Organic chemistry frontiers : an international journal of organic chemistry最新文献

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Mechanistic and machine learning insights into borrowing hydrogen reactions catalyzed by transition metal complexes with N-heterocyclic ligands 过渡金属配合物与n -杂环配体催化的借氢反应的机制和机器学习见解

Organic chemistry frontiers : an international journal of organic chemistry

Pub Date : 2025-10-13 DOI: 10.1039/d5qo01139f

Hui-Qi Mo , Cheng Hou

Pyrazole-based transition metal complexes have attracted increasing attention in borrowing hydrogen (BH) reactions, particularly when employing the metal–ligand cooperation (MLC) strategy to achieve high activity and selectivity. However, a systematic understanding of their mechanistic selectivity and the factors governing catalytic performance remains lacking. Herein, the BH reaction of alcohols catalyzed by such complexes was investigated using density functional theory (DFT) calculations in combination with machine learning (ML) methods. Three possible pathways—N2-site-assisted, O-site-assisted, and N1-site-assisted—were proposed, among which the N2-site-assisted route was identified as the most favorable. Both the dehydrogenation and hydrogenation steps proceed via an outer-sphere concerted transfer mechanism. Distortion/interaction analysis revealed that the ligand-assisted distortion energy plays a decisive role in determining the activation barrier. Furthermore, an ML model with high predictive accuracy (R² = 0.9570) was established to correlate catalytic performance with electronic and steric descriptors. Feature importance analysis identified the HOMO energy level, dipole moment, and molecular volume as key factors, reflecting the roles of electron-donating ability, transition-state polarization, and steric effects, respectively. This study not only deepens the mechanistic understanding of MLC-enabled BH reactions catalyzed by pyrazole-based transition metal complexes but also provides a predictive framework for the rational design of efficient and tunable catalysts.

吡唑基过渡金属配合物在借氢反应（BH）中引起了越来越多的关注，特别是在采用金属配体配合（MLC）策略以获得高活性和选择性时。然而，对它们的机械选择性和控制催化性能的因素仍然缺乏系统的了解。本文采用密度泛函理论（DFT）和机器学习（ML）相结合的方法研究了此类配合物催化的醇的BH反应。提出了三种可能的途径- N₂位点辅助，o位点辅助和N₁位点辅助，其中N₂位点辅助途径是最有利的。脱氢和加氢步骤都是通过外球协调转移机制进行的。畸变/相互作用分析表明，配体辅助畸变能对激活势垒的确定起决定性作用。此外，建立了一个预测精度高（R²= 0.96）的ML模型，将催化性能与电子和空间描述符联系起来。特征重要性分析发现HOMO能级、偶极矩和分子体积是关键因素，分别反映了给电子能力、过渡态极化和空间效应的作用。该研究不仅加深了对基于吡唑的过渡金属配合物催化mlc的BH反应机理的理解，而且为合理设计高效可调催化剂提供了预测框架。

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引用次数: 0

Regioselective formation of naphtho[2,1-b]selenophenes via cascade cyclization of 1,3-diynylpropargyl alcohols promoted by iron(iii) chloride and diorganyl diselenides 氯化铁（III）和二有机二烯醚促进1,3-二炔丙基醇级联环化形成萘[2,1-b]硒烯的区域选择性

Organic chemistry frontiers : an international journal of organic chemistry

Pub Date : 2025-10-13 DOI: 10.1039/d5qo01195g

Pedro Pauletto , Davi F. Back , Cristina Wayne Nogueira , Gilson Zeni

This manuscript reports a selective diorganyl diselenide/iron(iii)-promoted strategy for the synthesis of selenium-containing heterocycles, specifically naphtho[2,1-b]selenophene derivatives, via cascade cyclization reactions. Using 1,3-diynylpropargyl alcohols as key substrates and diorganyl diselenides as selenium sources, the optimized conditions involve iron(iii) chloride and dibutyl diselenide in dichloromethane under an inert atmosphere at room temperature, followed by the addition of the substrate and stirring for 12 hours. A series of 25 novel derivatives was synthesized in good yields, demonstrating the scope and versatility of the protocol, which was also extended to include diorganyl disulfides. However, the optimized conditions did not work for diorganyl ditellurides, even when some reaction parameters were changed. The reaction mechanism insights are discussed, and the synthetic utility of the resulting heterocycles as intermediates in further transformations is showcased. This cascade process enables the formation of four new bonds (carbon–carbon, carbon–selenium, selenium–carbon, and carbon–selenium) in a single reaction step.

