Tetrahedron Letters最新文献

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Synthesis of aza-polycyclic aromatic hydrocarbons as organic optoelectronic materials via the Povarov reaction Povarov反应合成氮杂-多环芳烃有机光电材料

IF 1.5 4区化学 Q3 CHEMISTRY, ORGANIC

Tetrahedron Letters

Pub Date : 2025-09-22 DOI: 10.1016/j.tetlet.2025.155836

Yuanrong Shan , Takaki Kanbara , Junpei Kuwabara

The Povarov reaction, a classical [4+2] cycloaddition of imines and unsaturated compounds, provides a versatile synthetic platform for the synthesis of nitrogen-doped π-conjugated molecules. This review highlights the recent advances in the application of the Povarov reaction in the synthesis of aza-polycyclic aromatic hydrocarbons (aza-PAHs), which are important components of emerging organic optical and electronic materials. The modularity, one-pot multicomponent compatibility, and broad catalyst scope of the Povarov reaction afford structurally diverse aza-PAHs. Representative examples spanning small molecules, conjugated polymers, covalent organic frameworks (COFs), and molecular cages are discussed, with particular emphasis on their functional properties, including photoluminescence, sensing, circularly polarized luminescence, hole-blocking, and electron transport properties in organic light-emitting diodes. Mechanistic insights into regioselectivity and π-extension are also reviewed to facilitate the future design of aza-PAHs. The Povarov reaction is a powerful synthetic tool for the development of advanced aza-PAH-based materials for optical and electronic applications.

Povarov反应是亚胺和不饱和化合物的经典[4+2]环加成反应，为合成氮掺杂π共轭分子提供了一个通用的合成平台。本文综述了近年来Povarov反应在合成氮杂多环芳烃（aza-PAHs）中的应用进展，氮杂多环芳烃是新兴有机光学和电子材料的重要组成部分。Povarov反应的模块化、一锅多组分相容性和广泛的催化剂范围，使得杂环芳烃结构多样。讨论了小分子、共轭聚合物、共价有机框架（COFs）和分子笼等具有代表性的例子，特别强调了它们的功能特性，包括有机发光二极管中的光致发光、传感、圆极化发光、空穴阻塞和电子传递特性。本文还综述了区域选择性和π-扩展的机理，为今后aza-PAHs的设计提供参考。Povarov反应是开发用于光学和电子应用的先进aza- pah基材料的强大合成工具。

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引用次数: 0

Visible-Light-Induced Regioselective Benzylic CH Oxidation of Substituted 6-Aryl-7,8,9,10-tetrahydrobenzo[c]phenanthridine 可见光诱导取代6-芳基-7,8,9,10-四氢苯并[c]菲蒽啶的区域选择性苄基CH氧化

IF 1.5 4区化学 Q3 CHEMISTRY, ORGANIC

Tetrahedron Letters

Pub Date : 2025-09-21 DOI: 10.1016/j.tetlet.2025.155828

Mukesh Kumar , Musfika Khatun , Simra Faraz , Satyajit Singh , Abu Taleb Khan

A practical and sustainable protocol for the photocatalytic oxidation of benzylic CH bonds, particularly within polycyclic heteroaromatic (PHA) frameworks, has been developed. In contrast to many previously reported systems, which often rely on long reaction times, narrow-spectrum LEDs, additives, or specialized photoreactors or setups, this method employs inexpensive eosin Y under white LED illumination with molecular oxygen supplied via a balloon. The transformation proceeds under mild conditions without the need for transition metals, hazardous oxidants, or auxiliary additives, and operates via a radical mechanism supported by inhibition studies. The broad substrate tolerance and operational simplicity of this protocol facilitate efficient access to benzylic ketones. Its utility is exemplified in the synthesis of a variety of 6-aryl-8,9-dihydrobenzo[c]phenanthridin-10(7H)-one derivatives, where the substituent at the 6-position plays a critical role in determining product outcome. This method represents one of the few reported examples of late-stage CH functionalization in PHAs under photocatalytic conditions.

