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

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An efficient method for the synthesis of π-expanded phosphonium salts† 一种合成π膨胀磷盐的有效方法

Organic chemistry frontiers : an international journal of organic chemistry

Pub Date : 2025-09-05 DOI: 10.1039/d5qo00708a

Krzysztof Górski , Łukasz W. Ciszewski , Antoni Wrzosek , Adam Szewczyk , Andrzej L. Sobolewski , Daniel T. Gryko

A new straightforward methodology for the synthesis of phosphonium salts integrated with a π-conjugated scaffold has been developed using phosphine oxides. It is now possible to obtain cyclic phosphonium salts possessing up to eight conjugated rings and bearing e.g. pyrrole, thiophene, indole or benzofuran scaffolds from abundant and commercially available materials in high yields. An enticing feature of this general strategy is that this one-step procedure typically does not require chromatographic purification. Still greater synthetic possibilities are related to the fact that even demanding scaffolds such as azulene, pyrene or fluorene can be bridged with the phospholium subunit. Starting from 1,4-dihydropyrrolo[3,2-b]pyrrole, heretofore rarely observed ladder-type bis-phosphonium salts were effectively prepared. This strategy was also extended into the preparation of cyclic arsonium salt. The ability to form phosphonium salts possessing such manifold scaffolds translated into diverse photophysical properties ranging from non-fluorescent dyes to thiophene-derivatives emitting quantitatively in the blue region. Geometry change induced by light absorption has a predominant influence on the fate of the molecules’ excited state. It was shown, in analogy to previous results, that cyclic tetraarylphosphonium salts migrate through the membrane of living cells to localize in the mitochondria similarly to the well-known triarylphosphonium salts.

本文提出了一种利用磷化氢氧化物合成磷盐与π共轭支架的新方法。现在可以从丰富的、可获得的商业材料中以高产量获得含有多达8个共轭环并含有吡咯、噻吩、吲哚或苯并呋喃等支架的环磷盐。这种通用策略的一个诱人的特点是，这一步程序通常不需要色谱纯化。更大的合成可能性与这样一个事实有关，即即使是要求很高的支架，如azulene、芘或芴，也可以与磷亚基桥接。从1,4-二氢吡咯[3,2-b]吡咯开始，有效地制备了迄今罕见的阶梯型双磷盐。这一策略也被推广到环胂盐的制备中。形成具有这种多种支架的磷盐的能力转化为不同的光物理性质，从非荧光染料到在蓝色区域定量发光的噻吩衍生物。由光吸收引起的几何变化对分子激发态的命运具有显性影响。与先前的结果类似，研究表明，环四芳基磷盐通过活细胞的膜迁移到线粒体中，类似于众所周知的三芳基磷盐。

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引用次数: 0

Retro-Mukaiyama aldol reaction-driven silicon catalysis† retromukaiyama Aldol反应驱动硅催化

Organic chemistry frontiers : an international journal of organic chemistry

Pub Date : 2025-09-05 DOI: 10.1039/d5qo00740b

Yongjing Dong , Yue Hu , Yiqing Wang , Liqun Jin , Yinjun Xie

The use of silicon reagents as catalysts has long been an attractive yet challenging goal due to difficulties in silicon catalyst regeneration. Herein, we report a novel silicon-catalyzed formal hydroformylation of alkynes with aldehydes to access α,β-unsaturated ketones with high efficiency under mild conditions. The success of this method relies on an innovative retro-Mukaiyama aldol reaction (RMAR)-driven silyl transfer strategy, which enables efficient regeneration of silicon catalysts. Preliminary mechanistic studies reveal the evolution of key silicon catalysts during this transformation. This protocol provides valuable insights for the design of new chemical transformations based on silicon catalysis.

