Advanced Synthesis & Catalysis最新文献

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Exploring Transition‐Metal‐Catalyzed Pathways to Indoles From Alkynes and Nitrogen Compounds 探索过渡金属催化从炔和氮化合物合成吲哚的途径

IF 4 2区化学 Q2 CHEMISTRY, APPLIED

Advanced Synthesis & Catalysis

Pub Date : 2026-02-17 Epub Date: 2026-02-27 DOI: 10.1002/adsc.70305

Tales A. C. Goulart , Roberto do Carmo Pinheiro , Gilson Zeni

Indoles represent a privileged scaffold in organic and medicinal chemistry, prompting continuous efforts toward efficient and versatile synthetic methodologies. In this review, we present a focused survey of recent advances (2020–2025) in the transition‐metal‐catalyzed synthesis of indoles from alkynes and nitrogen sources. Both intra‐ and intermolecular strategies are discussed, highlighting key developments involving cobalt, copper, gold, nickel, palladium, platinum, silver, rhodium, and ruthenium catalysts. Attention is given to mechanistic insights, with detailed discussions provided where necessary to enhance the reader's understanding of the underlying transformations. While this is not an exhaustive compilation of all literature available in the period, we emphasize the most representative and innovative contributions, acknowledging that space limitations may have excluded some high‐quality studies. This review aims to offer a clear and accessible overview of state‐of‐the‐art methodologies, serving as a valuable resource for researchers interested in the design and application of indole‐forming processes from readily available alkynes and nitrogen‐containing precursors.

吲哚在有机化学和药物化学中是一种特殊的支架，促使人们不断努力发展高效、通用的合成方法。在这篇综述中，我们重点介绍了过渡金属催化从炔和氮源合成吲哚的最新进展（2020-2025）。讨论了分子内和分子间的策略，重点介绍了涉及钴、铜、金、镍、钯、铂、银、铑和钌催化剂的关键发展。本书关注的是机械的见解，并在必要的地方提供了详细的讨论，以增强读者对潜在转换的理解。虽然这不是该时期所有文献的详尽汇编，但我们强调最具代表性和创新性的贡献，承认空间限制可能排除了一些高质量的研究。这篇综述的目的是提供一个清晰和可访问的最新方法概述，作为一个有价值的资源，为研究人员感兴趣的设计和应用从现成的炔和含氮前体形成吲哚的过程。

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引用次数: 0

Phosphine‐Catalyzed Enantioselective [3 + 2] Annulation of Allene‐1,3‐Dicarboxylates with Rhodanine‐Derived Alkenes 膦催化的烯- 1,3 -二羧酸与罗丹宁衍生烯烃的对映选择性[3 + 2]环化反应

IF 4 2区化学 Q2 CHEMISTRY, APPLIED

Advanced Synthesis & Catalysis

Pub Date : 2026-02-17 Epub Date: 2026-02-27 DOI: 10.1002/adsc.70274

Bo Wang , Zhiyang Cui , Honghao Sun , Jingrong Jin , Huizhe Lu , Leijie Zhou , Yanmei Xiong , Hongchao Guo

Despite notable advances achieved in the classic phosphine catalyzed allene–alkene [3 + 2] annulations, the scope of allenes mainly restrict to allenoates that bearing electron‐donating or neutral γ‐substituents. Reaction profile of electron‐withdrawing group‐substituted allenoates (e.g. allene‐1,3‐dicarboxylates (ADCs)) remained elusive yet in both symmetric and asymmetric patterns. Herein, we present a (S)‐SITCP‐catalyzed [3 + 2] reaction of ADCs with rhodanine‐derived alkenes, providing efficient access of chiral spiro[rhodanine‐cyclopentene] derivatives in good yields (up to 98%) with excellent enantio‐ (up to 99% ee) and diastereoselectivity (up to > 20:1 dr). Notably, ADCs exhibited unparalleled reactivity and enantioselectivity against their γ‐electron‐donating or neutral substituted analogs in this reaction.

