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Cationic 1-thia-3-aza-Claisen rearrangement entry to cyclic S-allylic isothioureas 环s -烯丙基异硫脲的阳离子1-thia-3-aza-Claisen重排入口
IF 2.2 3区 化学 Q2 CHEMISTRY, ORGANIC Pub Date : 2025-10-31 DOI: 10.1016/j.tet.2025.135035
Joseph Pisano, Yixiao Li, José S. Madalengoitia
Tertiary allylic amines tethered to primary amines react with thiophosgene in the presence of NaHCO3 to afford cyclic S-allylic isothioureas through a proposed cationic 1-thia-3-aza-Claisen rearrangement. Yields for the 2-carbon tether substrates range from 48 % to 65 %, while yields for the 3-carbon tether substrates range from 56 % to 99 %. Substrate scope studies indicate tolerance for a range of non-migrating groups on the tertiary amine while a range of allylic groups are tolerated as the migrating group. Competition studies between a crotyl and allyl group on the tertiary allylic amine show chemoselective rearrangement of the crotyl group over the allyl group. DFT calculations are consistent with the proposed cationic 1-thia-3-aza-Claisen rearrangement and the chemo selective rearrangement of a crotyl group over an allyl group.
叔烯丙基胺系在伯胺上,在NaHCO3的存在下与硫代膦发生反应,通过阳离子1-thia-3-aza-Claisen重排生成环s -烯丙基异硫脲。2碳系链底物的产率从48%到65%不等,而3碳系链底物的产率从56%到99%不等。底物范围研究表明对叔胺上一系列非迁移基团的耐受性,而对烯丙基作为迁移基团的耐受性。叔烯丙基胺上的丁烯基与烯丙基之间的竞争研究表明,丁烯基在烯丙基之上发生了化学选择性重排。DFT计算与提出的阳离子1-thia-3-aza-Claisen重排和丙基在烯丙基上的化学选择性重排一致。
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引用次数: 0
Vinylogous imidonaphthoquinone [2+2] photocycloadditions to bridged aza-anthraquinones 乙烯基亚胺萘醌[2+2]对偶氮蒽醌的光环添加
IF 2.2 3区 化学 Q2 CHEMISTRY, ORGANIC Pub Date : 2025-10-31 DOI: 10.1016/j.tet.2025.135026
Ian Merski, Jinya Yin, Ryan T. Vanderlinden, Jon D. Rainier
Described in this manuscript are intramolecular [2 + 2] photocycloadditions of readily available 2° vinylogous imidonaphthoquinones. In contrast to the reactivity of 3° vinylogous imidonaphthoquinones, subjecting the corresponding 2° substrates to 419 nm light results in the formation of novel bridged tetracyclic aza-anthraquinones from rare crossed [2 + 2] cycloaddition reactions.
在这篇论文中描述了分子内[2 + 2]光环加成的现成的2°葡萄基亚胺醌。与3°葡萄状亚胺醌的反应性相反,将相应的2°底物置于419 nm光下,可以通过罕见的交叉[2 + 2]环加成反应生成新型桥接四环偶氮蒽醌。
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引用次数: 0
Exploring the antibacterial potential of spirocyclic oxindole derivatives: Synthesis and biological evaluation 探索螺环氧吲哚衍生物的抗菌潜力:合成和生物学评价
IF 2.2 3区 化学 Q2 CHEMISTRY, ORGANIC Pub Date : 2025-10-30 DOI: 10.1016/j.tet.2025.135029
Olajide B. Omoyeni , Temitope O. Olomola , Nusrat O. Omisore , Taiwo F. Ojo , Craig A. Obafemi
A series of eight spirocyclic oxindole derivatives 1a–1d, 2a–2d was synthesized according to established methods; this included the previously unreported compound, 2c. The structures of all compounds were unequivocally characterised by spectroscopic analysis (IR, 1H NMR, 13C NMR) and high-resolution mass spectrometry (HRMS). The in vitro antibacterial activity was assessed against representative Gram-positive (Bacillus subtilis, Bacillus anthracis) and Gram-negative (Escherichia coli, Pseudomonas aeruginosa) bacterial strains by determining the minimum inhibitory concentration (MIC) and minimum bactericidal concentration (MBC). The compounds exhibited a range of bactericidal effects. Notably, derivative 2c demonstrated potent, broad-spectrum activity against B. subtilis, B. anthracis, and E. coli. Furthermore, both 2b and 2c exhibited significant efficacy against a clinically resistant strain of P. aeruginosa. In contrast, compounds 1a and 1d showed negligible antibacterial activity. These results underscore the potential of the spirocyclic oxindole scaffold in the development of novel antibacterial agents. This study provides a foundation for future work to optimize the structure-activity relationship and elucidate the precise mechanism of action of these compounds.