本文报道了一种选择性二有机基二硒化物/铁（III）促进策略，通过级联环化反应合成含硒杂环，特别是萘[2,1-b]硒烯衍生物。以1,3二炔丙基醇为主要底物，二有机基二硒化物为硒源，在室温惰性气氛下，二氯甲烷中加入氯化铁（III）和二丁基二硒化物，加入底物，搅拌12小时。一系列的25个新的衍生物以良好的产量合成，证明了该协议的范围和通用性，也扩展到包括二硫二有机基。然而，即使改变一些反应参数，优化的条件也不适用于二有机二碲化物。讨论了反应机理的见解，并展示了所得到的杂环化合物在进一步转化中的合成用途。这种级联过程可以在一个反应步骤中形成四种新键（碳-碳、碳-硒、硒-碳和碳-硒）。

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引用次数: 0

Cu-catalyzed cyanoalkyl-alkynylation of gem-disubstituted alkenes to construct all-carbon quaternary center compounds 铜催化宝石二取代烯烃的氰基烷基烷基化构造全碳季中心

Organic chemistry frontiers : an international journal of organic chemistry

Pub Date : 2025-10-13 DOI: 10.1039/d5qo01138h

Yuhang Luo , Xiangxiang Li , Xinjie Zhao , Baomin Yang , Yubo Wei , Guiping Qin

A copper-catalyzed cyanoalkyl-alkynylation of gem-disubstituted alkenes for the construction of alkynyl all-carbon quaternary centers is reported herein. This protocol enables the efficient synthesis of various cyano compounds with an alkynyl all-carbon quaternary center in good yields and overcomes the challenges posed by large steric hindrance and unstable alkylmetal species by using pyridine as a directing group. Preliminary mechanism studies indicated that a radical pathway might be potentially involved in this reaction.

本文报道了一种铜催化的宝石二取代烯烃的氰基烷基烷基化反应，以构建烷基全碳季中心。该方案通过使用吡啶作为导向基团，以较高的产率高效地合成了具有炔基全碳季中心的各种氰基化合物，克服了空间位阻大和烷基金属不稳定的挑战。初步的机理研究表明，自由基途径可能参与了该反应。

引用次数: 0

Facile N-directed Ru-catalyzed C(3)–H acylation of heterocyclopentadienes with acyl chlorides 易氮定向钌催化的C(3)-H与酰基氯化物的酰化反应

Organic chemistry frontiers : an international journal of organic chemistry

Pub Date : 2025-10-13 DOI: 10.1039/d5qo00965k

Konstantin E. Shepelenko , Irina G. Gnatiuk , Andrey A. Aleksandrov , Mikhayl E. Minyaev , Victor M. Chernyshev , Valentine P. Ananikov

The selective C3–H functionalization of 2-substituted heterocyclopentadienes (furan, thiophene and pyrrole) remains challenging owing to the typically higher reactivity of the C5–H and C4–H bonds. In this study, we report a facile method for the selective C3–H acylation of pharmaceutically and agrochemically relevant heterocyclopentadienes bearing N-donor directing groups at the 2-position. This approach utilizes readily available aliphatic, aromatic and heteroaromatic acyl chlorides under catalysis by a Ru/PPh₃ system generated in situ from commercially available, bench-stable precursors. The method exhibits broad tolerance toward various N-donor directing groups, including those with unprotected NH moieties potentially susceptible to N-acylation. Preliminary mechanistic studies suggest a reaction pathway involving C–H activation, which is rate-limiting and assisted by the carboxylate anion generated via the partial decomposition of the acyl chloride in a basic medium.