由于硅催化剂再生的困难，使用硅试剂作为催化剂一直是一个有吸引力但具有挑战性的目标。在此，我们报道了一种新的硅催化的炔与醛的形式氢甲酰化反应，在温和的条件下以高效率获得α，β-不饱和酮。该方法的成功依赖于逆mukaiyama醛醇反应（RMAR）驱动的硅基转移策略的创新，该策略能够实现硅催化剂的高效再生。初步的机理研究揭示了这一转变过程中关键硅催化剂的演变。该协议为基于硅催化的新化学转化的设计提供了有价值的见解。

引用次数: 0

Radical-polar crossover cyclization: visible-light-induced synthesis of γ-alkylated 1,1-disubstituted cyclopropanes via 1,6-hydrogen atom transfer† 自由基-极性交叉环化：通过1,6-氢原子转移在可见光诱导下合成γ-烷基化1,1-二取代环丙烷

Organic chemistry frontiers : an international journal of organic chemistry

Pub Date : 2025-09-05 DOI: 10.1039/d5qo00670h

Meiling Ye , Hang Wang , Min Liao , Zeyu Tian , Zhongzhen Yang , Yong Wu

A visible-light-induced radical-polar crossover cyclization (RPCC) reaction between homoallylic substrates and sulfamate esters for the synthesis of γ-alkylated 1,1-disubstituted cyclopropanes via 1,6-HAT processes has been reported. This protocol displays mild and metal-free conditions, excellent functional group tolerance and a broad range of substrates. Furthermore, the potential synthetic potential of this transformation is demonstrated by scale-up reactions and synthetic applications.

报道了在可见光诱导下，均烯丙基底物与氨基甲酸酯之间的自由基-极性交叉环化反应，通过1,6- hat工艺合成了γ-烷基化1,1-二取代环丙烷。该方案显示温和和无金属的条件，优异的官能团耐受性和广泛的底物范围。此外，这种转化的潜在合成潜力通过放大反应和合成应用得到了证明。

引用次数: 0

Rhodaelectro-catalyzed C–H activations directed by pharmacophores: enabling modification of bioactive compounds† rhodae催化的C-H活化由药物载体指导：使生物活性化合物的修饰

Organic chemistry frontiers : an international journal of organic chemistry

Pub Date : 2025-09-05 DOI: 10.1039/d5qo00808e

Shangyong Wu , Binbin Yuan , Yongke Lei , Xiaoli Su , Tristan von Münchow , João C. A. Oliveira , Xuewu Huang , Zhaojun Ding , Rongrong Xu , Lutz Ackermann , Jiayu Mo

In the realm of sustainable molecular synthesis, metallaelectro-catalysis has emerged as a highly potent platform over the past decade. While significant advancements have been achieved in this field, the development of strategies for late-stage C–H functionalization remains a formidable challenge. In this context, we present an electrochemical rhodium-catalyzed C–H activation strategy that facilitates the selective modification of bioactive compounds. The developed electrocatalysis strategy, enabling the efficient C–H/N–H activations and annulations with a variety of diaryl-, dialkyl-, and unsymmetric alkynes, demonstrates broad tolerance towards a range of medicinally relevant functional groups and thus provides expedient access to the modification of bioactive compounds.

在可持续分子合成领域，金属电催化在过去十年中已经成为一个非常有效的平台。虽然在这一领域取得了重大进展，但后期C-H功能化策略的发展仍然是一个艰巨的挑战。在这种情况下，我们提出了一种电化学铑催化的C-H活化策略，促进了生物活性化合物的选择性修饰。所开发的电催化策略，使C-H / N-H高效活化和环化各种二芳基、二烷基和不对称炔，对一系列医学相关官能团具有广泛的耐受性，从而为生物活性化合物的修饰提供了便利的途径。

引用次数: 0

Radical 1,4-acylcyanoalkylation of alkenes for the synthesis of ζ-ketonitriles† 烯烃自由基1,4-酰基氰化反应合成ζ-酮腈

Organic chemistry frontiers : an international journal of organic chemistry

Pub Date : 2025-09-05 DOI: 10.1039/d5qo00744e

Ying Tong , Jia-Yao Feng , Cuiyan Wu , Shi-Qing Zhang , Ming-Qi Yang , Sheng Du , Dong-Qing Yang , Keqi Tang , Chao Deng , Wen-Ting Wei

Two-component alkene coupling reactions serve as an efficient platform for the synthesis of complex molecular architectures. Leveraging the differences in activation energy barriers among carbon radical precursors and the polarity matching between radicals, this work reports the first example of radical 1,4-acylcyanoalkylation to synthesize challenging-to-access ζ-ketonitriles using two identical alkenes. In the metal-free system, 2-(tert-butylperoxy)-2-methylpropane (DTBP) respectively activates α-C–H bonds of aldehydes and alkyl nitriles to generate acyl and cyanoalkyl radicals. The reaction sequence involves selective radical addition of the acyl radical to two identical alkenes, followed by radical–radical coupling with the cyanoalkyl radical, thereby constructing three C–C bonds under simple conditions. Remarkably, when tertiary alkyl aldehydes are employed, decarbonylation preferentially occurs to form alkyl radicals, enabling 1,4-alkylcyanoalkylation of alkenes. Mechanistic studies and density functional theory (DFT) calculations reveal that the success of this 1,4-acylcyanoalkylation process is governed by both the preferential addition of acyl radicals to alkenes and the thermodynamic stability associated with the two-component alkene addition cascade.

