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Disulfides as sulfonylation reagents for the synthesis of sulfonated spiro[5.5]trienones under metal free conditions 二硫化物作为磺化试剂在无金属条件下合成磺化螺[5.5]三烯酮
IF 1.5 4区 化学 Q3 CHEMISTRY, ORGANIC Pub Date : 2025-11-01 DOI: 10.1016/j.tetlet.2025.155872
Dong Xia , Jinghong Yang , Hao Peng , Lihu Zhang , Xiaobo Bao
A new facile one pot tandem sulfonylation and 6-exo-trig cyzlization/dearomatization of biaryl ynones was developed. Under metal free conditions, diversified sulfonated spiro[5.5]trienones were prepared using disulfides as sulfonylating reagents.
提出了一种简便的联芳酮单锅串联磺化和6-外三甲基化/脱芳化反应新方法。在无金属条件下,以二硫化物为磺化剂,制备了多种磺化螺[5.5]三烯酮。
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引用次数: 0
Mini-update on the applications of Hypophosphites in organic synthesis with a special focus on sodium hypophosphite (NaH2PO2) 次磷酸钠在有机合成中的应用综述,重点介绍次磷酸钠(NaH2PO2)
IF 1.5 4区 化学 Q3 CHEMISTRY, ORGANIC Pub Date : 2025-10-31 DOI: 10.1016/j.tetlet.2025.155875
Vittal Seema , Murali Mohan Achari Kamsali , Laxman Mahadev Alakonda , Ravi Varala , Mohamed Hussein , Mohammed Mujahid Alam
Sodium hypophosphite (NaH₂PO₂) is an inexpensive, abundant, and environmentally friendly reagent widely used in organophosphorus synthesis. Its stability, low toxicity, and ease of handling make it a versatile “green” phosphorus source. This mini-review highlights recent developments (2019–2025) in its applications, including as a phosphorus donor, reducing agent, catalyst, deuterio-deiodinating agent, and deoxyamination reagent. Related reagents such as H₃PO₂ and Ca(H₂PO₂)₂ are also briefly discussed. Mechanistic insights are provided where relevant, alongside the advantages and limitations of current methodologies. This concise overview aims to guide researchers in harnessing hypophosphite reagents for efficient and sustainable organic synthesis.
次亚磷酸钠是一种廉价、丰富、环保的试剂,广泛应用于有机磷合成。其稳定性、低毒性和易于处理使其成为多功能的“绿色”磷源。这篇小型综述重点介绍了其应用的最新进展(2019-2025),包括作为磷供体、还原剂、催化剂、氘-脱碘剂和脱氧胺试剂。相关的试剂如H₃PO₂和Ca(H₂PO₂)₂也进行了简要的讨论。在相关的地方提供了机械的见解,以及当前方法的优点和局限性。这篇简明的综述旨在指导研究人员利用次磷酸酯试剂进行高效和可持续的有机合成。
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引用次数: 0
HFIP-promoted one-pot synthesis of (Pyrazolo[1,5-a]pyrimidinyl)(indolyl)methanes using Rongalite as a C1 synthon under mild conditions 在温和条件下,以荣格利特为C1合成物,hfip促进了(吡唑[1,5-a]嘧啶基)(吲哚基)甲烷的一锅合成
IF 1.5 4区 化学 Q3 CHEMISTRY, ORGANIC Pub Date : 2025-10-30 DOI: 10.1016/j.tetlet.2025.155876
Durgesh Sarothiya, Abhinay S. Chillal, Umesh A. Kshirsagar
In this report, we established an efficient synthetic strategy for the construction of heterodiarylmethanes via the coupling of pyrazolo[1,5-a]pyrimidine and indole using rongalite as methylene source under metal-free conditions at room temperature in HFIP solvent. Rongalite was used as a relatively benign and metal-free reagent and cost-effective C1 synthon. The present methodology offers a total of 21 examples, moderate to good yields of products and easy operations under the mild conditions. The newly synthesized molecules represent a unique class of functionalized heterocycles with potential biological relevance.
