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Recent advances in electrocatalytic multicomponent reactions for synthesizing organic chalcogenide compounds 电催化合成有机硫族化合物的多组分反应研究进展
IF 5.4 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2026-10-20 DOI: 10.1039/d6qo01329e
Miao-Ying Wang,Fei-Hu Cui,Hai-Tao Tang,Ying-Ming Pan
Chalcogen-containing compounds serve as essential scaffolds in drugs and natural products. Electrocatalytic multicomponent reactions offer a sustainable strategy for constructing organosulfur, organoselenium, and organotellurium compounds. By leveraging electrons as clean reactants, this method eliminates the need for additional chemical oxidants, reducing waste generation and environmental footprint. Precise regulation of reaction potential and current density enables adjustable reaction pathways, which improves reaction selectivity, efficiency and product purity. This review focuses on electrocatalytic multicomponent reactions for the synthesis of organic chalcogenide compounds, with emphasis on reaction design, process optimization, substrate scope and the mechanism of selectivity. It also discusses catalyst development and stability for sulfur, selenium and tellurium-based reaction systems. Current challenges, including limited substrate compatibility, catalyst deactivation and large-scale synthesis difficulties, are also analyzed. Future research directions include developing more efficient electrocatalysts, expanding applications in pharmaceutical synthesis, and integrating the method with renewable energy sources. The insights presented in this review are intended to guide the green and efficient synthesis of valuable organochalcogen compounds, and contribute to the development of sustainable organic chemistry.
含硫化合物是药物和天然产物中必不可少的支架。电催化多组分反应为构建有机硫、有机硒和有机碲化合物提供了一种可持续的策略。通过利用电子作为清洁的反应物,这种方法消除了对额外化学氧化剂的需求,减少了废物的产生和环境足迹。精确调节反应电位和电流密度,使反应途径可调,提高反应选择性,效率和产品纯度。综述了电催化多组分反应合成有机硫族化合物的研究进展,重点介绍了电催化多组分反应的设计、工艺优化、底物范围和选择性机理。还讨论了硫基、硒基和碲基反应体系催化剂的研制及其稳定性。目前的挑战,包括有限的底物相容性,催化剂失活和大规模合成困难,也进行了分析。未来的研究方向包括开发更高效的电催化剂,扩大在药物合成中的应用,以及将该方法与可再生能源相结合。本文的研究成果旨在指导有价值的有机化合物的绿色高效合成,为可持续有机化学的发展做出贡献。
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引用次数: 0
Correction: Nitrogen migration for amino acid synthesis: enzymes take control 修正:氨基酸合成的氮迁移:酶起控制作用
IF 5.4 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2026-10-19 DOI: 10.1039/d6qo90077a
Lilu Zhang,Eric Meggers
Correction for ‘Nitrogen migration for amino acid synthesis: enzymes take control’ by Lilu Zhang et al., Org. Chem. Front., 2026, https://doi.org/10.1039/d6qo01348a.