一个实用的和可持续的方案，光催化氧化的苄基CH键，特别是在多环杂芳烃（PHA）框架，已经开发。与许多先前报道的系统相比，这些系统通常依赖于长反应时间、窄光谱LED、添加剂或专门的光反应器或装置，该方法在白光LED照明下使用廉价的伊红Y，并通过气球提供分子氧。这种转化在温和的条件下进行，不需要过渡金属、有害氧化剂或辅助添加剂，并通过抑制研究支持的自由基机制进行。该方法广泛的底物耐受性和操作简单性促进了对苯酮的有效获取。它的用途在合成各种6-芳基-8,9-二氢苯并[c]菲蒽啶-10(7H)- 1衍生物中得到了例证，其中6-位置的取代基在决定产物产物中起着关键作用。该方法是少有报道的光催化条件下相芳烃中晚期CH功能化的例子之一。

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引用次数: 0

Silver-catalyzed regioselective synthesis of benzo[2,7] naphthyridines using ortho-alkynyl quinoline carbaldehyde and anthranilic acid derivatives 银催化邻炔基喹啉乙醛和邻氨基苯甲酸衍生物的区域选择性合成苯并[2,7]萘啶

IF 1.5 4区化学 Q3 CHEMISTRY, ORGANIC

Tetrahedron Letters

Pub Date : 2025-09-20 DOI: 10.1016/j.tetlet.2025.155835

Kapil Chahal , Ravikumar Badhavath , K. Velangini Sunidhi Reddy , Kirti Vashishtha , K. Rajender Reddy

This method represents a significant advancement in the synthesis of Benzo[2,7]naphthyridines. The silver-catalyzed cyclization of ortho-alkynyl aldehydes and anthranilic acids proceeds under mild conditions with minimal catalyst loading, providing high yields and excellent regioselectivity. Control experiments and deuteration studies were performed to evaluate the reaction mechanism. The broad substrate scope and scalability make this protocol especially valuable for synthesizing diverse 2,7-naphthyridine derivatives, which are important scaffolds in medicinal chemistry and materials science.

该方法是苯并[2,7]萘啶合成的重要进展。银催化邻炔基醛和邻氨基苯甲酸的环化反应在温和的条件下进行，催化剂负荷最小，产率高，区域选择性好。通过对照实验和氘化实验对反应机理进行了评价。广泛的底物范围和可扩展性使该方法特别适用于合成各种2,7-萘啶衍生物，这些衍生物是药物化学和材料科学中重要的支架。

引用次数: 0

Phosphoric acid-catalyzed regioselective amidation of para-quinone methides with acetonitrile 磷酸催化对醌与乙腈的区域选择性酰胺化

IF 1.5 4区化学 Q3 CHEMISTRY, ORGANIC

Tetrahedron Letters

Pub Date : 2025-09-20 DOI: 10.1016/j.tetlet.2025.155834

Xiu Liu , Hongjun Chen , Chenzhong Jin , Longzhi Zhu , Biquan Xiong

An efficient and atom-economical phosphoric acid-catalyzed amidation of para-quinone methides (p-QMs) with acetonitrile has been developed under mild conditions. Water serves as the sole source of both hydrogen and oxygen atoms, enabling 100 % atom economy in amide bond formation. The reaction exhibits excellent generality across a broad spectrum of electronically and sterically diverse p-QMs, facilitating efficient and highly regioselective synthesis of synthetically valuable N-diarylmethyl-substituted acetamides in good to excellent yields. Step-by-step control experiments and competitive deuterium-labeling KIE studies elucidated the reaction pathway and led to a plausible mechanism based on cumulative experimental evidences.