双组分烯烃偶联反应是合成复杂分子结构的有效平台。本文利用碳自由基前体之间活化能垒的差异和自由基之间的极性匹配，首次利用两个相同的烯烃进行1,4-酰基氰基烷基化，合成了难以接近的ζ-酮腈。在无金属体系中，2-（叔丁基过氧基）-2-甲基丙烷（DTBP）分别激活醛和烷基腈的α-C−H键，生成酰基和氰烷基自由基。反应顺序包括酰基自由基选择性加成到两个相同的烯烃上，然后与氰烷基自由基进行自由基-自由基偶联，从而在简单条件下构建3个C−C键。值得注意的是，当叔烷基醛被使用时，脱羰优先发生，形成烷基自由基，使烯烃的1,4-烷基氰烷基化。机理研究和密度泛函理论（DFT）计算表明，这种1,4-酰基氰化过程的成功是由酰基自由基对烯烃的优先加成和与双组分烯烃加成级联相关的热力学稳定性决定的。

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引用次数: 0

Site selective Heck arylation of N-vinyl-7-azaindole engineered by N-oxide activation: scope and mechanistic studies n -氧化活化工程n -乙烯基-7-叠氮树脂的位点选择性芳基化：范围和机制研究

Organic chemistry frontiers : an international journal of organic chemistry

Pub Date : 2025-09-05 DOI: 10.1039/d5qo00976f

Susanta Patra , Arunava Sengupta , Parthasarathi Das

The palladium-catalyzed site-selective arylation of N-vinyl-7-azaindole (AI) derivatives using (hetero)iodoarenes is reported. While N-vinyl-7-azaindole displays moderate regioselectivity, predominantly favoring α-arylation, N-oxide activation (AINO) induces a complete switch to exclusive β-arylation with high E-selectivity. Control experiments and DFT studies support the mechanistic basis of this switch, which arises from the formation of distinct metallocyclic π-complexes: a five-membered complex for α-arylation and a six-membered complex for β-arylation. These findings highlight N-oxide activation as a powerful strategy to control regioselectivity in Heck-type arylations of N-vinyl-7-azaindoles. The transformation proceeds under ligand-free conditions and showcases broad substrate scope and excellent functional group tolerance.

报道了钯催化的n -乙烯基-7-氮杂酚（AI）衍生物的（杂）碘芳烃位点选择性芳化反应。虽然n -乙烯基-7-氮杂吲哚具有中等的区域选择性，主要倾向于α-芳基化，但n -氧化物活化（AINO）诱导完全转换为β-芳基化，具有高e选择性。对照实验和DFT研究支持这种开关的机制基础，这是由于形成不同的金属环π配合物：α-芳基化的五元配合物和β-芳基化的六元配合物。这些发现强调了n -氧化物活化是控制n -乙烯基-7-偶氮唑heck型芳基化的区域选择性的有力策略。该转化在无配体条件下进行，显示出广泛的底物范围和优异的官能团耐受性。

引用次数: 0

Oligomeric monoterpenoid indole alkaloids from the flowers of Gelsemium elegans with anti-inflammatory and anti-fibrotic activities† 具有抗炎和抗纤维化活性的葛兰花低聚单萜类吲哚生物碱

Organic chemistry frontiers : an international journal of organic chemistry

Pub Date : 2025-09-05 DOI: 10.1039/d5qo00551e

Ji-Hong Gu , Ni-Ping Li , Hao-Ting Lin , Ling-Na Dai , Min-Jing Cheng , Jian Hong , Yi-Yi Li , Jun-Shan Liu , Wen-Cai Ye , Lei Wang

Gelsepolycines A–F (), six oligomeric monoterpenoid indole alkaloids with new skeletons, together with their biosynthetic precursors (), were isolated from the flowers of Gelsemium elegans. Compounds and represent the first examples of trimeric Gelsemium alkaloids that feature complex sterically compact frameworks with 17–19 chiral centers. Furthermore, these compounds were constructed through unprecedented C₁₄–C₁₉ and C₁₄–N₄ linkages. Interestingly, all these oligomeric alkaloids () could be derived from the same monomer precursor in the proposed biogenetic pathway. The anti-inflammatory and anti-fibrotic activities of these isolates were evaluated, and compound demonstrated potent effects in vitro and in vivo. The biomimetic synthesis of was achieved according to the proposed biogenetic pathway.