2取代杂环戊二烯（呋喃、噻吩和吡咯）的选择性C3-H功能化仍然具有挑战性，因为C5-H和C4-H键通常具有较高的反应活性。在这项研究中，我们报道了一种简便的方法，用于在2位上具有n给体导向基团的与医药和农业化学相关的杂环戊二烯的选择性C3-H基化。该方法利用现成的脂肪族、芳香族和杂芳香酰基氯化物，在Ru/PPh₃体系的催化下，由市售的、稳定的前体原位生成。该方法对各种n供体导向基团具有广泛的耐受性，包括那些未受保护的NH部分可能对n -酰化敏感的基团。初步的机理研究表明，该反应途径涉及限制C-H活化的羧酸阴离子通过部分溶剂溶解产生的酰基氯。

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引用次数: 0

Nickel-catalyzed synthesis of aryl ketones from arylsulfonium salts and nitriles 镍催化芳基磺酸盐和腈合成芳基酮

Organic chemistry frontiers : an international journal of organic chemistry

Pub Date : 2025-10-13 DOI: 10.1039/d5qo01173f

Ping Wu , Guan-Sheng Jiao , Cheng-Pan Zhang

A useful method for the preparation of aryl ketones from arylsulfonium salts and nitriles via nickel catalysis is described. The reaction proceeds smoothly under mild conditions and exhibits obvious advantages, such as high efficiency, good functional group tolerance, excellent chemoselectivity, and the ability to acylate complex drug molecules. This protocol provides a practical synthetic route for synthesizing a wide variety of aryl ketones and enables the selective coupling of arylsulfonium salts while retaining other functionalizable handles. Additionally, the easily available deuterated acetonitrile can be used as the nitrile source, which allows for deuteration with good yields and deuterium content up to 99%, permitting effective deuterium labeling of various complex drug molecules.

介绍了一种由芳基磺酸盐和腈经镍催化制备芳基酮的有效方法。该反应在温和的条件下进行顺利，具有效率高、官能团耐受性好、化学选择性好、能酰基化复合药物分子等明显的优势。该方案为各种芳基酮提供了一条实用的合成路线，并使芳基磺酸盐的选择性偶联保留了其他功能化的处理。此外，容易获得的氘化乙腈可以用作腈源，这使得氘化具有良好的产率和高达99%的氘含量，允许各种复杂药物分子的有效氘标记。

引用次数: 0

Ni-catalyzed reductive cross-couplings of diaryl disulfides with aryl bromides for biaryl synthesis through C–S bond cleavage† 镍催化二芳基二硫化物与芳基溴的还原交叉偶联，通过C-S键裂解合成联芳基

Organic chemistry frontiers : an international journal of organic chemistry

Pub Date : 2025-09-05 DOI: 10.1039/d5qo00546a

Xuan-Qi Zhang , Cai-Yu He , Shuang-Feng Song , Xue-Qiang Chu , Hao Xu , Xiaocong Zhou , Weidong Rao , Zhi-Liang Shen

In previous reports, the cross-couplings of diaryl disulfides with aryl halides in the presence of transition metal catalysts (e.g., Ni and Cu) and metal mediators (e.g., Mg and Zn) usually led to the corresponding aryl sulfides via old S–S bond cleavage and new C–S bond formation. In the present study, we found that the reductive cross-couplings of diaryl disulfides with aryl bromides proceeded via unusual C–S bond cleavage in the presence of a nickel catalyst, magnesium, and lithium chloride in THF at room temperature, leading to a variety of biaryls in modest to good yields. In addition, the reaction could be scaled up with ease. Mechanistic studies showed that the reaction possibly proceeds via the in situ production of an arylmagnesium compound as a reaction intermediate via LiCl-facilitated Mg insertion into aryl bromide. Most importantly, the combinatory use of the Ni(ii) catalyst and Mg mediator is key to the unusual cleavage of the C–S bond in diaryl disulfide to form the corresponding arylnickel(ii) species, which serves as another important intermediate in the present desulfurative cross-coupling reaction.

