Organic Chemistry Frontiers最新文献

英文中文

Photoredox Catalyzed Visible Light-Induced Reduction of Nitroarenes into Anilines 光氧化还原催化可见光诱导硝基芳烃还原成苯胺

IF 5.4 1区化学 Q1 CHEMISTRY, ORGANIC

Organic Chemistry Frontiers

Pub Date : 2025-12-24 DOI: 10.1039/d5qo01565k

Weiqiang Sun, Hao Guo, Aishun Ding

A photochemical methodology was developed for the reduction of nitroarenes, utilizing γ-terpinene as the reductant and 9-HTX- as the photocatalyst. This study gave another way to generate 9-HTX- species from TX and γ-terpinene rather than TX and TfOH. Under the catalysis of 9-HTX-*, an in situ formed long-lived and super-reducing species, various nitroarenes were successfully converted into the corresponding anilines via the key amino radical intermediates. This reaction offers a mild and effective approach for synthesizing anilines with broad applicability.

以γ-萜烯为还原剂，9-HTX-为光催化剂，建立了硝基芳烃的光化学还原方法。本研究为TX和γ-萜烯生成9-HTX-提供了一种替代TX和TfOH的方法。在原位形成的长寿命超还原物质9-HTX-*的催化下，各种硝基芳烃通过关键的氨基自由基中间体成功转化为相应的苯胺。该反应为合成苯胺提供了一种温和而有效的方法，具有广泛的适用性。

引用次数: 0

Isoquinoline-Catalyzed Visible-Light-Mediated 1,2-/1,4-Thiosulfonylation Difunctionalization Reaction of Thiosulfates with Alkenes 异喹啉催化可见光介导的硫代硫酸盐与烯烃的1,2-/1,4-硫代磺酰化双官能化反应

IF 5.4 1区化学 Q1 CHEMISTRY, ORGANIC

Organic Chemistry Frontiers

Pub Date : 2025-12-23 DOI: 10.1039/d5qo01570g

Molai Zhao, Yang Fu, Min Peng, Ya-Wen Wang, Chuanhua Qu, He Zhong Jiang, Jiahong Li, Rui Tan

We have developed a novel method for the 1,2-/1,4thiosulfonylation bifunctional reaction of thiosulfates with nonaromatic olefins. This approach eliminates the need for metal catalysts or photocatalysts, offering an environmentally friendly, convenient, and effi-cient process. Under visible light irradiation, inexpensive and readily available isoquinoline serves as an energy transfer catalyst to facilitate the homolytic cleavage of the S-SO₂ bond in thiosulfates, enabling the 1,2-/1,4-thiosulfonylation bifunctionalization of either a single non-aromatic olefin or two different non-aromatic olefins, thereby constructing C-S and C-SO₂ bonds in one step. This method is expected to provide significant impetus for innovative advancements in the fields of organic synthesis methodology and medicinal chemistry.

提出了一种新的硫代硫酸盐与非芳烯烃进行1,2-/1,4硫代磺酰化双官能团反应的方法。这种方法消除了对金属催化剂或光催化剂的需求，提供了一种环保、方便和高效的工艺。在可见光照射下，廉价且易得的异喹啉作为能量转移催化剂，促进硫代硫酸盐中S-SO 2键的均解裂解，使1,2-/1,4-硫代磺酰基双官能化，既可以是单一的非芳烃，也可以是两个不同的非芳烃，从而一步构建C-S和C-SO 2键。该方法有望为有机合成方法和药物化学领域的创新进步提供重大动力。

引用次数: 0

Multi-site thiolation enables rapid and precise synthesis of 2-pyridone thioethers 多位点硫代化使2-吡啶酮硫醚的快速、精确合成成为可能