本研究在HFIP溶剂中,在室温无金属条件下,以荣长石为亚甲基源,通过吡唑[1,5-a]嘧啶与吲哚的偶联,建立了一种高效的合成策略。熔铝酸盐是一种相对无害、无金属的试剂,也是一种经济高效的C1合成剂。本方法共提供了21个例子,在温和的条件下,产品收率中等至良好,操作简便。新合成的分子代表了一类独特的功能化杂环,具有潜在的生物学意义。
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引用次数: 0
Halogenated Pyridine Derivatives from Cycloaddition / Cycloreversion of Oxazinone and Haloalkyne Precursors. 恶嗪酮和卤代炔前体环加成/环还原的卤代吡啶衍生物。
IF 1.5 4区 化学 Q3 CHEMISTRY, ORGANIC Pub Date : 2025-10-30 Epub Date: 2025-08-05 DOI: 10.1016/j.tetlet.2025.155765
Elizabeth A Davis, Megan S Hammett, Jonathan R Scheerer

This study explores the merged cycloaddition/cycloreversion of 1,4-oxazinone substrates with haloalkyne 2π reaction components. Haloalkynes proved generally competent in the Diels-Alder operation and exerted a small influence on the regioselection of the reaction sequence as compared to the reaction sequence with the derived terminal alkyne precursors. Following tandem cycloreversion and elimination of CO2, the haloalkynes showed a modest preference for formation of 4-halo pyridine products over 3-halo isomeric variants.

本研究探讨了1,4-恶嗪酮底物与卤代炔2π反应组分的合并环加成/环还原反应。卤代烃在Diels-Alder操作中表现良好,与衍生端炔前体的反应序列相比,卤代烃对反应序列的区域选择影响较小。经过串联环还原和CO2的消除,卤代烃相对于3环异构体更倾向于生成4环吡啶产物。
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引用次数: 0
Step-wise flow synthesis of l-ascorbic acid from L-sorbose l-山梨糖分步流动合成l-抗坏血酸
IF 1.5 4区 化学 Q3 CHEMISTRY, ORGANIC Pub Date : 2025-10-28 DOI: 10.1016/j.tetlet.2025.155851
Maduabuchi Angus Modum , Stefan Smulik , James W. Kim , Andrea Gorrell , Kalindi D. Morgan
Transformation of L-sorbose via sequential acetonide protection, oxidation, and lactonization is a pivotal route towards vitamin C synthesis, yet traditional batch and large fermentation processes have not been radically re-imagined in decades. Herein, we report a step-wise flow platform that accomplishes three key transformations of L-sorbose in minutes with high yields and minimal purification. In the first module, L-sorbose undergoes diacetonide protection in a PTFE coil reactor at 0–5 °C, reaching 95 % (crude) conversion in 30 min. The protected sugar is then oxidized inline to the corresponding 2-keto-L-gluconic acid with final direct lactonization to l-ascorbic acid. Thus, under current conditions, the total conversion of L-sorbose to Vitamin C is achieved in 90 total minutes with 85 % crude Vitamin C yield and 57 % pure Vitamin C yield.
l -山梨糖通过连续的丙酮保护、氧化和内酯化转化是合成维生素C的关键途径,但传统的批量和大型发酵过程在几十年来没有从根本上重新设想。在此,我们报告了一个逐步流动平台,在几分钟内以高产量和最少的纯化完成l -山梨糖的三个关键转化。在第一个模块中,L-sorbose在0-5°C的聚四氟乙烯盘管反应器中接受二丙酮保护,在30分钟内达到95%(粗)转化率。然后,受保护的糖被氧化成相应的2-酮- l-葡萄糖酸,最后直接内酯化成l-抗坏血酸。因此,在目前的条件下,l -山梨糖到维生素C的总转化在90分钟内实现,粗维生素C收率为85%,纯维生素C收率为57%。
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引用次数: 0
Benzindole-based donor-acceptor-donor ratiometric-type fluorescent probe for hydrazine 基于苯并吲哚的供-受体-供-供比例型联氨荧光探针
IF 1.5 4区 化学 Q3 CHEMISTRY, ORGANIC Pub Date : 2025-10-25 DOI: 10.1016/j.tetlet.2025.155873
Guiqin Yu , Xuming Liu , Yan Ming , Bei Wang, Xiang Liu
A novel benzindole-based donor–acceptor–donor (D–A–D) fluorescent probe (HST) has been rationally designed and synthesized for the highly selective and sensitive detection of hydrazine (N₂H₄). The sensing mechanism is based on the hydrazine-triggered nucleophilic addition to the conjugated double bond, which disrupts the intramolecular charge transfer (ICT) process, resulting in significant fluorescence quenching. HST demonstrates remarkable features including a large Stokes shift (136 nm), rapid response within 3 min, excellent selectivity, and a low detection limit (3.47 μM). Furthermore, HST enables direct, naked-eye recognition of hydrazine under both visible and UV light. These findings suggest HST as a promising tool for practical applications in environmental and biological hydrazine monitoring.
