Asian Journal of Organic Chemistry最新文献

英文中文

Tuning the Electronic Properties of Benzimidazoles via D‐A‐D/A Functionalization for Enhanced Organic Resistive Memory Performance 通过D-A-D/A功能化调节苯并咪唑的电子特性以增强有机电阻性记忆性能

IF 2.7 4区化学 Q1 CHEMISTRY, ORGANIC

Asian Journal of Organic Chemistry

Pub Date : 2026-01-01 Epub Date: 2025-12-07 DOI: 10.1002/ajoc.70267

Agrawal Khusi , Murali Ardra , Predhanekar Mohamed Imran , Samuthira Nagarajan

The donor‐acceptor system is vital, with benzimidazole emerging as a notable acceptor for memory devices. In this work, a new benzimidazole‐linked benzothiophene was synthesized via Pd‐catalyzed Suzuki cross‐coupling, featuring D‐A‐D and D‐A‐A compounds. UV–vis analysis indicated strong intramolecular interactions and a band gap of 3.12–3.25 eV, suggesting advantageous charge transport properties for memory applications. SEM and thin‐film XRD confirmed improved molecular ordering, substrate coverage, and high crystallinity in the thin films. Non‐volatile binary WORM memory behavior was exhibited by the synthesized compounds. The methoxy‐substituted compound showed effective memory performance with a low threshold voltage (−1.08 V) and an ON/OFF ratio of 10³, while the dibenzofuran‐substituted compound exhibited a higher ON/OFF ratio of 10⁴ and a threshold voltage of −2.62 V. D‐A‐based compounds with varying substituents demonstrated favorable retention time (10³ s) and endurance up to 100 cycles. The observed resistive switching mechanism results from both charge trapping and charge transfer effects. This study underscores the significant impact of substituent alterations in D‐A molecules on molecular arrangement, electron trap depth, and thin film morphology, and all of which significantly influence memory performance in organic devices.

供体-受体系统是至关重要的，苯并咪唑作为一种显著的受体出现在记忆装置中。本研究通过pd催化铃木交叉偶联合成了一种新的苯并咪唑连接的苯并噻吩，具有D-A-D和D-A-A化合物。紫外可见分析表明，该材料具有较强的分子内相互作用，带隙为3.12-3.25 eV，具有良好的电荷输运特性。SEM和薄膜XRD证实了薄膜的分子有序性、衬底覆盖率和高结晶度。合成的化合物具有非易失性二进制WORM记忆行为。甲氧基取代的化合物具有较低的阈值电压（- 1.08 V）和103的ON/OFF比，而二苯并呋喃取代的化合物具有较高的ON/OFF比（104）和- 2.62 V的阈值电压。具有不同取代基的d基化合物具有良好的保留时间（103 s）和长达100次循环的耐久性。所观察到的电阻开关机制是电荷捕获和电荷转移效应共同作用的结果。这项研究强调了D-A分子中取代基的改变对分子排列、电子陷阱深度和薄膜形态的重要影响，所有这些都显著影响有机器件的记忆性能。

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引用次数: 0

ABNO‐Catalyzed Oxidative Dehydrogenation of N‐Heterocycles in the Synthesis of N‐Heteroarenes abno催化n -杂环氧化脱氢合成n -杂芳烃

IF 2.7 4区化学 Q1 CHEMISTRY, ORGANIC

Asian Journal of Organic Chemistry

Pub Date : 2026-01-01 Epub Date: 2025-11-09 DOI: 10.1002/ajoc.70256

Hongtao Yang , Hui Han , Limin Wang , Hao‐Yang Wang , Jianwei Han

We report a method for catalyzing the oxidative dehydrogenation of tetrahydroquinoline and indoline derivatives under metal‐free conditions. With 9‐azabicyclo[3.3.1]nonane N‐oxyl (ABNO) as the catalyst in the presence of potassium tert‐butoxide (^tBuOK), this approach facilitates the efficient oxidative dehydrogenation of partially saturated N‐heterocyclic arylamines to their aromatic counterparts, offering an alternative approach for N‐heterocycle synthesis.