Gelsemium elegans花中分离到了六种具有新骨架的低聚单萜类吲哚生物碱A-F（1-6）及其生物合成前体（7-8）。化合物1和4-6是具有17-19个手性中心的复杂立体紧凑框架的三聚Gelsemium生物碱的第一个例子。此外，这些化合物是通过前所未有的C14-C19和C14-N4键构建的。有趣的是，所有这些低聚生物碱（1-6）都可以在提出的生物遗传途径中从相同的单体前体7中衍生出来。对这些分离物的抗炎和抗纤维化活性进行了评价，化合物3在体外和体内均表现出强有力的作用。根据提出的生物发生途径，实现了3的仿生合成。

引用次数: 0

Polymer-bridged nanofibrils in a high-molar-mass polyester via co-assembly of benzenetricarboxamide end groups and an additive† 通过苯三羧胺端基和添加剂的共组装在高摩尔质量聚酯中的聚合物桥接纳米纤维

Organic chemistry frontiers : an international journal of organic chemistry

Pub Date : 2025-09-05 DOI: 10.1039/d5qo00087d

Sophia Thiele , Michael Giffin , Matthieu Wendling , Daniel Görl , Christopher J. G. Plummer , Holger Frauenrath

Benzenetricarboxamide (BTA) derivatives are versatile compounds widely employed as nucleating agents in commercial semicrystalline plastics and as supramolecular ligands in self-assembling telechelic polymer-based organogels, hydrogels, and bulk elastomers. However, their effectiveness as supramolecular modifiers is typically limited to low-molar-mass apolar polymers. Here, we report the supramolecular aggregation of a BTA-end-functionalized semicrystalline aliphatic polyester with a number-average molar mass several times its entanglement molar mass, blended with a matching low-molar-mass BTA additive. In these blends, the BTA end groups and additive co-assemble to form a new phase comprising a network of polymer-bridged nanofibrils. This network gives rise to a high-melt-strength rubbery regime that is absent from the pure telechelic polyester but extends to temperatures well above its melting point in the blends. Moreover, the nanofibrils prove to be highly efficient nucleating agents for crystallization of the polyester, significantly outperforming bulk additive precipitates. Our findings hence demonstrate that the co-assembly of polymer end groups with a low-molar-mass additive may facilitate supramolecular aggregate formation in polymer matrices where end-modification alone is insufficient, leading to materials with increased melt strength, crystallization rates, thermal dimensional stability, and valuable benefits for industrial applications.

苯三羧胺（BTA）衍生物是一种用途广泛的化合物，广泛用作商业半结晶塑料的成核剂，以及自组装远旋聚合物基有机凝胶、水凝胶和体弹性体的超分子配体。然而，它们作为超分子改性剂的有效性通常仅限于低摩尔质量的极性聚合物。在这里，我们报告了BTA端功能化半晶脂肪族聚酯的超分子聚集，其数字平均摩尔质量是其纠缠摩尔质量的几倍，与匹配的低摩尔质量BTA添加剂混合。在这些共混物中，BTA端基和添加剂共同组装形成由聚合物桥接纳米纤维网络组成的新相。这种网络产生了高熔点强度的橡胶体系，这是纯远旋聚酯所没有的，但在共混物中延伸到远高于熔点的温度。此外，纳米原纤维被证明是聚酯结晶的高效成核剂，显著优于大块添加剂沉淀。因此，我们的研究结果表明，聚合物端基与低摩尔质量添加剂的共组装可以促进聚合物基质中超分子聚集体的形成，而单端改性是不够的，从而提高材料的熔体强度、结晶速率和热尺寸稳定性，从而为工业应用带来宝贵的好处。

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引用次数: 0

Kinetic resolution of trifluoromethylated heterobenzhydrols via hydrogen-acceptor-free Ir-catalyzed heteroaryl-selective C–H silylation† 通过无氢受体ir催化的异芳基选择性C - H硅基化动力学拆分三氟甲基化杂苯氢