研究了在温和条件下，磷酸催化乙腈酰胺化对醌类化合物（p-QMs）的高效、原子经济的方法。水作为氢原子和氧原子的唯一来源，在酰胺键形成中实现了100%的原子经济性。该反应在广泛的电子和空间多样性的p-QMs中表现出优异的通用性，促进了高效和高区域选择性的合成有合成价值的n -二芳基甲基取代的乙酰胺，收率很高。逐步对照实验和竞争性氘标记KIE研究阐明了反应途径，并基于累积的实验证据得出了一个合理的机制。

引用次数: 0

Dual-type photodynamic therapy enabled by fluorinated BODIPY-liposome hybrids for enhanced antibacterial efficacy 双型光动力疗法启用氟化bodipy -脂质体混合物，以增强抗菌功效

IF 1.5 4区化学 Q3 CHEMISTRY, ORGANIC

Tetrahedron Letters

Pub Date : 2025-09-18 DOI: 10.1016/j.tetlet.2025.155830

Zhihua Chen , Jincheng Zhu , Mengxing Wang , Qinglin Wu , Yichun Xu , Lei Cui , Kewen Zheng

The widespread misuse of antibiotics has accelerated bacterial evolution, precipitating a global antimicrobial resistance (AMR) crisis. Photodynamic therapy (PDT) has recently emerged as a promising alternative due to its non-invasiveness, cost-effectiveness and broad-spectrum antimicrobial activity. Boron-dipyrromethene (BODIPY) derivatives constitute a promising class of organic photosensitizers with experimentally verified photodynamic activity. However, conventional BODIPY-based photosensitizers face significant limitations: their inherent hydrophobicity reduces reactive oxygen species (ROS) generation efficiency, diminishes antimicrobial coverage, and may paradoxically promote resistance development. Furthermore, their exclusive production of Type I PDT, without complementary Type II mechanisms, substantially restricts their therapeutic potential. ‌Herein, a series of photosensitizers (PSs) with antibacterial properties was developed by leveraging electron push-pull systems coupled with heavy-atom effects. In addition to enhance the aqueous solubility of photosensitizers, three types were encapsulated into liposomes via the thin film hydration method. Benefiting from sufficient molecular rotors and high electronegativity of fluorine, the developed BDP-F Lips exhibit superior ROS generation capacity under laser irradiation, concurrently producing both Type I and Type II PDT, thereby demonstrating excellent antibacterial efficacy.

抗生素的广泛滥用加速了细菌的进化，引发了全球抗菌素耐药性危机。近年来，光动力疗法（PDT）因其无创性、成本效益和广谱抗菌活性而成为一种很有前途的替代方法。硼-二吡咯甲烷（BODIPY）衍生物是一类具有良好光动力学活性的有机光敏剂。然而，传统的基于bodipi的光敏剂面临着显著的局限性：其固有的疏水性降低了活性氧（ROS）的生成效率，降低了抗菌药物的覆盖范围，并可能矛盾地促进耐药性的发展。此外，它们只生产I型PDT，没有补充II型机制，这大大限制了它们的治疗潜力。本文通过利用电子推挽系统和重原子效应，开发了一系列具有抗菌性能的光敏剂（ps）。为了提高光敏剂的水溶性，采用薄膜水化法将三种光敏剂包封在脂质体中。得益于充足的分子转子和氟的高电负性，所研制的BDP-F Lips在激光照射下具有优越的ROS生成能力，可同时产生I型和II型PDT，从而具有优异的抗菌效果。

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引用次数: 0

Ru(II)-catalyzed regioselective [3+2] spiroannulation of 4-arylquinazolin-2(1H)-ones with ynones Ru（II）催化4-芳基喹唑啉-2(1H)- 1与炔酮的区域选择性[3+2]旋环反应

IF 1.5 4区化学 Q3 CHEMISTRY, ORGANIC

Tetrahedron Letters

Pub Date : 2025-09-18 DOI: 10.1016/j.tetlet.2025.155824

T. Ravi Teja , Ch. Ajay , S. Karthik , B. Sridhar , B.V. Subba Reddy

A novel spiroannulation reaction between 4-arylquinazolinones and ynones has been developed to produce highly rigid spiroquinazolinone scaffolds through a [3+2] spirocyclization utilizing a catalytic amount of Ru(II) complex. This innovative strategy generates a broad spectrum of rigid spiro compounds in excellent yields with significant regioselectivity. Importantly, this process involves the CH functionalization of aryl (sp2)H bond followed by a nucleophilic addition of alkenyl ruthenium to imine functionality