合理设计和合成了一种新型的苯并吲哚基给体-受体-给体(D-A-D)荧光探针(HST),用于高选择性和高灵敏度检测联氨(N₂H₄)。该传感机制基于肼引发的共轭双键的亲核加成,破坏了分子内电荷转移(ICT)过程,导致显著的荧光猝灭。HST具有Stokes位移大(136 nm)、3 min内快速响应、高选择性和低检出限(3.47 μM)等显著特性。此外,HST可以在可见光和紫外光下直接、裸眼识别肼。这些发现表明HST在环境和生物联氨监测中具有实际应用前景。
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引用次数: 0
Transition metal-free fluorosulfonylation of cyclopropanol for the synthesis of aliphatic sulfonyl fluorides 环丙醇无过渡金属氟磺化合成脂肪族磺酰氟化合物
IF 1.5 4区 化学 Q3 CHEMISTRY, ORGANIC Pub Date : 2025-10-23 DOI: 10.1016/j.tetlet.2025.155867
Jianquan Hong, Qiang Wang, Xifei Chen, Shengying Gu, Chunxiang Li, Jie Wang, Xinxin Gong, Xiaoyu Wang, Feng Zheng, Changge Zheng
We developed a practical synthesis method for aliphatic sulfonyl fluorides through transition metal-free fluorosulfonylation strategy. The reaction of cyclopropanol with K2S2O5 and NFSI is enforced under mild conditions. This reaction system is suitable for cyclopropanols such as aryl, benzyl, and alkyl cyclopropanol, to achieve the corresponding sulfonyl fluoride compounds in moderate to good yields, wide substrate range, good compatibility, and simple operation.
通过无过渡金属氟磺化策略,开发了一种实用的脂肪族磺酰氟化合物合成方法。环丙醇与K2S2O5和NFSI在温和条件下发生反应。该反应体系适用于芳基、苄基、烷基环丙醇等环丙醇,可制得相应的磺酰氟化合物,产率中高,底物范围广,配伍性好,操作简单。
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引用次数: 0
Efficient synthesis of aryl sulfonyl fluorides via an economical reductive fluorosulfonation strategy under mild conditions 在温和条件下通过经济的还原性氟磺化策略高效合成芳基磺酰氟
IF 1.5 4区 化学 Q3 CHEMISTRY, ORGANIC Pub Date : 2025-10-22 DOI: 10.1016/j.tetlet.2025.155865
Sangni Jiang , Zhihui Lu
This study presents a novel and cost-effective method for synthesizing aryl sulfonyl fluorides using economically accessible starting materials, including the Et3N·HF complex as a safe HF surrogate. Upon reaction with SO2, this reagent generates the fluorosulfonating reagent triethylamine fluorosulfinate (FSO2Et3NH+) in-situ. Acting as both a reducing agent and a reactive intermediate, it enables efficient reactions with aromatic diazonium salts at room temperature without requiring additional oxidants. The approach facilitates the synthesis of diverse aryl sulfonyl fluorides in high yields, addressing limitations of prior methods that often rely on costly reagents or catalysts.