对“氨基酸合成中的氮迁移:酶控制”的修正(张莉莉等人)。化学。前面。, 2026, https://doi.org/10.1039/d6qo01348a。
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引用次数: 0
Theoretical Insights into Lewis Acid-Promoted C-C Bond Cleavage in Ni-Catalyzed Cyclobutanone Activation via Sequential Insertion/β-Carbon Elimination 通过顺序插入/β-碳消除,Lewis酸促进的C-C键切割在ni催化环丁酮活化中的理论见解
IF 5.4 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2026-10-19 DOI: 10.1039/d6qo01279e
Li-Li Liao,Hui-Lin Luo,Yu-Fu Gao,Li-Cai Liu,Chuan-Kun Ran,Chuan-Xi Nie,Yi-Fei Chen,Zhen Zhang,Xiangge Zhou,Da-Gang Yu
Direct oxidative addition and β-carbon elimination are the two fundamental pathways for the transition metal (TM)-catalyzed carbon-carbon (C–C) bond activation. Despite significant progress, how cyclobutanone frameworks switch between the distinct C–C bond activation modes remains insufficiently understood. Herein, density functional theory (DFT) calculations were performed to elucidate the mechanistic role of Lewis acid in modulating activation pathways and promoting C–C bond cleavage during the Ni-catalyzed ring-opening/reductive carboxylation of ortho-bromo-3-phenylcyclobutanones with CO2. This reaction initiates via C–Br bond oxidative addition to Ni(0) center followed by reduction to give the aryl-Ni(I) species. For the subsequent C–C bond activation, coordination of a Lewis acid to the carbonyl oxygen of cyclobutanone shifts the mechanistic preference from conventional C–C bond oxidative addition to a sequential migratory insertion/β-carbon elimination pathway. Frontier molecular orbital (FMO) analysis and global reactivity index (GRI) analysis indicate that Lewis acid coordination significantly lowers the LUMO energy of the carbonyl (C=O) moiety, markedly enhancing its electrophilicity. Further geometry analysis, interaction region indicator (IRI) analysis, and energy decomposition analysis (EDA) reveal that the Lewis acid stabilizes the key insertion transition state through favorable non-covalent interactions specifically involving C–H•••Cl and lone pair•••π interactions, dominated primarily by electrostatic and orbital interactions. Subsequent Lewis acid-promoted CO2 insertion and reduction take place, affording final carboxylated product and regenerating Ni(0) complex. These findings not only elucidate the pivotal role of Lewis acid in cyclobutanone activation but also offer valuable guidelines for designing Lewis-acid-assisted C–C bond cleavage and cross-coupling reactions.
直接氧化加成和β-碳消除是过渡金属(TM)催化碳-碳(C-C)键活化的两种基本途径。尽管取得了重大进展,但环丁酮框架如何在不同的C-C键激活模式之间切换仍然没有得到充分的了解。本文通过密度泛函理论(DFT)计算,阐明了Lewis酸在镍催化邻溴-3-苯基环丁酮与CO2开环/还原羧化反应中调节活化途径和促进C-C键裂解的机理。该反应通过C-Br键氧化加成Ni(0)中心,然后还原生成芳基Ni(I)。对于随后的C-C键激活,Lewis酸与环丁酮羰基氧的配位将机制偏好从传统的C-C键氧化加成转变为顺序的迁移插入/β-碳消除途径。前沿分子轨道(FMO)分析和全局反应性指数(GRI)分析表明,Lewis酸配位显著降低羰基(C=O)部分的LUMO能量,显著增强其亲电性。进一步的几何分析、相互作用区域指示(IRI)分析和能量分解分析(EDA)表明,Lewis酸通过有利的非共价相互作用来稳定键插入过渡态,特别是C-H••••Cl和孤对•••π相互作用,主要是静电和轨道相互作用。随后发生Lewis酸促进的CO2插入和还原,产生最终的羧化产物并再生Ni(0)配合物。这些发现不仅阐明了Lewis酸在环丁酮活化中的关键作用,而且为设计Lewis酸辅助的C-C键裂解和交叉偶联反应提供了有价值的指导。
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引用次数: 0
Diastereodivergent azetidine synthesis anion-relay-chemistry-enabled [2 + 2] cycloaddition of alkynes with -aryl imines 非对映发散氮杂啶的合成阴离子接力化学使[2 + 2]炔与-芳基亚胺的环加成
IF 5.4 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2026-10-19 DOI: 10.1039/d6qo01012a
Xiaomeng Gong,Yingying Xue,Zhuzhu Zhang,Guohong Tang,Xiangrong Xu,Liang Li,Ruipeng Li,Shouchu Tang
Azetidines are privileged structural motifs in medicinal chemistry, yet diastereodivergent synthesis of highly substituted variants from simple precursors remains elusive. Herein, we report an anion-relay-chemistry (ARC)-enabled [2 + 2] cycloaddition of alkynyl 1,3-dithianes with N-aryl imines. Crucially, the 1,3-dithiane unit serves as an anion-stabilizing structural element that enables the carbanionic relay process while remaining a synthetically versatile sulfur-containing handle. This strategy bypasses the limitations of conventional photocycloadditions and enables access to a previously inaccessible reactivity mode. Notably, base loading precisely controls diastereochemical outcomes, allowing programmable synthesis of either cis- or trans-azetidines from identical substrates. The protocol proceeds under mild conditions, exhibits a broad substrate scope, and delivers densely functionalized products in good yields with excellent selectivity. The resulting azetidines serve as versatile intermediates for rapid access to β-lactams and β-aminoketones. This work establishes a general platform for stereodivergent azetidine synthesis.