Organic chemistry frontiers : an international journal of organic chemistry

Pub Date : 2025-09-05 DOI: 10.1039/d5qo00725a

Ryu Tadano , Takeshi Yasui , Yoshihiko Yamamoto

Kinetic resolution of benzhydrols via intramolecular C–H silylation is an efficient method for the preparation of chiral benzhydrols. However, the previously reported methods required sterically demanding phenyl rings to achieve group-selective C–H silylation. Herein, we report the kinetic resolution of trifluoromethylated heterobenzhydrols, bearing both phenyl and thiophene rings, via heteroaryl-selective C–H silylation. We conducted computational studies on the factors influencing the enantioselectivity and heteroaryl selectivity.

分子内C−H硅基化反应是制备手性苯甲醇的一种有效方法。然而，先前报道的方法需要要求立体苯基环来实现基团选择性C−H硅基化。在这里，我们报告了三氟甲基化的杂苯氢基，同时带有苯基和噻吩环，通过异芳基选择性C−H硅基化的动力学分解。对影响对映体选择性和杂芳基选择性的因素进行了计算研究。

引用次数: 0

NaH-promoted one-pot oxidation/aromatization and C-3H chalcogenation of indoline: atmospheric control-based selective intermediates† 钠促进吲哚的一锅氧化/芳构化和C-3H加硫：基于大气控制的选择性中间体

Organic chemistry frontiers : an international journal of organic chemistry

Pub Date : 2025-09-05 DOI: 10.1039/d5qo00576k

Suman Majee , Km. Anjali , Shaily Agarwal , Vishnu Poonia , Alok Kumar Singh , Biswajit Guchhait , Devalina Ray

A sub-stoichiometric sodium hydride promoted strategy with diselenides and disulphides has been devised for the one-pot cascade oxidation/aromatization and regioselective C-3 selenylation/sulfenylation of indolines under transition metal-free conditions. The newly introduced protocol facilitates the synthesis of C-3 chalcogenated indoles with exceptional flexibility and efficiency. The chalcogenation reaction was successfully performed under both aerobic and inert conditions leading to the formation of C-3 chalcogenated indoles via two different intermediates. Mechanistic insights were derived from various controlled experiments and trapping of reaction intermediates under both sets of conditions, with structural verification achieved via spectral analysis. The prevalence of the radical route was validated by EPR spectroscopy and radical quenching experiments. A broad range of 3-arylthioindoles and 3-arylselenylindoles containing electron donating and withdrawing substituents were obtained in high to excellent yields with this modest and environmentally benign protocol. Additionally, post-transformation of sulfenylated derivatives has further led to the generation of a diarylsulfoxide core of pharmaceutical interest. The reaction is applicable to gram scale synthesis without significant loss of product yield, indicating its application for large-scale synthesis. Interestingly, the biological evaluation of the 5-bromo-3-((4-(trifluoromethyl)phenyl)selanyl)-1H-indole and 3-((4-chlorophenyl)thio)-1H-indole revealed significant activity against rapidly growing mycobacteria (RGM).

在无过渡金属的条件下，采用亚化学计量氢化钠促进二硒和二硫化物的一锅级联氧化/芳香化反应和区域选择性C-3硒/亚砜化反应。新引入的方案促进了C-3硫代吲哚的合成，具有特殊的灵活性和效率。在好氧和惰性条件下，通过两种不同的中间体生成了C-3硫代吲哚。机理的见解是从各种控制实验和捕获反应中间体的两种条件下得出的，并通过光谱分析对它们进行结构变化。通过EPR光谱和自由基猝灭实验验证了自由基路径的优越性。用这种温和的环境友好的方法，以高收率获得了多种含有电子释放和撤回取代基的3-芳基硫吲哚和3-芳基硒基吲哚。此外，转化后的磺化衍生物进一步导致了二芳基亚砜的产生，这是药物研究的核心。该反应适用于克级合成，产物收率无明显损失，具有大规模合成的应用前景。有趣的是，5-溴-3-（（4-（三氟甲基）苯基）selanyl）- 1h -吲哚和3-（（4-氯苯基）硫）- 1h -吲哚的生物学评价显示出对快速生长分枝杆菌（RGM）的显著活性。

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