IF 5.4 1区化学 Q1 CHEMISTRY, ORGANIC

Organic Chemistry Frontiers

Pub Date : 2025-12-23 DOI: 10.1039/d5qo01352f

Xingchi Li, Taoyuan Liang, Guan Huang, Shuangliang Zhao, Zhuan Zhang

The direct and selective functionalization of 2-pyridones remains a fundamental challenge in synthetic chemistry. While conventional strategies targeting the C=C double bond offer some solutions, achieving broad site-selectivity and site-diversity continues to be limited. Reported methods have largely focused on single-position modifications, and site-selective multi-functionalization remains an attractive goal. Herein, we report I₂- and Ru₃(CO)₁₂/I₂-catalyzed strategies enabling multi-site thiolation of 2-pyridones with disulﬁdes. This approach allows for selective C5-thiolation, C3-thiolation, as well as C3,C5- and C3,C6-dithiolation, under tunable and controllable reaction conditions. These transformations proceed with excellent regioselectivity, broad substrate scope, and good functional group tolerance. Furthermore, late-stage modifications and product derivatization demonstrate the synthetic utility and versatility of this protocol. Mechanistic investigations suggest that the mono-thiolation proceeds via a radical pathway involving thiyl radicals, while the di-thiolation likely follows a chelation-assisted ruthenation pathway. Overall, this work provides a robust platform for site-specific and multi-site functionalization of 2-pyridones, paving the way for rapid construction of structurally diverse sulfur-containing heterocycles.

2-吡啶酮的直接和选择性功能化仍然是合成化学中的一个基本挑战。虽然针对C=C双键的传统策略提供了一些解决方案，但实现广泛的位点选择性和位点多样性仍然是有限的。报道的方法主要集中在单位点修饰，而位点选择性多功能化仍然是一个有吸引力的目标。在这里，我们报道了I2-和Ru3(CO)12/I2催化策略，使2-吡啶酮与二硫化物的多位点硫基化。该方法允许在可调节和可控的反应条件下选择性地进行C5-硫基化、C3-硫基化以及C3，C5-和C3， c6 -二硫基化。这些转化具有优异的区域选择性，广泛的底物范围和良好的官能团耐受性。此外，后期修改和产品衍生证明了该协议的综合实用性和多功能性。机制研究表明，单硫基化是通过涉及巯基自由基的自由基途径进行的，而二硫基化可能是通过螯合辅助的钌化途径进行的。总的来说，这项工作为2-吡啶酮的位点特异性和多位点功能化提供了一个强大的平台，为快速构建结构多样的含硫杂环铺平了道路。

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引用次数: 0

A Versatile and Practical One-Pot Strategy for a Greener, Waste-Minimized Synthesis of Aryloxy- and Alkyloxy-Substituted Metallophthalocyanines via Tandem SNAr-cyclotetramerization 通过串联snar环四聚化合成芳基和烷基氧基取代金属酞菁的通用实用一锅策略

IF 5.4 1区化学 Q1 CHEMISTRY, ORGANIC

Organic Chemistry Frontiers

Pub Date : 2025-12-23 DOI: 10.1039/d5qo01267h

Federica Palmeri, Venanzio Raglione, Laura Mancini, Gloria Zanotti

Phthalocyanines represent molecules of considerable scientific interest, yet their synthesis remains challenging, particularly under environmentally sustainable conditions. Due to the increasingly urgent need for developing sustainable and efficient synthetic methodologies, we report a general, practical, and potentially scalable one-pot procedure for the synthesis of aryloxy- and alkyloxy-substituted metallophthalocyanines. This method integrates a nucleophilic aromatic substitution on the phthalonitrile precursors with a subsequent metal-templated cyclotetramerization, all within a single reaction vessel, thus eliminating the need for intermediate isolation and minimizing solvent and reagents consumption. The protocol is compatible with a wide variety of phenols and alcohols, including sterically hindered or electron-withdrawing substituents, and can be performed using standard laboratory glassware and conventional heating, suggesting its practical suitability for scale-up. Selected phthalocyanines were obtained with up to nearly fourfold higher yields compared to literature-reported two-step procedures (e.g., 27% vs. 7% for tetra(3,5-bis(trifluoromethyl)phenoxy)zinc-phthalocyanine) and were characterized by UV–vis, IR, NMR spectroscopy, and mass spectrometry. Environmental efficiency, assessed through E-factor calculations, achieves over 90% reduction in waste generation relative to literature-reported two-step procedures, demonstrating the advantages of our one-pot strategy in terms of environmental sustainability, operational simplicity together with waste reduction and broader applicability to green phthalocyanine synthesis.