尽管经典的磷化氢催化的烯-烯[3 + 2]环取得了显著的进展，但烯的范围主要局限于携带供电子或中性γ取代基的烯丙酸酯。吸电子基团取代的烯丙酸酯（例如，烯- 1,3 -二羧酸酯（adc））的反应谱仍然难以捉摸，但在对称和不对称模式下都是如此。在此，我们提出了一个(S)‐SITCP‐催化的adc与罗丹宁衍生烯烃的[3 + 2]反应，提供了手性螺旋[罗丹宁‐环戊烯]衍生物的高效途径，收率高（高达98%），对映率高（高达99% ee），非对映选择性高（高达20:1 dr）。值得注意的是，在该反应中，adc对其提供γ电子或中性取代类似物表现出无与伦比的反应活性和对映选择性。

引用次数: 0

Photocatalytic, Electrocatalytic, and Photoelectrocatalytic Radical‐Mediated Three‐Component Cascade Cyclization Reactions: Facile Access to N‐Heterocyclic Compounds 光催化、电催化和光电催化自由基介导的三组分级联环化反应：易于获得N杂环化合物

IF 4 2区化学 Q2 CHEMISTRY, APPLIED

Advanced Synthesis & Catalysis

Pub Date : 2026-02-17 Epub Date: 2026-02-27 DOI: 10.1002/adsc.70306

Fang Wang , Xiaoyu Xie , Bo Ye , Lei Wang , Bihong Zhu

N‐Heterocyclic compounds (NHCs) are widely encountered in natural products and pharmaceuticals with diverse biological activities, and constitute fundamental structural motifs in numerous organic compounds. Consequently, investigations into the synthesis and modification of these NHCs hold particular significance for chemists and pharmacologists. Of particularly note, multicomponents cascade cyclization reactions allow for creation of many bonds, even stereocenters, in a single step while maintaining predictable stereochemistry have drawn increasing interest, and its broader application has been reinforced by radical chemistry. Photocatalysis and electrocatalysis are two powerful strategies to promote the chemical reactions that have received tremendous attention in recent years. Moreover, photoelectrochemical, a fusion of electrochemical and photochemical, completes reactions that were once challenging, stands out as an effective tool. In these ways, a number of diversly NHCs are constructed. Herein, the most recent contributions on photocatalytic, electrocatalytic, and photoelectrocatalytic radical‐mediated three‐component cascade cyclization reactions to access NHCs are reviewed, providing more possible avenues for future work in this growing area.

N -杂环化合物（NHCs）广泛存在于具有多种生物活性的天然产物和药物中，是许多有机化合物的基本结构基序。因此，研究这些NHCs的合成和修饰对化学家和药理学家具有特别重要的意义。特别值得注意的是，多组分级联环化反应允许在一个步骤中产生许多键，甚至是立体中心，同时保持可预测的立体化学，这引起了越来越多的兴趣，其更广泛的应用已被自由基化学所加强。光催化和电催化是近年来备受关注的两种促进化学反应的有力手段。此外，光电化学，一种电化学和光化学的融合，完成了曾经具有挑战性的反应，作为一种有效的工具脱颖而出。通过这些方式，构建了许多不同的国家卫生保健中心。本文综述了光催化、电催化和光电催化自由基介导的三组分级联环化反应获得NHCs的最新研究成果，为这一不断发展的领域的未来工作提供了更多可能的途径。

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引用次数: 0

Photoredox‐Catalyzed Chlorosulfonylation of gem‐Difluoroalkenes 光氧化还原催化的宝石二氟烯烃氯磺化反应

IF 4 2区化学 Q2 CHEMISTRY, APPLIED

Advanced Synthesis & Catalysis

Pub Date : 2026-02-17 Epub Date: 2026-02-27 DOI: 10.1002/adsc.70311

Raheel Ahmad , Yibo Tian , Tongtong Wang , Sakhawat Shah , Liqiao Han , Fengqian Zhao , Junliang Wu

A visible‐light‐catalyzed chlorosulfonylation reaction of gem‐difluoroalkenes has been successfully developed using sulfonyl chloride as both the sulfonyl group and chlorine source. The reaction proceeds under mild, additive‐free conditions, generating α,α‐difluoromethyl‐β‐chlorosulfones with excellent regioselectivity and broad substrate scope. The β‐chlorosulfone product serves as versatile intermediate, readily converting into valuable derivatives such as β‐azido sulfone. This method provides rapid access to functional fluorinated scaffolds relevant to medicinal chemistry.