我们报道了一种在无金属条件下催化四氢喹啉和吲哚啉衍生物氧化脱氢的方法。该方法以9-氮杂环[3.3.1]壬烷n -氧基（ABNO）为催化剂，在叔丁二氧化钾（tBuOK）存在下，促进部分饱和n -杂环芳胺氧化脱氢生成相应的芳香族化合物，为n -杂环合成提供了一种替代方法。

引用次数: 0

Discovery of a Novel Cyclobutanol Scaffold With Anti‐Inflammatory Activity and Its Modular Synthesis 具有抗炎活性的新型环丁醇支架的发现及其模块化合成

IF 2.7 4区化学 Q1 CHEMISTRY, ORGANIC

Asian Journal of Organic Chemistry

Pub Date : 2026-01-01 Epub Date: 2025-12-13 DOI: 10.1002/ajoc.70283

Chhabi Lal Chaudhary , Kalpana Ghimire , Kiran Yadav , Hyunjin Kim , Joo‐Won Nam , Jun‐Goo Jee , Jung‐Ae Kim , Byeong‐Seon Jeong , Hyunji Lee

The discovery of novel molecular scaffolds broadens chemical space and supports innovative therapeutics. We identified the underexplored scaffold N‐((3‐hydroxycyclobutyl)(piperidin‐4‐yl)methyl)amide from the ChemBridge database using the similarity ensemble approach (SEA). Seven commercial analogs displayed modest cytotoxicity against prostate (PC‐3, LNCaP) and pancreatic (PANC‐1) cancer cells but significantly inhibited LPS‐induced ROS and nitrite production in RAW 264.7 macrophages, suggesting anti‐inflammatory potential. To expand this scaffold, we developed a modular synthesis. A Ni‐catalyzed reductive coupling of a tosyl‐protected iodopiperidine with 3‐(benzyloxy)cyclobutane‐1‐carboxylic acid successfully provided a key ketone intermediate. Reductive amination and acylation yielded amide derivatives, demonstrating synthetic feasibility. Sodium naphthalenide enabled concurrent O‐benzyl and N‐tosyl deprotection, streamlining the sequence to six steps from simple starting materials. This modular route permits late‐stage incorporation of diverse acyl fragments for analog diversification. Overall, N‐((3‐hydroxycyclobutyl)(piperidin‐4‐yl)methyl)amide is a synthetically accessible scaffold with promising anti‐inflammatory activity, offering a foundation for further optimization and therapeutic development.

新分子支架的发现拓宽了化学领域，支持了创新疗法。我们使用相似集合方法（SEA）从ChemBridge数据库中确定了未开发的支架N-（（3-羟基环丁基）（胡椒苷-4-基）甲基）酰胺。7种商业类似物对前列腺（PC-3, LNCaP）和胰腺（PANC-1）癌细胞表现出适度的细胞毒性，但显著抑制lps诱导的RAW 264.7巨噬细胞的ROS和亚硝酸盐产生，提示抗炎潜力。为了扩展这个支架，我们开发了模块化合成。在镍催化下，甲酰基保护的碘哌啶与3-（苯氧基）环丁烷-1-羧酸成功地进行了还原偶联反应，得到了一个关键的酮类中间体。还原胺化和酰化制得酰胺衍生物，证明了合成的可行性。萘化钠使o -苄基和n -甲苯基同时脱保护，简化了从简单的起始材料到六个步骤的序列。这种模块化的路线允许后期纳入不同的酰基片段模拟多样化。综上所述，N-（（3-羟基环丁基）（胡椒苷-4-基）甲基）酰胺是一种具有良好抗炎活性的可合成支架，为进一步优化和治疗开发提供了基础。

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引用次数: 0

Direct Synthesis of β,γ‐Disubstituted Butenolides via Regioselective β‐Addition of Deconjugated Butenolides to Donor–Acceptor Cyclopropanes Under Lewis Acid Catalysis Lewis酸催化下β，γ-二取代丁烯内酯的区域选择性合成-去共轭丁烯内酯加成于供体-受体环丙烷