酞菁代表了具有重大科学意义的分子，但它们的合成仍然具有挑战性，特别是在环境可持续的条件下。由于越来越迫切需要发展可持续和高效的合成方法，我们报告了一种通用的、实用的、潜在的可扩展的一锅法合成芳氧基和烷基氧基取代的金属酞菁。该方法将邻苯二腈前驱体上的亲核芳香取代与随后的金属模板环四聚化结合在一起，所有这些都在一个反应容器内，从而消除了中间分离的需要，并最大限度地减少了溶剂和试剂的消耗。该方案与多种酚和醇兼容，包括空间位阻或吸电子取代基，并可使用标准实验室玻璃器皿和传统加热进行，表明其实际适用于扩大规模。与文献报道的两步法相比，所选酞菁的产率高达近四倍（例如，27%比7%的四（3,5-二（三氟甲基）苯氧基）锌酞菁），并通过紫外-可见、红外、核磁共振光谱和质谱进行了表征。通过e因子计算评估的环境效率，与文献报道的两步程序相比，减少了90%以上的废物产生，证明了我们的一锅策略在环境可持续性、操作简单、减少废物和更广泛适用于绿色酞菁合成方面的优势。

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引用次数: 0

Theoretical Insight: Dual Roles of Electron-Pair Donors and Acceptors in Activating and Mediating Iodine Atom Transfer 理论洞察：电子对供体和受体在激活和介导碘原子转移中的双重作用

IF 5.4 1区化学 Q1 CHEMISTRY, ORGANIC

Organic Chemistry Frontiers

Pub Date : 2025-12-23 DOI: 10.1039/d5qo01593f

Taiming Bai, Ming Lei, Hui Li

Lewis bases (Lbs) act as electron-pair donors and react with BH₃ to form Lbs→BH₃ complexes. In catalytic systems, these precursors generate two key reactive species: the Lbs→ BH₂ • radical species, which directly activates the C(sp³)-I bonds in alkyl iodides (R-I) via iodine atom transfer (IAT) , leading to the generation of alkyl radicals; and the Lb→BH ₂ ⁺ cationic species, which facilitates XAT by enhancing C-I bond polarization. The energy barrier for the IAT process mediated solely by Lbs → BH₂• is 19.7 kcal•mol⁻¹, whereas in the presence of the Lb → BH₂⁺ cationic complex, the barrier decreases to 15.9 kcal•mol⁻¹, significantly reducing the kinetic barrier.This work provides a new mechanism for generating alkyl radicals from a theoretical computational perspective. By systematically evaluating 28 distinct Lbs → BH₃ complexes and computationally analyzing key elementary steps and competing reactions, we establish preliminary structure-activity relationships that elucidate the influence of Lewis bases on the XAT mechanism. The synergistic cooperation between engineered Lbs→BH₃ complexes and copper catalysts not only promotes efficient C-N coupling but also provides a robust theoretical foundation and innovative design principles for the development of related catalytic transformations.