以磺酰氯为磺酰基和氯源，成功地进行了可见光催化的宝石二氟烯烃氯磺化反应。该反应在温和、无添加剂的条件下进行，生成具有优异区域选择性和广泛底物范围的α， α -二氟甲基- β -氯砜。β -氯砜产品作为多功能中间体，很容易转化为有价值的衍生物，如β -叠氮砜。该方法提供了快速获取与药物化学相关的功能性氟化支架的途径。

引用次数: 0

Expanding the Toolbox for Hydrogen Atom Transfer Catalysis: Sulfides as Structurally Diverse Catalysts Under Photoredox Conditions 扩展氢原子转移催化工具箱：硫化物作为光氧化还原条件下结构多样的催化剂

IF 4 2区化学 Q2 CHEMISTRY, APPLIED

Advanced Synthesis & Catalysis

Pub Date : 2026-02-17 Epub Date: 2026-02-27 DOI: 10.1002/adsc.70293

Tetsuya Sengoku , Shun Nishioka , Yu Kokoda , Yoshifumi Noguchi , Toshiyasu Inuzuka

A new class of sulfide‐based catalysts that enable hydrogen atom transfer (HAT) under visible‐light‐driven photoredox conditions is reported. Based on the potential of indirect HAT processes, alkyl aryl sulfides that undergo single‐electron oxidation to generate radical cations were designed as candidate HAT catalysts. A wide variety of alkyl aryl sulfides exhibit catalytic activity, promoting the CH alkylation of a broad range of substrates, including alcohols, ethers, hydrocarbons, and aldehydes, in the presence of an acridinium photocatalyst. The reactions proceed under mild conditions without additional bases or additives. Mechanistic studies, including fluorescence quenching and deuterium labeling, indicate a pathway involving radical cation intermediates. DFT calculations indicate that the 2‐thiazolyl structure on the sulfide enhances the catalyst activity by shifting the HAT from an S‐centered pathway to an N‐centered pathway. This study establishes sulfides as modular platforms for photoredox‐mediated HAT catalysis.

报道了一类新的硫化物基催化剂，可在可见光驱动的光氧化还原条件下实现氢原子转移（HAT）。基于间接HAT过程的潜力，设计了单电子氧化生成自由基阳离子的烷基芳基硫化物作为HAT的候选催化剂。各种各样的烷基芳基硫化物表现出催化活性，在吖啶光催化剂的存在下，促进了广泛底物的C - H烷基化，包括醇、醚、碳氢化合物和醛。反应在温和的条件下进行，没有附加的碱或添加剂。机制研究，包括荧光猝灭和氘标记，表明了一个涉及自由基阳离子中间体的途径。DFT计算表明，硫化物上的2 -噻唑基结构通过将HAT从S中心途径转变为N中心途径来提高催化剂活性。本研究建立了硫化物作为光氧化还原介导的HAT催化的模块化平台。

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引用次数: 0

Visible‐Light‐Driven Organocatalyzed Chemoselective Oxidation of Benzylamines 可见光驱动的有机催化苯胺的化学选择性氧化

IF 4 2区化学 Q2 CHEMISTRY, APPLIED

Advanced Synthesis & Catalysis

Pub Date : 2026-02-17 Epub Date: 2026-02-27 DOI: 10.1002/adsc.70303

Chunbo Bo , Mengyao Niu , Fei Chen , Zhi‐Hong Du , Min Li , Jichang Liu , Donghui Wei , Ning Liu