IF 2.7 4区化学 Q1 CHEMISTRY, ORGANIC

Asian Journal of Organic Chemistry

Pub Date : 2026-01-01 Epub Date: 2026-02-03 DOI: 10.1002/ajoc.202500632

Kaushik Singha , Papiya Mandal , Koena Ghosh

We report the first Lewis acid catalyzed β‐selective nucleophilic addition of β,γ‐unsaturated‐γ‐butenolides to donor–acceptor cyclopropanes (DACs). The transformation proceeds smoothly under mild conditions to afford β,γ‐disubstituted butenolide derivatives in moderate to high yields, demonstrating an enol‐ester‐type reactivity of lactone. The reaction displays excellent regioselectivity, thereby expanding the reactivity of deconjugated butenolides beyond conventional α‐ and γ‐functionalization. The reaction was successfully scaled up to the gram scale.

我们报道了路易斯酸催化β，γ-不饱和-γ-丁烯内酯在给受体环丙烷（dac）上的β-选择性亲核加成反应。在温和的条件下，转化过程顺利进行，得到中高产率的β，γ-二取代丁烯内酯衍生物，显示出内酯的烯醇酯型反应性。该反应表现出优异的区域选择性，从而扩大了脱共轭丁烯内酯的反应活性，超越了传统的α-和γ-功能化。该反应成功地扩大到克级。

引用次数: 0

Photocatalytic [3+2] Cyclization of Cyclopropylamines With gem‐Difluoroalkenes: Accessing gem‐Difluorinated Cyclopentylamines 宝石-二氟烯烃光催化环丙胺[3+2]环化：获得宝石-二氟化环戊胺

IF 2.7 4区化学 Q1 CHEMISTRY, ORGANIC

Asian Journal of Organic Chemistry

Pub Date : 2026-01-01 Epub Date: 2026-02-03 DOI: 10.1002/ajoc.70298

Wenyi XuZhang , Zifan Yang , Lu Bai , Xiating Jiang , Linjun Liu , Xiaodong Qiu

A photocatalyzed [3+2] cyclization protocol has been developed using cyclopropylamine and gem‐difluoroalkene as the synthetic precursors. Frameworks of gem‐difluorinated cyclopentylamines with the potential for pharmacodynamic promotion are produced in simple conditions and good yields. A certain iridium photocatalyst was carefully screened for the successful proceeding of this reaction. Mechanistic studies disclosed the quenching of the excited iridium photocatalyst by cyclopropylamine, and sequential radical addition to the double bond ensured the formation of cyclopentane. Functional groups such as halogens, esters, cyano, and aliphatic olefins were all tolerated to make this strategy an easy access to the fluorinated cyclopentylamines. Substrates employing heteroaryl‐substituted and tetra‐substituted gem‐difluoroalkenes also make this strategy a method for preparing gem‐difluorinated molecules with elaborate structures.

以环丙胺和宝石二氟烯烃为前驱体，建立了光催化[3+2]环化反应方案。具有药效学促进潜力的宝石二氟化环戊胺骨架在简单的条件和良好的产量下生产。为使该反应顺利进行，对一种铱光催化剂进行了仔细筛选。机理研究揭示了受激铱光催化剂被环丙胺猝灭，双键上连续的自由基加成保证了环戊烷的生成。卤素、酯类、氰基和脂肪烯烃等官能团都是可耐受的，这使得这种方法很容易获得氟化环戊胺。采用异芳基取代和四取代宝石二氟烯烃的底物也使该策略成为制备具有复杂结构的宝石二氟化分子的方法。

引用次数: 0

Palladium/Copper Dual Catalysis in the Cross‐Coupling of Stable Diphosphine Disulfides and Terminal Alkynes in the Presence of Molecular Iodine 钯/铜双催化稳定二硫化氢和末端炔在分子碘存在下的交叉偶联