本研究提出了一种新颖而经济的方法来合成芳基磺酰氟化合物,使用经济上可获得的起始材料,包括Et3N·HF配合物作为安全的HF替代品。该试剂与SO2反应,原位生成氟磺化试剂氟亚磺酸三乙胺(FSO2−Et3NH+)。作为还原剂和反应中间体,它可以在室温下与芳香重氮盐有效反应,而不需要额外的氧化剂。该方法有助于以高收率合成各种芳基磺酰氟,解决了以前通常依赖昂贵试剂或催化剂的方法的局限性。
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引用次数: 0
A novel synthetic route to a process-related impurity of alectinib 一种新的合成途径来获得与alectinib工艺相关的杂质
IF 1.5 4区 化学 Q3 CHEMISTRY, ORGANIC Pub Date : 2025-10-21 DOI: 10.1016/j.tetlet.2025.155869
Sai Zhao , Lijuan Zhu , Nian Tong , Qi Qi
A novel synthetic route has been developed for the preparation of a key drug impurity of alectinib, a highly potent ALK inhibitor used in the treatment of non-small cell lung cancer. This impurity, designated as compound 1 and chemically identified as 9-ethyl-6,6-dimethyl-8-[4-(1,4-oxazinan-4-yl)hexahydropyridin-1-yl]-11-oxo-6,11-dihydrobenzo[d]naphtho[3,2-b]furan-3‑carbonitrile, originates from the initial cyclization step in the synthetic procedure of alectinib. In comparison to the method described in the patent, the new route offers several advantages, including higher yields, reduced Pd catalyst loading, and enhanced sustainability. This approach is expected to contribute significantly to the advancement of process chemistry and to improved quality control in the manufacture of alectinib.
制备了用于治疗非小细胞肺癌的高效ALK抑制剂alectinib的关键药物杂质的新合成路线。该杂质被命名为化合物1,化学鉴定为9-乙基-6,6-二甲基-8-[4-(1,4-恶嗪-4-基)六氢吡啶-1-基]-11-氧-6,11-二氢苯并[d]萘-[3,2-b]呋喃-3 -碳腈,起源于alectinib合成过程的初始环化步骤。与专利中描述的方法相比,新路线具有几个优点,包括更高的产率,减少Pd催化剂负载,增强可持续性。该方法有望对工艺化学的进步和改善alectinib生产的质量控制做出重大贡献。
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引用次数: 0
First total synthesis of acronyculatin S 首个首字母缩略词S的全合成
IF 1.5 4区 化学 Q3 CHEMISTRY, ORGANIC Pub Date : 2025-10-21 DOI: 10.1016/j.tetlet.2025.155868
Na Wang , Xilan Jiang , Yujiao He , Mengqi Wang , Yuanwei You , Yufei Che , Dexiu Cui , Hongbo Dong
Acronyculatin S is a naturally occurring benzofuran derivative isolated from Acronychia pedunculata and has been reported to exhibit antibacterial activity. In this study, the first total synthesis of acronyculatin S was achieved through a concise and scalable route involving a Friedel–Crafts acylation, a Sonogashira coupling, and an europium(III)-catalyzed Claisen rearrangement as key steps. However, antibacterial evaluation of the synthetic sample against a panel of Gram-positive bacterial strains revealed no significant inhibitory activity under the tested conditions (MIC > 64 μg/mL). This work provides a reliable synthetic route for accessing acronyculatin S and related analogues, facilitating further studies on the chemical and biological properties of this class of natural products.
首字母缩略词S是一种天然存在的苯并呋喃衍生物,从长尾首字母缩略词中分离出来,据报道具有抗菌活性。在这项研究中,首个首字母缩略蛋白S的全合成是通过一个简洁和可扩展的途径实现的,其中包括Friedel-Crafts酰化,Sonogashira偶联和铕(III)催化的Claisen重排作为关键步骤。然而,合成样品对一组革兰氏阳性菌株的抗菌评价显示,在测试条件下(MIC > 64 μg/mL)没有显著的抑制活性。本工作为获取首字母缩略素S及相关类似物提供了可靠的合成途径,为进一步研究该类天然产物的化学和生物学特性提供了便利。
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引用次数: 0
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Tetrahedron Letters
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