Accurately controlling chemoselectivity is a challenging goal in the synthesis of important pharmaceuticals, pesticides, and functional materials. In this work, we report the first example of chemoselective oxidation of benzylamine to producing benzonitriles, benzaldehydes, and imines, respectively, through the regulation of reaction solvent and additive under 400 nm light irradiation using Rose Bengal as a photocatalyst. The organic compounds are successfully used as photocatalysts for the first time in the oxidative cyanation of benzylamine in photocatalytic systems. Control experiments, mechanism studies, and density functional theory calculations revealed that the reaction undergoes a photolytical single‐electron transfer process, and the cleavage of the benzylic CH bond is the rate‐determining step in the reaction. Noted that the active species of Rose Bengal‐acetamidine hydrochloride was found and structurally verified by X‐ray single‐crystal diffraction analysis.

在重要的药物、农药和功能材料的合成中，精确控制化学选择性是一个具有挑战性的目标。在本研究中，我们首次报道了以玫瑰为光催化剂，在400 nm光照射下，通过调节反应溶剂和添加剂，苯胺化学选择性氧化分别生成苯并腈、苯甲醛和亚胺。本文首次成功地将有机化合物作为光催化剂应用于光催化体系中苯胺氧化氰化反应。控制实验、机理研究和密度泛函理论计算表明，该反应经历了一个光解单电子转移过程，而苯基C - H键的裂解是反应速率的决定步骤。通过X射线单晶衍射分析，发现了活性物质——盐酸玫瑰乙脒，并进行了结构验证。

引用次数: 0

Photocatalytic Silacyclization of 1,7‐Enynes via Selective Functionalization of Si‐H/Silyl C(sp3)‐H Bonds: Access to Densely Functionalized Silacycles 通过Si - H/Silyl C(sp 3) - H键的选择性功能化光催化1,7 -炔的硅环化：获得密集功能化的硅环

IF 4 2区化学 Q2 CHEMISTRY, APPLIED

Advanced Synthesis & Catalysis

Pub Date : 2026-02-17 Epub Date: 2026-02-27 DOI: 10.1002/adsc.70285

Ravikumar Ladumor , Sermadurai Selvakumar

We report a highly efficient protocol for the synthesis of silacycles through oxidative annulation cascade with 1,7‐enynes via selective functionalization of Si‐H/silyl C(sp³)‐H bonds of hydrosilanes. Simple N‐aminopyridinium salt acts as hydrogen atom transfer reagents for the in situ generation of sulfamidyl radical under photoredox catalytic condition. Notably, this protocol demonstrates broad substrate scope with shorter reaction time and viable to the late‐stage functionalization of natural products and pharmaceuticals.

我们报道了一种高效的方案，通过氢硅烷的Si - H/硅基C(sp 3) - H键的选择性功能化，通过1,7 -炔的氧化环级联合成硅环。简单N -氨基吡啶盐作为氢原子转移试剂，在光氧化还原催化条件下原位生成磺胺基自由基。值得注意的是，该方法具有较短的反应时间和较宽的底物范围，可用于天然产物和药物的后期功能化。

引用次数: 0

Front Cover: Visible-Light-Driven Organocatalyzed Chemoselective Oxidation of Benzylamines (Adv. Synth. Catal. 4/2026) 封面：可见光驱动的有机催化化学选择性氧化的苯胺（Adv. Synth）。Catal。4/2026)

IF 4 2区化学 Q2 CHEMISTRY, APPLIED

Advanced Synthesis & Catalysis

Pub Date : 2026-02-17 DOI: 10.1002/adsc.70369

Chunbo Bo, Mengyao Niu, Fei Chen, Zhi-Hong Du, Min Li, Jichang Liu, Donghui Wei, Ning Liu

Organocatalyzed Chemoselective Oxidation

The cover uses the archery process as a metaphor, depicting the scene of the shooter selectively shooting arrows towards three different targets, symbolizing the selectivity of the chemical process. The bow is composed of the catalyst, providing the driving force; Arrows represent reaction materials, while different targets correspond to different products. Under the combined action of light and catalyst, by adjusting the reaction conditions (such as oxidant, reaction solvent), three different types of products can be generated respectively. More information can be found in the Research Article by Jichang Liu, Donghui Wei, Ning Liu, and co-workers (10.1002/adsc.70303).

