jianwei Wu , Jian Wang , Enshen Zhang , Yongjia Shang , Xinwei He
The cascade reaction of cyclic 2‐diazo‐1,3‐diketones and diarylamines is efficiently developed, enabling straightforward access to a series of 2‐aminocyclopentenones in good to excellent yields (71–90%). The procedure is proposed to go through a sequence of Wolff rearrangement via initial ketene formation, nucleophilic addition/keto‐enol tautomerization, and Rh2(OAc)4‐catalyzed decarbonylative amination followed by an oxidation process. A broad range of substrates are compatible with this mild reaction system, thereby providing a facile and practical approach for constructing important skeleton of aminocyclopentenone.
环2 -重氮- 1,3 -二酮和二芳胺的级联反应被有效地开发出来,可以直接获得一系列的2 -氨基环戊烯酮,收率很高(71-90%)。该过程经过一系列的Wolff重排,包括初始的烯酮形成,亲核加成/酮烯醇互变异构,以及Rh2(OAc)4催化的脱羰胺化,然后是氧化过程。广泛的底物与这种温和的反应体系兼容,从而为构建氨基环戊酮的重要骨架提供了一种简便实用的方法。
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引用次数: 0
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Advanced Synthesis & Catalysis
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