氮杂基在药物化学中是一种特殊的结构基序,但从简单前体合成高度取代的非对映发散变体仍然难以捉摸。在此,我们报道了阴离子接力化学(ARC)使[2 + 2]炔基1,3-二硫烷与n-芳基亚胺的环加成。至关重要的是,1,3-二硫烷单元作为阴离子稳定结构元件,使碳离子接力过程成为可能,同时保持合成通用的含硫手柄。这种策略绕过了传统的光循环添加的限制,并能够获得以前无法获得的反应性模式。值得注意的是,碱负载精确地控制非对映化学结果,允许从相同的底物可编程合成顺式或反式氮杂啶。该工艺在温和的条件下进行,表现出广泛的底物范围,并以良好的收率和优异的选择性提供密集功能化的产物。由此产生的氮杂啶作为快速进入β-内酰胺和β-氨基酮的多功能中间体。本研究为立体发散氮杂啶合成奠定了基础。
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引用次数: 0
Electrosynthesis of 1H-and 2H-Indazoles by Reduction of o-Nitrobenzylamines, a Versatile and Sustainable Access 邻硝基苄胺还原电合成1h -和2h -吲哚,一种通用和可持续的方法
IF 5.4 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2026-10-19 DOI: 10.1039/d6qo01360k
Eric F. R. Pertermann,Daniel Doellerer,Claudia M Kammler,Thomas Weyhermueller,Sebastian Beil,Bernd Werner,Siegfried R. Waldvogel
Indazoles represent an important pharmacologically active class of compounds. However, reliable and sustainable pathways from simple substrates remain scarce. We report an easily applicable and sustainable electrochemical synthesis of various 1H-and 2H-indazoles via direct reduction of o-nitrobenzylamines, avoiding stoichiometric reagents and elevated temperatures. The protocol enables access to 50 distinct structures with isolated yields up to 96% and a broad tolerance for functional groups and heterocycles. Additionally, we demonstrate electrochemical post-functionalization, access to APIs and their precursors, as well as robust scalability.
茚唑是一类重要的具有药理活性的化合物。然而,从简单基质中获得可靠和可持续的途径仍然很少。我们报道了一种易于应用和可持续的电化学合成各种1h和2h -吲哚,通过直接还原邻硝基苄胺,避免化学计量试剂和高温。该方案可以获得50种不同的结构,分离收率高达96%,对官能团和杂环具有广泛的耐受性。此外,我们还展示了电化学后功能化、api及其前体的访问以及强大的可扩展性。
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引用次数: 0
Palladium-Catalyzed Multi-Fold Domino Cyclization for Access to N-Doped PAHs; Recyclable [Pd]-System, Light Emitting Applications 钯催化多重多米诺环化制备n掺杂多环芳烃可回收[Pd]-系统,发光应用
IF 5.4 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2026-10-16 DOI: 10.1039/d6qo01172a
Jakkula Naveen,Satyanarayana Gedu
Herein, we report an efficient, sustainable, and green domino strategy for the divergent synthesis of N-doped indeno[1,2-c]pyrrolo[3,2,1-ij]quinoline derivatives, first of their kind from 2,6-bis(arylethynyl)anilines under PEG-400/palladium-recyclable conditions via four to five new chemical bonds in a single process. The Pd-catalyst/PEG-400 was recycled and reused for up to four consecutive cycles. The protocol demonstrates excellent functional-group tolerance and a broad substrate scope, while its synthetic utility is highlighted by successful scale-up reactions and the incorporation of drug-derived substrates. Importantly, the resulting compounds display strong orange-red fluorescence, as evidenced by UV-visible absorption, fluorescence, lifetime, and quantum yield analyses. Notably, LED-coating experiments revealed that blue LEDs coated with these compounds emit orange-red light, underscoring their promising potential as orange-red light-emitting materials.