在以往的报道中，在过渡金属催化剂（如Ni、Cu）和金属介质（如Mg、Zn）的存在下，二芳基二硫化物与芳基卤化物的交叉偶联通常通过旧S-S键断裂和新的C-S键形成而产生相应的芳基硫化物。在本研究中，我们发现，在室温下，在镍催化剂、镁和氯化锂的存在下，二芳基二硫化物与芳基溴化物的还原交叉偶联通过异常的C-S键裂解进行，导致各种双芳基在中等到良好的产量。此外，该反应可以很容易地按比例放大。机理研究表明，该反应可能是通过原位生产芳基镁化合物作为反应中间体，通过licl促进Mg插入芳基溴而进行的。最重要的是，Ni（II）催化剂和Mg介质的组合使用是导致二芳基二硫化物中C-S键异常断裂形成相应的芳基镍（II）物质的关键，而芳基镍（II）物质是本脱硫交叉偶联反应的另一个重要中间体。

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引用次数: 0

Chemodivergent temperature-controlled switchable iron-catalysed annulation of o-vinylaniline with isatin derivatives† 化学发散温控可切换铁催化邻乙烯苯胺与Isatin衍生物的环化

Organic chemistry frontiers : an international journal of organic chemistry

Pub Date : 2025-09-05 DOI: 10.1039/d5qo00626k

Sakshi Singh , Samir Kumar Mondal , Shantanu Pal

Chemodivergent approaches strive to enable achieving regioselective and site-divergent transformations of multiple products from identical, readily accessible starting materials by changing the reaction parameters, but are challenging due to the complexity of precisely controlling the chemodiversity. Herein, we report a novel FeCl₃-catalyzed one-pot strategy involving switching the temperature to enable the selective synthesis of 5-methyl-7-phenyldibenzo[b,h][1,6] naphthy-ridin-6(5H)-one or 3-phenyl-1H-indole from o-vinylaniline and N-substituted isatin. Notably, the reaction exhibits temperature-controlled chemodivergence, selectively yielding either intramolecular or intermolecular products. This approach demonstrates a wide substrate scope, affording structurally diverse scaffolds under mild conditions. Furthermore, it provides an efficient route for synthesizing symmetrical urea derivatives and offers a potential pathway for directly synthesizing tryptanthrin and related bioactive molecules.

化学发散方法能够通过改变相同的、容易获得的起始材料的参数来实现多种产品的区域选择性和位点发散转化，这是理想的，但由于精确控制化学多样性的复杂性，这一方法具有挑战性。本文报道了一种新颖的FeCl₃催化的一锅策略，通过切换温度，使邻乙烯苯胺和n-取代isatin选择性合成5-甲基-7-苯基二苯并[b，h][1,6]萘啶-6(5H)- 1或3-苯基- 1h -吲哚。值得注意的是，该反应表现出温度控制的化学发散，选择性地产生分子内或分子间产物。这种方法展示了广泛的基质，在温和的条件下提供结构多样的支架。为对称脲衍生物的合成提供了有效途径，为直接合成色氨酸及相关生物活性分子提供了潜在途径。

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引用次数: 0

Copper(i)-catalyzed tandem C–N coupling/condensation cyclization for the synthesis of benzothiadiazine 1-oxides† 铜(I)催化串联C−N偶联/缩合环化合成苯并噻嗪1 -氧化物

Organic chemistry frontiers : an international journal of organic chemistry

Pub Date : 2025-09-05 DOI: 10.1039/d5qo00681c

Sihan Zhou , Qingle Zeng

A highly efficient and straightforward strategy for the synthesis of benzothiadiazine 1-oxides has been developed, involving a copper(i)-catalyzed tandem C–N coupling/condensation cyclization of ortho-haloaryl organyl NH-sulfoximines and aromatic/aliphatic amidines. This protocol exhibits several notable advantages, including the absence of a requirement for an additional nitrogen source, a broad substrate scope, mild reaction conditions, and significant potential for application in the industrial production of benzothiadiazine 1-oxides.