IF 2.7 4区化学 Q1 CHEMISTRY, ORGANIC

Asian Journal of Organic Chemistry

Pub Date : 2026-01-01 Epub Date: 2026-02-03 DOI: 10.1002/ajoc.70296

Yuki Yamamoto , Kota Iino

A rapid, convenient, one‐pot strategy for the synthesis of 1‐alkynylphosphine sulfides has been developed via Pd/Cu‐catalyzed cross‐coupling between terminal alkynes and P^V–I interelement compound generated from the reaction with air‐ and moisture‐stable tetraphenyldiphosphine disulfides and molecular iodine. The transformation proceeds smoothly under mild conditions, completing within 1 h and affording high conversions to the corresponding 1‐alkynylphosphine sulfides in up to 90% yields. This method provides a practical, efficient route to 1‐alkynylphosphine derivatives using air‐ and moisture‐stable reagents, overcoming the limitations of previous strategies.

利用Pd/ cu催化末端炔与空气和水分稳定的四苯基二膦二硫化物和分子碘反应生成的PV-I元素间化合物的交叉偶联，建立了一种快速、方便的一锅合成1-炔基膦硫化物的策略。在温和的条件下，转化过程顺利进行，在1小时内完成，并以高达90%的收率提供相应的1-炔基膦硫化物的高转化率。该方法为1-炔基膦衍生物的制备提供了一条实用、高效的途径，克服了以往方法的局限性。

引用次数: 0

Copper(I)‐Catalyzed CuAIAC/Allylation Cascade: Modular Synthesis of Fully Substituted Allyl N,N′‐Bicyclic Pyrazolidinones 铜(I)催化的CuAIAC/烯丙基级联：全取代烯丙基N，N ' -双环吡唑烷酮的模块化合成

IF 2.7 4区化学 Q1 CHEMISTRY, ORGANIC

Asian Journal of Organic Chemistry

Pub Date : 2026-01-01 Epub Date: 2025-12-07 DOI: 10.1002/ajoc.70272

Weiguo Wang , Yanqin Wang , Zhihao Zuo , Jingyu Wang , Younan Wang

A copper(I)‐catalyzed CuAIAC/allylation cascade reaction exploiting alkynes, azomethine imines, and allyl bromides has been developed for providing rapid access to fully substituted allyl N,N′‐bicyclic pyrazolidinones, involving the formation of C(sp²)–C(sp³) bond. The interception of the in situ generated cuprate‐pyrazolidinonate intermediate with allyl bromide plays a crucial role in the success of the reaction. In addition, scale‐up synthesis and late‐stage modification of bioactive complex molecules could be achieved. This method also features in complete regioselectivity, broad functional group compatibility, and mild reaction conditions.

研究了一种铜(I)催化的CuAIAC/烯丙基级联反应，利用炔烃、亚胺和烯丙基溴，快速获得完全取代的烯丙基N，N ' -双环吡唑烷酮，并形成C(sp2) -C （sp3）键。烯丙基溴对原位生成的铜-吡唑烷酸中间体的拦截对反应的成功起着至关重要的作用。此外，还可以实现生物活性复合物分子的规模化合成和后期修饰。该方法具有完全的区域选择性、广泛的官能团相容性和温和的反应条件。

引用次数: 0

Self‐Assembled Zn/Co‐Based Coordination Polymer Sensors for Detection of Nitrobenzene and Nitroimidazole Antibiotics 自组装Zn/ co基配位聚合物传感器检测硝基苯和硝基咪唑类抗生素