封面使用射箭过程作为隐喻，描绘了射手有选择地向三个不同的目标射出箭的场景，象征着化学过程的选择性。弓由催化剂组成，提供动力；箭头表示反应物质，不同的靶对应不同的产物。在光和催化剂的共同作用下，通过调整反应条件（如氧化剂、反应溶剂），可分别生成三种不同类型的产物。更多信息可参见刘继昌、魏东辉、刘宁等人的研究论文（10.1002/adsc.70303）。

引用次数: 0

Engineering Cumene Dioxygenase for Regioselective Hydroxylation of Monoterpenes and Monoterpenoids 单萜烯和单萜类化合物区域选择性羟基化的工程异丙烯双加氧酶

IF 4 2区化学 Q2 CHEMISTRY, APPLIED

Advanced Synthesis & Catalysis

Pub Date : 2026-02-17 Epub Date: 2026-02-27 DOI: 10.1002/adsc.70323

Jona T. Schelle , Julian L. Wissner , Isabell Muth , Carla Calvó‐Tusell , Jonathan Berger , Marc Garcia‐Borràs , Gloria Saab‐Rincón , Bernhard Hauer

Terpenes represent the most abundant class of natural products, with monoterpenes and their hydroxylated derivatives being highly sought after in the flavor and fragrance as well as pharmaceutical industry. However, the selective oxyfunctionalization of these compounds remains challenging. Cumene dioxygenase (CDO) from Pseudomonas fluorescens IP01 has emerged as a promising biocatalyst for monoterpene hydroxylation, though achieving precise regioselectivity control has proven nontrivial. Here, we report the successful engineering of CDO to achieve exceptional regioselective control over this challenging substrate class. The identification of L333A as an important generalist variant proved fundamental, not only enhancing product formation but also opening the way for the conversion of novel monoterpene substrates. Through iterative site‐saturation mutagenesis, we developed enhanced variants which achieved up to 90% selectivity for (R)‐ and (S)‐limonene‐10‐ol as well as up to 67% for (R)‐ and (S)‐perillyl alcohol while exhibiting additionally improved total product formation. Furthermore, engineered variants significantly broadened the substrate scope of CDO, enabling hydroxylation of all four pinene isomers as well as the monoterpenoids geraniol and (−)‐linalool with selectivities of up to 99%. In summary, this work demonstrates the remarkable potential of tailored Rieske oxygenases for the sustainable production of valuable hydroxylated monoterpenes.

萜烯是最丰富的一类天然产物，单萜烯及其羟基化衍生物在香料和香料以及制药工业中受到高度追捧。然而，这些化合物的选择性氧化官能化仍然具有挑战性。来自荧光假单胞菌IP01的异丙烯双加氧酶（CDO）已成为一种很有前途的单萜羟基化生物催化剂，尽管实现精确的区域选择性控制已被证明是不容易的。在这里，我们报告了CDO的成功工程，以实现对这种具有挑战性的基板类的特殊区域选择性控制。L333A作为一个重要的多面手变异的鉴定被证明是根本性的，不仅促进了产物的形成，而且为新的单萜烯底物的转化开辟了道路。通过反复的位点饱和诱变，我们开发了增强的变体，对(R)‐和(S)‐柠檬烯‐10‐醇的选择性高达90%，对(R)‐和(S)‐紫苏醇的选择性高达67%，同时表现出额外改善的总产物形成。此外，工程变体显著拓宽了CDO的底物范围，使所有四种蒎烯异构体以及单萜类香叶醇和(−)-芳樟醇的羟基化选择性高达99%。总之，这项工作证明了定制Rieske加氧酶在可持续生产有价值的羟基化单萜烯方面的显着潜力。