根据建立的方法合成了一系列8个螺环氧吲哚衍生物1a-1d、2a-2d;这包括以前未报道的化合物2c。所有化合物的结构通过光谱分析(IR, 1H NMR, 13C NMR)和高分辨率质谱(HRMS)进行了明确的表征。通过测定其最低抑菌浓度(MIC)和最低杀菌浓度(MBC),对革兰氏阳性菌株(枯草芽孢杆菌、炭疽芽孢杆菌)和革兰氏阴性菌株(大肠杆菌、铜绿假单胞菌)进行体外抑菌活性评价。这些化合物表现出一系列的杀菌作用。值得注意的是,衍生物2c对枯草芽孢杆菌、炭疽芽孢杆菌和大肠杆菌具有有效的广谱活性。此外,2b和2c对铜绿假单胞菌临床耐药菌株均有显著疗效。相比之下,化合物1a和1d的抗菌活性可以忽略不计。这些结果强调了螺环氧吲哚支架在开发新型抗菌剂方面的潜力。本研究为进一步优化这些化合物的构效关系和阐明其确切的作用机制奠定了基础。
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引用次数: 0
Visible-light catalytic aerobic oxidation of aldehydes 可见光催化醛的好氧氧化
IF 2.2 3区 化学 Q2 CHEMISTRY, ORGANIC Pub Date : 2025-10-30 DOI: 10.1016/j.tet.2025.135039
Jia-Le Fu , Jia-Lun Luo , Xue-Feng Zhao , Dan Zhang , Tao Wu , Hongwei Si , Peng-Fei Dai
The oxidation of aldehydes to corresponding carboxylic acids catalyzed by tetra-n-butylammonium decatungstate (TBADT) under visible light in CH3CN or H2O have been realized for the first time. Mono-aldehydes and dialdehydes, especially aldehydes bearing with electron-withdrawing groups (e.g.: –NO2, –CO2R, –CHO, –COR, –CN, –CF3, etc.) and vulnerable groups (e.g.: –OH, -SMe, etc.) are well compatible with in moderate to good yields. And detailed mechanistic investigations have revealed the catalytic role of TBADT in the oxidation. A gram-scale synthesis has been implemented with a gas-liquid flow reaction model. Meanwhile, economical and environmentally friendly reagents make this transformation more possible for the industrial applications.
首次实现了十钨酸四正丁铵(TBADT)在可见光下在CH3CN或H2O中催化醛类氧化生成相应的羧酸。单醛类和二醛类,特别是带吸电子基团(如-NO2、-CO2R、-CHO、-COR、-CN、-CF3等)的醛类和带吸电子基团(如-OH、-SMe等)的醛类均具有较好的相容性,产率中高。详细的机理研究揭示了TBADT在氧化过程中的催化作用。采用气液流动反应模型实现了克级合成。同时,经济环保的试剂使这一转变更有可能用于工业应用。
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引用次数: 0
Electrochemically driven benzoazepine-tethered acrylate synthesis 电化学驱动苯并氮卓系链丙烯酸酯合成
IF 2.2 3区 化学 Q2 CHEMISTRY, ORGANIC Pub Date : 2025-10-30 DOI: 10.1016/j.tet.2025.135033
Musarrat Fatma, Faiz Ahmed Khan
Herein, we present an intramolecular palladium catalyzed cascade electrochemical reaction in an undivided cell at room temperature to afford benzoazepine-tethered acrylate derivatives. The reaction pathway is proposed to occur initially via selective iodination followed by 7-endo-dig selective cyclization followed by Heck coupling at room temperature using palladium catalyst. The reaction features broad substrate scope with good yields under mild condition and effectively underlines the role of expanding palladium assisted electrochemical transformation.