在此,我们报道了一种高效、可持续和绿色的多米诺骨牌策略,用于在PEG-400/钯可回收条件下,首次从2,6-二(芳乙基)苯胺中合成n掺杂的茚[1,2-c]吡咯[3,2,1-ij]喹啉衍生物,通过单一过程中的4到5个新化学键。Pd-catalyst/PEG-400可连续循环使用4次。该方案显示出优异的官能团耐受性和广泛的底物范围,而其合成效用通过成功的放大反应和药物衍生底物的结合而突出。重要的是,所得化合物显示出强烈的橘红色荧光,正如紫外可见吸收,荧光,寿命和量子产率分析所证明的那样。值得注意的是,led涂层实验显示,涂有这些化合物的蓝色led发出橙红色光,强调了它们作为橙红色发光材料的潜力。
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引用次数: 0
Synthesis of Polyhydroxyalkyl Oxazoles from Unprotected Aldoses and Tetramethylguanidine 无保护醛糖和四甲基胍合成多羟基烷基恶唑
IF 5.4 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2026-10-16 DOI: 10.1039/d6qo01251e
Mian Liu,Lianyou Zheng,Junxiang Bai,Qiansong Gao,Zhuoqi Zhang,Lingling Shi,Jinbao Xiang
A facile one-pot approach has been developed for the synthesis of polyhydroxyalkyl oxazoles directly from unprotected aldoses and tetramethylguanidine (TMG), using n-Bu₄NOAc as the additive under mild heating. The protecting-group-free process features operational simplicity and broad substrate scope. This method provides direct access to valuable polyhydroxyalkyl oxazoles and offers a practical strategy for the direct derivatization of carbohydrate feedstocks.
以n-Bu₄NOAc为添加剂,在温和加热条件下,以无保护醛糖和四甲基胍(TMG)为原料,采用一锅法直接合成了聚羟基烷基恶唑。无保护组工艺具有操作简单、基材适用范围广的特点。这种方法提供了直接获得有价值的聚羟基烷基恶唑,并为碳水化合物原料的直接衍生化提供了一种实用的策略。
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引用次数: 0
Mechanistic Origin of TBAI-Controlled Regioselectivity Reversal in the Palladium-Catalyzed Hydrocarboxylation of Terminal Aryl Alkynes with Oxalic Acid 钯催化末端芳基炔与草酸羟基化反应中tbai控制区域选择性逆转的机理
IF 5.4 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2026-10-16 DOI: 10.1039/d6qo01302c
Yishi Li,Jianqi Chen,Xuyu Qin,Juan Li
Regiodivergent hydrocarboxylation of terminal alkynes provides efficient access to branched and linear α,β-unsaturated carboxylic acids, yet the mechanistic origin of additive-controlled regioselectivity remains unclear. Here, density functional theory calculations reveal how tetrabutylammonium iodide (TBAI) reverses the regioselectivity of Pd/Xantphos-catalyzed hydrocarboxylation of terminal aryl alkynes with oxalic acid. In the absence of TBAI, oxalic acid directly protonates the terminal carbon of the Pd-bound alkyne in concert with Pd–C bond formation, whereas pathways involving water as the immediate proton donor or a discrete Pd–H intermediate are disfavored. This distortion-controlled proton-transfer/palladation pathway selectively generates the branched alkenylpalladium intermediate. In the presence of TBAI, iodide coordination alters the catalyst speciation and enables formation of an iodide-ligated Pd–H species followed by regioselective hydropalladation, thereby producing the linear alkenylpalladium intermediate. In both cases, subsequent carbonylation proceeds preferentially through direct migratory CO insertion, followed by hydrogen oxalate-assisted hydrolysis. The calculated hydrolysis barriers qualitatively reproduce the experimental substrate- and ligand-dependent yield trends. Distortion–interaction and noncovalent-interaction analyses further associate the substrate effects primarily with structural distortion and the superior performance of Xantphos with its rigid, preorganized coordination environment. These findings establish iodide-induced catalyst speciation and pathway switching as the origin of the regioselectivity reversal and provide mechanistic guidance for controlling Pd-catalyzed regiodivergent hydrocarboxylation.