路易斯碱（Lbs）作为电子对供体，与BH3反应形成lb→BH3配合物。在催化体系中，这些前驱体产生两个关键的反应种：Lbs→BH2•自由基，通过碘原子转移（IAT）直接激活烷基碘化物（R-I）中的C(sp3)- 1键，导致烷基自由基的生成；Lb→BH 2 +阳离子，通过增强C-I键极化促进XAT。单独由Lb→BH 2•介导的IAT过程的能垒为19.7 kcal•mol⁻¹，而在Lb→BH 2•阳离子配合物的存在下，能垒降低到15.9 kcal•mol⁻¹，显著降低了动能垒。本研究从理论计算角度为烷基自由基的生成提供了一种新的机制。通过系统评价28种不同的lb→BH3配合物，计算分析关键的基本步骤和竞争反应，我们建立了初步的构效关系，阐明了Lewis碱基对XAT机理的影响。设计的lb→BH3配合物与铜催化剂之间的协同作用不仅促进了C-N的高效耦合，而且为相关催化转化的发展提供了坚实的理论基础和创新的设计原则。

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引用次数: 0

Class-II-aldolase-mimicking polyfunctional Lewis acid/azolium–aryloxide catalysts in direct enantioselective nitro-aldol additions ii类模拟醛缩酶的多功能路易斯酸/偶氮芳基氧化物催化剂在硝基醛醇直接对映选择性加成中的应用

IF 4.7 1区化学 Q1 CHEMISTRY, ORGANIC

Organic Chemistry Frontiers

Pub Date : 2025-12-23 DOI: 10.1039/D5QO01558H

Khushbu Jangid, Lisa A. Schmoltzi, Alexander Allgaier, Radhika Kataria, Daniel M. Wanner, Justin Herrmann, Janis Gschwind, Silvio Münch, Joris van Slageren, Johannes Kästner and René Peters

The catalytic asymmetric nitroaldol reaction is a powerful tool for accessing chiral 1,2-difunctionalized motifs, and numerous catalytic systems have been reported. Despite considerable progress in achieving high levels of stereocontrol, key challenges persist. In particular, optimal selectivity often requires cryogenic conditions, resulting in prolonged reaction times and limited practicality. In this article, a novel concept for asymmetric nitroaldol additions is introduced through a polyfunctional catalyst. This system integrates a Lewis acid, Co(II), with an azolium–aryloxide betaine, and exhibits mechanistic features reminiscent of class-II aldolases. The proposed mode of action is supported by comprehensive DFT calculations, microkinetic simulations, and detailed spectroscopic analyses. By the unique synergistic interplay of the Lewis acidic metal center, the aryloxide as Brønsted base and the corresponding aromatic alcohol serving as both hydrogen bond donor and Brønsted acid, high stereoselectivity was accomplished even at slightly elevated temperature for MeNO₂. Like in class-II-aldolases, the aldehyde is activated by H-bonding to the aromatic alcohol and not by the Lewis acid. The latter serves to stabilize and direct the nitronate. The computational studies further demonstrate that the catalyst‘s key functional groups precisely orchestrate all accompanying transformations. As a result of the mild reaction conditions, not necessitating the use of an external base, the method also proved to be applicable to readily enolizable aliphatic aldehydes, such as phenylacetaldehyde.

催化不对称硝基醇反应是获得手性1,2-二功能化基序的有力工具，已有许多催化体系的报道。尽管在实现高水平立体控制方面取得了相当大的进展，但主要挑战仍然存在。特别是，最佳选择性通常需要低温条件，导致反应时间延长，实用性有限。本文介绍了一种通过多官能团催化剂进行不对称硝基醇加成的新概念。该系统将Lewis酸Co（II）与偶氮芳基甜菜碱结合，并表现出II类醛缩酶的机制特征。提出的作用模式是由全面的DFT计算，微动力学模拟和详细的光谱分析支持。通过Lewis酸性金属中心的独特协同作用，羰基氧化物作为Brønsted碱，相应的芳香醇作为氢键供体和Brønsted酸，即使在稍微升高的温度下也能实现对MeNO2的高立体选择性。像ii类醛缩酶一样，醛是由与芳香醇的氢键激活的，而不是由路易斯酸激活的。后者起到稳定和引导硝酸钠的作用。计算研究进一步表明，催化剂的关键官能团精确地协调了所有伴随的转化。由于反应条件温和，不需要使用外部碱，该方法也被证明适用于容易烯化的脂肪族醛，如苯乙醛。