提出了一种高效、直接的合成苯并噻二嗪1-氧化物的方法，包括铜(I)催化邻卤芳基有机基nh -亚砜亚胺和芳香/脂肪族脒的串联C-N偶联/缩合环化。该工艺有几个显著的优点，包括不需要额外的氮源，底物范围广，反应条件温和，在苯并噻唑二嗪1-氧化物的工业生产中具有很大的应用潜力。

引用次数: 0

The construction of aromatic rings by photocatalytic radical-induced cyclization reactions 光催化自由基诱导环化反应构建芳环

Organic chemistry frontiers : an international journal of organic chemistry

Pub Date : 2025-09-05 DOI: 10.1039/d5qo00667h

Xi-Ni Luo , Dong-Qing Yang , Hong-Lin Wu , Jia-Yao Feng , Sheng Du , Yu He , Rong-Nan Yi , Jun-Qi Zhang , Keqi Tang , Wen-Ting Wei

Photocatalytic radical-induced cyclization reactions offer an efficient paradigm for constructing aromatic rings due to their unique environmental friendliness, independence from electronic effects, and high functional group tolerance. However, the high reactivity of intermediates in radical reactions, particularly the challenges of controlling it proceeds in an orderly manner according to the expected pathway and the reaction terminates after the ring is formed, which leads to diminished precision in the construction of aromatic rings. Compared to traditional cyclization methods for synthesizing aromatic rings, photocatalysis enables direct cleavage of high-bond-energy chemical bonds under mild conditions, eliminating the need for high temperature, high pressure, or stoichiometric oxidants. Furthermore, photocatalytic systems can serve as a bridge to connect multiple reaction steps, thereby streamlining the process and enhancing efficiency. Recently, significant progress has been made in applying photocatalytic radical-induced cyclization for the construction of aromatic rings. However, to date, there has been no comprehensive summary of this area reported. In this review, we try to provide a comprehensive perspective on the construction of aromatic rings via photocatalytic radical-induced cyclization. The discussion is organized into five sections based on the type of aromatic ring formed: monoheteroatom-doped aromatic rings, diheteroatom-doped aromatic rings, triheteroatom-doped aromatic rings, all-carbon aromatic rings, and non-classical aromatic rings. This review is particularly focused on elucidating reaction mechanisms, the synergistic effect of catalysts and light sources, and the applications of this strategy in pharmaceutical synthesis and materials science.

光催化自由基诱导的环化反应由于其独特的环境友好性、不受电子效应的影响和高官能团耐受性，为构建芳香环提供了一种有效的范例。然而，自由基反应中中间体的高反应活性，特别是控制中间体的挑战，是按照预期的途径有序进行的，在环形成后反应就终止了，这导致了芳香环构建精度的降低。与传统的合成芳环的环化方法相比，光催化可以在温和的条件下直接裂解高键能化学键，不需要高温、高压或化学计量氧化剂。此外，光催化系统可以作为连接多个反应步骤的桥梁，从而简化过程并提高效率。近年来，应用光催化自由基诱导环化技术构建芳香环的研究取得了重大进展。然而，到目前为止，还没有关于这一领域的全面总结报告。本文综述了光催化自由基诱导环化构建芳香族环的研究进展。根据形成的芳香环类型分为五个部分：单杂原子掺杂芳香环、双杂原子掺杂芳香环、三杂原子掺杂芳香环、全碳芳香环和非经典芳香环。本文重点阐述了反应机理、催化剂和光源的协同效应以及该策略在药物合成和材料科学中的应用。

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引用次数: 0

Palladium-catalyzed cascade synthesis of tricyclic quinolin-2(1H)-ones from 1,7-enynes and hydroxylamines† 钯催化1,7-炔和羟胺级联合成三环喹啉-2(1H)-酮

Organic chemistry frontiers : an international journal of organic chemistry

Pub Date : 2025-09-05 DOI: 10.1039/d5qo00697j

Jiajun Zhao , Xiaolong Wang , Yan Cao , Jun Ying

A palladium-catalyzed cascade radical cyclization and C–H amination of 1,7-enynes with perfluoroalkyl iodides and hydroxylamine has been developed for the rapid construction of tricyclic quinolin-2(1H)-one scaffolds. The reaction proceeded smoothly to give a series of tricyclic quinolin-2(1H)-one derivatives in high yields. Notably, the late-stage modifications of various drugs were realized by using this method.

研究了钯催化的1,7-炔与全氟烷基碘化物和羟胺的级联自由基环化和C-H胺化反应，用于快速构建三环喹啉-2(1H)- 1支架。反应进行顺利，得到了一系列高收率的三环喹啉-2(1H)- 1衍生物。值得注意的是，利用这种方法实现了各种药物的后期修饰。

引用次数: 0

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