在此,我们提出了室温下分子内钯催化的级联电化学反应,以获得苯并氮卓系链丙烯酸酯衍生物。该反应途径首先通过选择性碘化,然后在室温下以钯为催化剂进行7-末端选择性环化,最后进行Heck偶联。该反应具有底物范围广,产率高,反应条件温和的特点,有效地突出了扩大钯辅助电化学转化的作用。
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引用次数: 0
Photoinduced cyclopropanation of olefins via silicoborate-mediated radical transfer 通过硅酸盐介导的自由基转移光诱导烯烃环丙烷化
IF 2.2 3区 化学 Q2 CHEMISTRY, ORGANIC Pub Date : 2025-10-28 DOI: 10.1016/j.tet.2025.135027
Zhen-Ye Wu , Jiang-Hong Liu , Qing Liu , Li Hai , Zhong-Zhen Yang , Yong Wu
Under visible-light irradiation, a metal-free photocatalytic system enables the generation of reactive silicon-centered radicals from a silicate reagent. The radicals undergo efficient addition to olefins, followed by polarity inversion, elimination of the leaving group, and strain-driven cyclization to afford cyclopropane-functionalized silicon products. Notably, this protocol avoids transition-metal catalysts and exhibits broad functional group tolerance. The reaction provides a sustainable strategy for constructing strained carbocycles under mild conditions.
在可见光照射下,无金属光催化体系能够从硅酸盐试剂中产生反应性硅中心自由基。自由基经过高效加成烯烃、极性反转、离去基消除和应变驱动环化得到环丙烷功能化硅产物。值得注意的是,该方案避免了过渡金属催化剂,并表现出广泛的官能团耐受性。该反应为在温和条件下构建应变碳环提供了一种可持续的策略。
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引用次数: 0
Recent advances in total syntheses of cage-like sesquiterpenoids 笼状倍半萜类化合物的全合成研究进展
IF 2.2 3区 化学 Q2 CHEMISTRY, ORGANIC Pub Date : 2025-10-27 DOI: 10.1016/j.tet.2025.135025
YunXia Yang, Xingang Xie, Xuegong She
In recent years, cage-like compounds have attracted extensive attention in chemistry, biology and drug discovery due to their unique spatial structures and remarkable bioactive properties. This paper systematically reviewed the structurally diverse cage-like sesquiterpenoids discovered and isolated from natural drug resources during the 2017–2025 period, focusing on their novel backbone features, extensive bioactivity profiles, and in-depth discussion of the latest advances in their total synthetic works. By analyzing the construction strategies and methodologies for these complex molecules, we aimed to provide some perspective theoretical insights and practical guidance for the total synthesis of this type of intricate natural products.
近年来,笼状化合物以其独特的空间结构和显著的生物活性在化学、生物学和药物研究领域引起了广泛的关注。本文系统综述了2017-2025年间从天然药物资源中发现和分离的结构多样的笼状倍半萜类化合物,重点介绍了它们新颖的骨架特征、广泛的生物活性特征,并对其全合成工作的最新进展进行了深入讨论。通过分析这些复杂分子的构建策略和方法,旨在为这类复杂天然产物的全合成提供一些前瞻性的理论见解和实践指导。
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引用次数: 0
Asymmetric synthesis of chiral 4,5,6-trisubstituted-3,4-dihydropyrimidinethiones catalyzed by chiral Brønsted acid 手性Brønsted酸催化不对称合成4,5,6-三取代-3,4-二氢嘧啶硫酮
IF 2.2 3区 化学 Q2 CHEMISTRY, ORGANIC Pub Date : 2025-10-27 DOI: 10.1016/j.tet.2025.134999
Lingkai Kong, Zhe Li, Chunzhi Ju, Peng Wang, Guangliang Zhang, Suoqin Zhang
The low steric hindrance of small-substituent 2,4-diketones presents a significant challenge for effective asymmetric induction.An efficient and highly enantioselective catalytic system was developed for the Biginelli reaction to access chiral 4,5,6-trisubstituted-3,4-dihydropyrimidinethiones. Through catalyst screening, chiral imidodiphosphoric acid was found to outperform conventional chiral phosphoric acids. Under the optimized conditions, up to 99 % ee and 52–92 % isolated yields were achieved. This method offers a valuable strategy for the asymmetric synthesis of bioactive pyrimidine derivatives with potential pharmaceutical applicatioins.