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引用次数: 0

Discovery and synthesis of (+)/(–)-muyoquinone A, a pair of rare cyclopropane bridge-containing pentacyclic benzoquinone dimers with cytotoxic activity （+）/(-)-多醌A的发现和合成，一对罕见的具有细胞毒性的含环丙烷桥的五环苯醌二聚体

IF 4.7 1区化学 Q1 CHEMISTRY, ORGANIC

Organic Chemistry Frontiers

Pub Date : 2025-12-23 DOI: 10.1039/D5QO01312G

Hai-Yan Cao, Cheng Yi, Yu-Wei Niu, Ke-Liang Chen, Yang Liu, Fang-Fang Lai and Yun-Bao Liu

(±)-Muyoquinone A (1a/1b), a pair of rare racemic cyclopropane bridge-containing pentacyclic benzoquinone dimers with a tricyclo[2.2.2.0^2,7]octane core, were isolated from the endophytic fungus Muyocopron laterale. The structure was unambiguously established by spectroscopic and single-crystal X-ray diffraction analysis. We identified a biomimetic total synthesis of muyoquinone A (1) in seven steps by taking advantage of an intermolecular Diels–Alder homodimerization/dehydrogenation/intramolecular Diels–Alder cycloaddition cascade. (±)-Muyoquinone A (1a/1b) exhibited a selective in vitro cytotoxic effect against several human cancer cell lines (IC₅₀ 3.06–8.29 μM). Meanwhile, the racemic mixture showed stronger cytotoxic activities than the corresponding enantiomers.

（±）-Muyoquinone A （1a/1b）是从内生真菌Muyocopron laterale中分离得到的一对罕见的具有三环[2.2.2.02,7]辛烷值核心的外消旋环丙烷桥接五环苯醌二聚体。通过光谱和单晶x射线衍射分析，确定了其结构。我们利用Diels-Alder分子间同二聚/脱氢/ Diels-Alder分子内环加成级联七个步骤，确定了仿生全合成muyo醌a(1)。（±）-Muyoquinone A （1a/1b）对多种人类癌细胞具有选择性体外细胞毒作用（IC50值为3.06 ~ 8.29 μM）。同时，外消旋混合物比相应的对映体具有更强的细胞毒活性。

引用次数: 0

Dehydrogenative Aromatization of Cyclohexanone Derivatives for the Synthesis of Site-selective Substituted Phenols and Anilines 环己酮衍生物脱氢芳构化合成选择性取代酚和苯胺

IF 5.4 1区化学 Q1 CHEMISTRY, ORGANIC

Organic Chemistry Frontiers

Pub Date : 2025-12-23 DOI: 10.1039/d5qo01442e

Dahong Jiang, Quanfeng Liang, Haiqing Li, Fang Fan

Aromatic compounds containing phenol or aniline functionalities are ubiquitous building blocks in various fields both in academic and industrial chemistry. Traditionally, substituted phenols and anilines are synthesized via electrophilic or nucleophilic aromatic substitution, but the regioselectivity is constrained by the substituents. The dehydrogenative aromatization of cyclohexanone derivatives, as an alternative, has a transformative influence on the synthesis of phenol or aniline derivatives that can overcome the limitation of ortho-, meta-, or para-orientations. This review mainly focuses on the recent research progress since 2020 concerning the two types of dehydrogenative aromatization: oxidative and acceptorless, in synthesizing substituted phenols and anilines. Representative examples are examined and classified by catalysis patterns. The associated reaction mechanisms and applications are also included, which offers a comprehensive and up-to-date overview of these compounds for synthesis purposes.