利用Ru（II）络合物的催化量，通过[3+2]的螺旋环化反应，开发了一种新的4-芳基喹唑啉酮和炔酮之间的螺旋环化反应，生产出高刚性的螺旋喹唑啉酮支架。这种创新的策略产生了广泛的刚性螺旋化合物，具有优异的产量和显著的区域选择性。重要的是，这一过程涉及芳基（sp2）氢键的CH官能化，随后是亚胺官能化的烯基钌的亲核加成

引用次数: 0

Isosulochrin xanthone and isosulochrin depsidone heterodimers from the endophytic fungus Colletotrichum sp. NF02092 内生真菌Colletotrichum sp. NF02092的异桃金酮山酮和异桃金酮异二聚体

IF 1.5 4区化学 Q3 CHEMISTRY, ORGANIC

Tetrahedron Letters

Pub Date : 2025-09-18 DOI: 10.1016/j.tetlet.2025.155832

Xing Guo , Yang Zhao , Yan Wang, Huiming Ge, Bo Zhang

In this study, we isolated and characterized two polyketides (1 and 2), along with reported depsidone derivative (3) from fermentation broth of the marine fish-derived endophytic fungus Colletotrichum sp. NF02092. The structures of 1 and 2 were deduced on the basis of comprehensive analysis of HRESIMS and NMR spectroscopic data. Both compounds are heterodimers formed by the fusion of the core structure isosulochrin with a xanthan (1) and a depsidone (2), respectively. However, neither 1 nor 2 exhibited significant antimicrobial activity or cytotoxic activities.

在这项研究中，我们从海洋鱼类来源的内生真菌Colletotrichum sp. NF02092的发酵液中分离并鉴定了两种聚酮（1和2）以及报道的depsidone衍生物(3)。在综合分析hremsims和NMR数据的基础上，推导出了1和2的结构。这两种化合物都是异质二聚体，分别由核心结构异氯草苷与黄原胶(1)和depsidone(2)融合而成。然而，1和2都没有表现出显著的抗菌活性或细胞毒活性。

引用次数: 0

Efficient and improved synthesis of kukoamine D and N1,N5,N14-tris(dihydrocaffeoyl)spermine kukoamine D和N1，N5， n14 -三（二氢咖啡因基）精胺的高效改进合成

IF 1.5 4区化学 Q3 CHEMISTRY, ORGANIC

Tetrahedron Letters

Pub Date : 2025-09-17 DOI: 10.1016/j.tetlet.2025.155831

Lijuan Zhai, Lili He, Jingwen Ji, Yuanyu Gao, Jian Sun

Natural products kukoamine D and N¹,N⁵,N¹⁴-tris(dihydrocaffeoyl)spermine, two hydrocaffeoylspermine alkaloids predominantly isolated from Solanaceae plants, exhibit diverse pharmacological activities. However, low natural contents and inefficient synthesis methods limit their applications. Commencing with tert-butyloxycarbonyl (Boc)-protected 1,4-butanediamine, we synthesized kukoamine D and N¹,N⁵,N¹⁴-tris(dihydrocaffeoyl)spermine via an eight-step sequence, achieving overall yields of 29 % and 20 %, respectively. We used a one-pot two-step, nitrile reductive amination method using a nickel chloride (NiCl₂·6H₂O)/sodium borohydride (NaBH₄) system, followed by active esters amidation. The synthesis is simple, cost effective, and scalable. This approach provides a practical route for the industrial production of structurally similar natural products, facilitating pharmacological studies and analog development.