IF 2.7 4区化学 Q1 CHEMISTRY, ORGANIC

Asian Journal of Organic Chemistry

Pub Date : 2026-01-01 Epub Date: 2025-11-20 DOI: 10.1002/ajoc.202500625

Hao Shu , Wenhui Yao , Guorong Peng , Gao Li , Yanhong Zhang

The on‐time detection of hazardous chemicals is very important in ecological environments. In this work, two new transition metal‐based coordination polymers were synthesized by solvothermal method, namely [Zn(2,5‐dpa)(phen)·H₂O]_n (CP‐1) and [Co(2,5‐dpa)(dmphen)]_n (CP‐2) (2,5‐dpa = 2,5‐pyridinedicarboxylic acid, phen = 1,10‐phenanthroline, dmphen = 2,9‐dimethyl‐1,10‐phenanthroline). The structures of CP‐1 and CP‐2 were analyzed by single‐crystal x‐ray diffraction. The results show that CP‐1 and CP‐2 exhibit 1D chain structure despite the use of different auxiliary ligands. Luminescence sensing experiments showed that CP‐1 can serve as a highly sensitive sensor for the selective detection of nitrobenzene (NB), as well as nitroimidazole antibiotics metronidazole (MDZ) and ornidazole (ODZ). The detection limits were found to be as low as 1.16 × 10⁻⁵ M for NB, 1.53 × 10⁻⁵ M for MDZ, and 1.26 × 10⁻⁵ M for ODZ, respectively. The possible sensing mechanisms were subsequently analyzed through in‐depth experimental and computational research.

在生态环境中，有害化学物质的实时检测是非常重要的。本文采用溶剂热法合成了两种新的过渡金属基配位聚合物[Zn(2,5-dpa)（phen）·H2O]n （CP-1）和[Co(2,5-dpa)(dmphen)]n (CP-2) （2,5-dpa = 2,5-吡啶二羧酸，phen = 1,10-菲罗啉，dmphen = 2,9-二甲基-1,10-菲罗啉）。用单晶x射线衍射分析了CP-1和CP-2的结构。结果表明，尽管使用了不同的辅助配体，CP-1和CP-2仍呈现1D链结构。发光传感实验表明，CP-1可以作为一种高灵敏度的传感器选择性检测硝基苯（NB），以及硝基咪唑类抗生素甲硝唑（MDZ）和奥硝唑（ODZ）。NB、MDZ和ODZ的检出限分别为1.16 × 10−5 M、1.53 × 10−5 M和1.26 × 10−5 M。随后，通过深入的实验和计算研究，分析了可能的感知机制。

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引用次数: 0

Design of New Efficient Carborane Molecular Scaffolds Utilizing Functionalization of C=C Double Bonds in Boron‐Substituted Allylcarboranes 利用硼取代烯基碳硼烷中C=C双键功能化设计新型高效碳硼烷分子支架

IF 2.7 4区化学 Q1 CHEMISTRY, ORGANIC

Asian Journal of Organic Chemistry

Pub Date : 2026-01-01 Epub Date: 2025-12-07 DOI: 10.1002/ajoc.70270

Victoria M. Alpatova , Evgeny G. Rys , Alexander F. Smol'yakov , Elena G. Kononova , Valentina A. Ol'shevskaya

Some synthetic transformations of the double bonds in the available boron‐substituted allylcarboranes to access a diverse range of new functionalized carborane compounds were described. Addition reactions to the C═C double bond in 9‐allyl‐o‐carborane or 9‐ally‐m‐carborane, such as bromination under the action of NBS/LiBr system or bromoazidation, proceeded under the action of NBS/Me₃SiN₃ and Zn(OTf)₂ as a catalyst successfully provided corresponding dibromo‐ or bromoazide carborane derivatives. Further transformations of the double bond in allylcarboranes were related to oxidation reactions leading to the formation of practically important carborane epoxides under the treatment of mono‐ and diallylcarboranes with mCPBA. Nucleophilic ring opening reactions of the epoxide ring in 9‐(2,3‐epoxypropyl)‐m‐carborane, which was used as an example with N‐ or S‐nucleophiles, were performed, and a number of corresponding carborane‐substituted β‐alcohols were synthesized. The reductive opening of epoxide ring in mono‐ and diepoxypropyl‐substituted carboranes under the action of LiAlH₄ resulted in the formation of secondary boron‐substituted carborane alcohols. An efficient rearrangement of the epoxide ring in 9‐(2,3‐epoxypropyl)‐m‐carborane into the corresponding methylketone using Zn(OTf)₂ as a catalyst is also described. Synthesized compounds were characterized using various spectroscopic techniques like IR, ¹H, ¹¹B NMR, and mass spectrometry data. The structure of five compounds was supported with single‐crystal x‐ray diffraction.