小取代基2,4-二酮的低空间位阻对有效的不对称诱导提出了重大挑战。为获得手性4,5,6-三取代-3,4-二氢嘧啶硫酮,建立了一种高效、高对映选择性的Biginelli反应催化体系。通过催化剂筛选,发现手性咪胺二磷酸的催化性能优于常规手性磷酸。在此条件下,分离率可达52 ~ 92%,ee可达99%。该方法为不对称合成具有生物活性的嘧啶衍生物提供了一种有价值的方法。
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引用次数: 0
A green electrochemical synthesis in the Aloysia citrodora leaf extract substrate 以香茅叶提取物为底物的绿色电化学合成
IF 2.2 3区 化学 Q2 CHEMISTRY, ORGANIC Pub Date : 2025-10-27 DOI: 10.1016/j.tet.2025.135021
Mohadese Mohtaji , Ameneh Amani , Sadegh Khazalpour
In this work the electrooxidation of verbascoside (VB), the primary active component in Aloysia citrodora leaf extract, was investigated. The research focuse on how VB's electrooxidation, specifically its participation in a Michael addition with aryl sulfinic acids. High-performance liquid chromatography coupled with mass spectrometry (HPLC-MS) analysis has revealed the electrochemical synthesis of two sulfinic acid derivatives (mono- and bis-) using verbascoside as a core molecule. This study also proposes a plausible mechanism for the electrooxidation of verbascoside in the presence of 4-chlorosulfinic acid, which can be useful for predicting the oxidative pathway of verbascoside.
本文研究了香茅叶提取物中主要活性成分毛蕊花苷(VB)的电氧化作用。研究的重点是VB的电氧化,特别是它在与芳基亚磺酸的Michael加成反应中的参与。高效液相色谱-质谱(HPLC-MS)分析揭示了以毛蕊花苷为核心分子,电化学合成了两种亚磺酸衍生物(单-和双-)。本研究还提出了毛蕊花糖苷在4-氯亚磺酸存在下的电氧化机制,为预测毛蕊花糖苷的氧化途径提供了依据。
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引用次数: 0
Mechanical force-induced luminescence enhancement and chromism of organic luminogens: synthesis, recent advances and perspectives 有机发光源的机械力致发光增强与致变色:合成、最新进展与展望
IF 2.2 3区 化学 Q2 CHEMISTRY, ORGANIC Pub Date : 2025-10-26 DOI: 10.1016/j.tet.2025.135023
Hanrong Liu, Junhui Jia
Mechanochromic luminescent (MCL) materials are a class of novel intelligent materials that exhibit reversible change in luminescence color and/or intensity upon external mechanical force stimulation, demonstrating significant application potential in fields of force sensors, anti-counterfeiting materials, optical storage, bioimaging, and inkless printing, etc. Over the past few decades, in sharp contrast to the traditional fluorescence quenching phenomenon, MCL materials with enhanced luminescence effects have attracted considerable attention due to their unique “off-on” or “turn-on” behavior, where the luminescence intensity or efficiency significantly increased under mechanical force. Focusing on this intriguing property, this review summarizes the latest advances in “turn-on” MCL organic luminophores, categorizing them based on structural features and associated luminescence mechanisms. It emphasizes the critical roles of intermolecular interactions and packing modes in regulating mechanochromic behavior and mechanical force-induced luminescence enhancement performance. Furthermore, this review prospects future development directions and challenges for mechanical force-induced chromic materials with luminescence enhancement, including the development of novel high-efficiency materials, exploration of practical application potential, and in-depth investigation of underlying luminescence mechanisms.
机械致色发光材料(Mechanochromic luminescence, MCL)是一类在外力作用下发光颜色和强度发生可逆变化的新型智能材料,在力传感器、防伪材料、光学存储、生物成像、无墨印刷等领域具有重要的应用潜力。在过去的几十年里,与传统的荧光猝灭现象形成鲜明对比的是,发光效果增强的MCL材料由于其独特的“off-on”或“on -on”行为,在机械力作用下发光强度或效率显著提高,引起了人们的广泛关注。针对这一有趣的特性,本文综述了“开启”MCL有机发光团的最新进展,并根据其结构特征和相关发光机制对其进行了分类。它强调了分子间相互作用和包装模式在调节机械致变色行为和机械力致发光增强性能中的关键作用。展望了机械力致发光增强铬材料未来的发展方向和面临的挑战,包括开发新型高效材料、探索实际应用潜力以及深入研究潜在的发光机制。
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引用次数: 0
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Tetrahedron
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