天然产物kukoamine D和N1，N5,N14-tris（二氢咖啡因基）精胺是两种主要从茄科植物中分离出来的氢咖啡因基精胺生物碱，具有多种药理活性。然而，天然含量低和合成方法效率低限制了其应用。从叔丁基羰基（Boc）保护的1,4-丁二胺开始，经过8步合成了kukoamine D和N1，N5,N14-tris（二氢咖啡因基）精胺，总产率分别为29%和20%。采用氯化镍（NiCl2·6H2O）/硼氢化钠（NaBH4）体系进行一锅两步腈还原胺化，然后进行活性酯化。这种合成方法简单、经济、可扩展。这种方法为结构相似的天然产物的工业生产提供了一条实用的途径，促进了药理学研究和类似物的开发。

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引用次数: 0

Diastereoselective, photocatalytic [2 + 2] dimerizations of alkenylboronic acids promoted by sugar alcohols 糖醇促进烯基硼酸的非对映选择性光催化[2 + 2]二聚化反应

IF 1.5 4区化学 Q3 CHEMISTRY, ORGANIC

Tetrahedron Letters

Pub Date : 2025-09-15 DOI: 10.1016/j.tetlet.2025.155827

Anastasia Charlery, Shrey P. Desai, Matthew T. Zambri, Mark S. Taylor

In the presence of the sugar alcohol meso-erythritol, trans-2-arylvinylboronic acids undergo regio- and diastereoselective, photocatalytic [2 + 2] cycloadditions, generating all-trans-substituted cyclobutane-1,2-bis(boronic acid) derivatives. A covalent templating mechanism is proposed, involving in situ formation of a 2:1 boronic acid:tetraol adduct – likely a mixed boronic ester/hemiboronic ester. The protocol has been applied to various substituted trans-2-arylvinylboronic acid derivatives, providing access to chiral, C2-symmetric cyclobutane derivatives that would be challenging to synthesize by other means.

在糖醇中位赤藓糖醇的存在下，反式2-芳基乙烯基硼酸经过区域选择性和非对映选择性光催化[2 + 2]环加成，生成全反式取代的环丁烷-1,2-二（硼酸）衍生物。提出了一种共价模板机制，涉及原位形成2:1硼酸：四醇加合物-可能是混合硼酯/半硼酯。该方案已应用于各种取代的反式2-芳基乙烯基硼酸衍生物，提供了手性，c2对称的环丁烷衍生物，这将是具有挑战性的合成其他方法。

引用次数: 0

Structure–selectivity correlation in asymmetric baeyer–villiger oxidation of 3-arylcyclobutanones by a flavinium ion-pair catalyst 黄离子对催化3-芳基环丁酮不对称baeyer-villiger氧化的结构-选择性关系

IF 1.5 4区化学 Q3 CHEMISTRY, ORGANIC

Tetrahedron Letters

Pub Date : 2025-09-13 DOI: 10.1016/j.tetlet.2025.155826

Junya Fujimoto , Eika Suruga , Natsuhiko Sugimura , Kana Yamamoto

The stereoselective Baeyer–Villiger oxidation of 3-arylcyclobutanones was achieved using a flavinium-based ion-pair catalyst system. Systematic variation of catalyst and substrate structures revealed key structure–selectivity relationships. A simplified catalyst bearing a single stereocenter demonstrated improved or comparable enantioselectivity relative to the original catalyst. Substrates bearing substituents capable of hydrogen–bond donor substituents on the aromatic ring showed enhanced enantioselectivity, with the optimal catalyst–substrate combination affording the γ-lactone product in up to 99% ee.

采用黄基离子对催化体系实现了3-芳基环丁酮的立体选择性Baeyer-Villiger氧化反应。催化剂和底物结构的系统变化揭示了关键的结构-选择性关系。与原始催化剂相比，具有单一立体中心的简化催化剂表现出更好的或相当的对映选择性。在芳香环上具有氢键供体取代基的底物表现出增强的对映选择性，最佳的催化剂-底物组合可提供高达99% ee的γ-内酯产物。

引用次数: 0

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