含有酚或苯胺功能的芳香族化合物在学术和工业化学的各个领域都是无处不在的基石。传统上，取代的苯酚和苯胺是通过亲电或亲核的芳香取代来合成的，但区域选择性受到取代基的限制。作为一种选择，环己酮衍生物的脱氢芳构化对苯酚或苯胺衍生物的合成具有变革性影响，这些衍生物可以克服邻位、间位或对位取向的限制。本文主要综述了2020年以来在取代酚类和苯胺类合成中氧化和无受体两种脱氢芳构化方法的最新研究进展。根据催化模式对代表性的例子进行了检查和分类。相关的反应机理和应用也包括在内，它提供了一个全面的和最新的概述，这些化合物的合成目的。

引用次数: 0

Visible light-driven construction of isoxazoline/isoxazole scaffolds via [2+2+1] cyclization of alkenes with tert-butyl nitrite 亚硝酸盐叔丁基烯烃[2+2+1]环化在可见光下构建异恶唑啉/异恶唑支架

IF 5.4 1区化学 Q1 CHEMISTRY, ORGANIC

Organic Chemistry Frontiers

Pub Date : 2025-12-23 DOI: 10.1039/d5qo01546d

Yanfu Jiang, Jiantao Zhang, Xian Jiang, Renhua Su, Liuzhuang Xing, Xin Yang, Weibing Liu

A visible light-driven [2+2+1] cyclization of alkenes with tert-butyl nitrite (TBN) has been developed for the efficient construction of isoxazoline and isoxazole scaffolds. This protocol operates under mild conditions—utilizing ambient air as an oxygen source, room temperature, and visible-light irradiation—enabling both cross- and self-coupling of a wide range of alkenes with high functional group tolerance (including unprotected alcohols and terminal alkynes). The method has been successfully applied to the late-stage modification of bioactive drug molecules. Mechanistic studies reveal that O₂ serves as the key oxygen atom source for the carbonyl group in the products. This work represents a sustainable and practical strategy for heterocycle synthesis, aligning with the principles of green chemistry by minimizing energy input, avoiding transition metals, and employing benign reaction media.

为了高效构建异恶唑啉和异恶唑支架，研究了一种由亚硝基叔丁基（TBN）驱动的[2+2+1]烯烃环化反应。该方案在温和条件下操作-利用环境空气作为氧气源，室温和可见光照射-使具有高官能团耐受性的各种烯烃（包括未保护的醇和末端炔）的交叉和自偶联成为可能。该方法已成功应用于生物活性药物分子的后期修饰。机理研究表明，O₂是产物中羰基的关键氧原子源。这项工作代表了一种可持续和实用的杂环合成策略，符合绿色化学的原则，通过减少能量输入，避免过渡金属和使用良性反应介质。

引用次数: 0

Preparation and Catalytic Properties of Benziodolium Salts 苯并碘鎓盐的制备及其催化性能

IF 5.4 1区化学 Q1 CHEMISTRY, ORGANIC

Organic Chemistry Frontiers

Pub Date : 2025-12-23 DOI: 10.1039/d5qo01379h

Haruhi Hirai, Akira Tsubouchi, Kazunori Miyamoto, Akira Yoshimura, Akio Saito

Dibenziodolium salts have recently emerged as useful iodine (III)-type halogen bonding (XB) donors. However, although benziodolium salts with one less benzene ring are expected to exhibit different reactivity from dibenziodolium salts, their function as a XB donor has not been clarified. Herein, a new and simple synthetic method of benziodolium salts and their application as organic Lewis acids are reported.

二苯并碘鎓盐最近被发现是有用的碘（III）型卤素键（XB）供体。然而，虽然少一个苯环的苯并碘鎓盐预计会表现出与二苯并碘鎓盐不同的反应性，但它们作为XB供体的功能尚未明确。本文报道了一种简便的合成苯并碘鎓盐的新方法及其作为有机路易斯酸的应用。

引用次数: 0

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