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引用次数: 0

Harnessing Carbenoid Reactivity From Imidazoles and Oxiranes 利用咪唑和氧烷类化合物的类碳反应性

IF 4 2区化学 Q2 CHEMISTRY, APPLIED

Advanced Synthesis & Catalysis

Pub Date : 2026-02-17 Epub Date: 2025-12-14 DOI: 10.1002/adsc.70218

Matthias R. Steiner , Johanna M. Uher , Jürgen Lindner , Cordula M. Zeiler , Christian Slugovc

The combination of azole compounds, such as 1‐methylimidazole and oxiranes (e.g., phenyl glycidyl ether) gives carbenoid reactivity at elevated temperatures. Benzoin condensation was performed with 5 mol% azole and 10 mol% oxirane under air at temperatures of 70°C and above, achieving conversions of up to 85% of benzaldehyde and yields of up to 64% of benzoin. The lower benzoin yield is due to the formation of oxidative benzoin follow‐up products under these reaction conditions. A variety of combinations of azole compounds and oxiranes have been shown to catalyze benzoin condensation. Thus, a modular, potentially inexpensive method of generating carbenoid reactivity has been revealed. The proposed mechanism for catalyst formation involves oxirane opening by, for example, 1‐methylimidazole, which forms a zwitterionic methylimidazolium adduct with the oxirane. Then, the acidic proton in the 2‐position of the imidazolium core is deprotonated by the zwitterion's alkoxide releasing the corresponding N‐heterocyclic carbene (NHC). In addition to its primary function, surplus oxirane serves as a scavenger, removing acidic byproducts that are formed from the aldehyde through oxidative NHC catalysis. This property enables benzoin condensation without the exclusion of oxygen. The practical utility of this catalytic system was demonstrated by polymerizing simple bifunctional aldehyde/oxirane monomers—namely, 4‐(2‐oxiranylmethoxy)‐benzaldehyde, 3‐(2‐oxiranylmethoxy)‐benzaldehyde, and vanillin‐based 2‐methoxy‐4‐(2‐oxiranylmethoxy)‐benzaldehyde—using 5 mol% 1‐methylimidazole in a solventless manner and without excluding air. The monomers polymerized via both the formyl and the oxirane groups, yielded thermosets with glass transition temperatures above 100°C.

唑类化合物，如1‐甲基咪唑和氧烷（如苯基甘油醚）的组合在高温下产生类碳化合物的反应性。在70℃及以上的空气条件下，用5 mol%的唑和10 mol%的氧环烷进行苯甲酰缩合，苯甲醛的转化率高达85%，苯甲酰的收率高达64%。较低的安息香产率是由于在这些反应条件下形成了氧化安息香的后续产物。各种各样的唑类化合物和氧环烷的组合已被证明可以催化苯并安息香缩合。因此，揭示了一种模块化的、潜在廉价的产生类碳化合物反应性的方法。所提出的催化剂形成机制涉及氧环烷的打开，例如，1‐甲基咪唑，它与氧环烷形成两性离子甲基咪唑加合物。然后，咪唑核心2位的酸性质子被两性离子的烷氧化物去质子化，释放出相应的N -杂环碳（NHC）。除了它的主要功能外，剩余的氧环烷还可以作为一种清除剂，通过氧化NHC催化去除醛形成的酸性副产物。这一特性使安息香得以在不排除氧气的情况下进行缩合。该催化体系的实用性通过使用5mol % 1 -甲基咪唑在无溶剂和不排除空气的情况下聚合简单双功能醛/氧环烷单体，即4 -（2 -氧基甲氧基）-苯甲醛、3 -（2 -氧基甲氧基）-苯甲醛和香兰素基2 -甲氧基- 4 -（2 -氧基甲氧基）-苯甲醛得到了证明。通过甲酰基和氧环基聚合的单体，产生了玻璃化转变温度高于100℃的热固性聚合物。

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