介绍了硼取代烯基碳硼烷中双键的一些合成转化，以获得各种新的功能化碳硼烷化合物。在NBS/Me3SiN3和Zn(OTf)2的催化作用下，9-烯丙基-邻碳硼烷或9-烯丙基-间碳硼烷中C = C双键的加成反应，如在NBS/LiBr体系作用下的溴化反应或溴化反应，成功地得到了相应的二溴或溴叠氮碳硼烷衍生物。烯丙基碳硼烷中双键的进一步转变与氧化反应有关，在单烯丙基碳硼烷和双烯丙基碳硼烷与mCPBA处理下形成了实际重要的碳硼烷环氧化物。以9-（2,3-环氧丙基）-m-碳硼烷为例，与N-亲核试剂或s -亲核试剂进行了环氧环的亲核开环反应，合成了相应的碳硼烷取代β醇。在LiAlH4的作用下，单、二氧基丙基取代碳硼烷环氧环的还原开环，生成了仲硼取代碳硼烷醇。用Zn(OTf)2作为催化剂，将9-（2,3-环氧丙基）-m-碳硼烷中的环氧环有效地重排成相应的甲基酮。合成的化合物使用各种光谱技术进行表征，如IR， 1H， 11B NMR和质谱数据。单晶x射线衍射证实了这五种化合物的结构。

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Formal [3+3] Cyclization Between 3‐Alkynyl‐3‐hydroxyisoindolinones and Substituted Phenols to 2H‐Chromene Based Spiro‐isoindolinones 3-炔基-3-羟基异吲哚酮与取代酚之间的[3+3]形式环化成2h -铬基螺旋异吲哚酮

IF 2.7 4区化学 Q1 CHEMISTRY, ORGANIC

Asian Journal of Organic Chemistry

Pub Date : 2026-01-01 Epub Date: 2025-11-20 DOI: 10.1002/ajoc.70260

Huan‐Zhu Xue , Zhi‐Kui Cao , Mei‐Ting Zhao , Kai‐Cheng Yang , Long Chen

We herein reported a formal [3+3] cyclization reaction between 3‐alkynyl‐3‐hydroxyisoindolinones and substituted phenols, which offered an efficient procedure for the preparation of 2H‐chromene‐based spiro‐isoindolinones. 10 mol% of inexpensive catalyst (Cu(ClO₄)₂·6H₂O or Fe(OTf)₃) proved to be the best to promote the tandem regioselective 1,4‐addition of phenols to the in situ generated β,γ‐alkynyl‐α‐ketimine/intramolecular O‐Michael addition to afford the desired products under mild conditions (25°C, 0.5–24 h) with a broad substrate scope (31 examples) in up to 99% yield. The synthetic utility was demonstrated by the scaled synthesis and further elaboration of the obtained products to polycyclic compounds bearing isoindolinone, 2H‐chromene and five or six‐membered O‐heterocycles.

本文报道了3-炔基-3-羟基异吲哚酮与取代酚之间的正式[3+3]环化反应，为制备2h -铬基螺-异吲哚酮提供了一种有效的方法。结果表明，10 mol%的廉价催化剂(Cu（ClO4)2·6H2O或Fe(OTf)3）最有利于促进原位生成的β，γ-炔基-α-酮胺/分子内O-Michael加成的串联区域选择性1,4-苯酚加成，在温和的条件下（25°C, 0.5-24 h）和广泛的底物范围（31个例子）下获得所需的产物，收率高达99%。通过规模化合成和进一步加工得到含异吲哚酮、2h -铬和五元或六元o杂环的多环化合物，证明了合成的实用性。

引用次数: 0

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