末端炔的区域发散性羟基化提供了分支和线性α,β-不饱和羧酸的有效途径,但加性控制区域选择性的机制起源尚不清楚。这里,密度泛函理论计算揭示了四丁基碘化铵(TBAI)如何逆转Pd/ xantphos催化末端芳基炔与草酸羟基化的区域选择性。在缺乏TBAI的情况下,草酸直接使pd结合的炔的末端碳与Pd-C键形成相一致,而涉及水作为直接质子供体或离散Pd-H中间体的途径则不受欢迎。这种扭曲控制的质子转移/钯化途径选择性地产生支链烯基钯中间体。在TBAI存在的情况下,碘化物配位改变了催化剂的形态,使碘化连接的Pd-H形成,随后发生区域选择性水钯化,从而产生线性烯基钯中间体。在这两种情况下,随后的羰基化优先通过直接迁移CO插入进行,然后是草酸氢辅助水解。计算的水解障碍定性地再现了实验底物和配体依赖的产率趋势。扭曲相互作用和非共价相互作用分析进一步将底物效应主要与结构扭曲联系起来,而Xantphos的优越性能与其刚性、预组织的配位环境联系起来。这些发现确立了碘化物诱导的催化剂形态形成和途径转换是区域选择性逆转的起源,并为控制pd催化的区域发散性羟基化提供了机制指导。
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引用次数: 0
Expression of concern: Dithiocarbamate mediated thioamidation C–C single bond cleavage of styrene: study of the protocol in decarbonylative and decarboxylative thioamidations 关注表达:二硫代氨基甲酸酯介导的硫胺化:苯乙烯的C-C单键裂解:脱羰和脱羧硫胺化的协议研究
IF 5.4 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2026-10-15 DOI: 10.1039/d6qo90072k
Debabrata Patra,Amit Saha
Expression of concern for ‘Dithiocarbamate mediated thioamidation via C–C single bond cleavage of styrene: study of the protocol in decarbonylative and decarboxylative thioamidations’ by Debabrata Patra et al., Org. Chem. Front., 2024, 11, 1150–1156, https://doi.org/10.1039/D3QO01921G.
Debabrata Patra等人对“通过苯乙烯的C-C单键裂解介导的二硫代氨基甲酸盐硫胺化:脱羧和脱羧硫胺化协议的研究”的关注表达。化学。前面。, 2024, 11, 1150-1156, https://doi.org/10.1039/D3QO01921G。
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引用次数: 0
Construction of Supramolecular Polymers and Structural Transformation Based on Multiple Noncovalent Interactions 基于多重非共价相互作用的超分子聚合物的构建与结构转化
IF 5.4 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2026-10-14 DOI: 10.1039/d6qo01188h
Linlin Liu,Yan Zhang,Yuzhen Wang,Tiantian Miao,Zhihao Xu,Hui Li
In this work, we report the construction and structural transformation of new supramolecular polymers. Four monomers, M1, M2, M3 and M4, were designed and synthesized. M1, M3, M4 and Zn(OTf)2 can self-assemble into supramolecular linear polymers (SLP) through pillararene-based host–guest interaction and terpyridine-based complementary metal coordination. Upon addition of monomer M2 to the SLP solution, the SLP further transformed into supramolecular cross-linked polymers (SCP) via crown ether-based host–guest interaction. Furthermore, the obtained SCP formed a supramolecular polymer gel at high concentrations, and the reversible gel–sol transformation could be realized in response to multiple stimuli. This research provides inspiration for the design and preparation of supramolecular polymers with different topological structures.
在这项工作中,我们报道了新的超分子聚合物的构建和结构转变。设计合成了M1、M2、M3、M4四个单体。M1、M3、M4和Zn(OTf)2可以通过柱芳烃为主的主客体相互作用和三吡啶为主的互补金属配位自组装成超分子线性聚合物(SLP)。在SLP溶液中加入单体M2后,SLP通过冠醚主客体相互作用进一步转化为超分子交联聚合物(SCP)。所得SCP在高浓度下可形成超分子聚合物凝胶,在多种刺激下可实现可逆的凝胶-溶胶转化。该研究为设计和制备具有不同拓扑结构的超分子聚合物提供了灵感。
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引用次数: 0
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Organic Chemistry Frontiers
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