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Synthesis of 4-amino-7-oxyindoles via dearomatization of 4-alkyl-2-alkynylanilines and dual fragment incorporation with O-benzoylhydroxylamines 4-烷基-2-烷基苯胺脱芳及与邻苯甲酰羟胺双片段结合合成4-氨基-7-氧吲哚。
IF 2.7 3区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2026-01-07 DOI: 10.1039/D5OB01832C
Zhengping Wu, Renhua Fan and Qiuqin He

O-Benzoylhydroxylamines have been widely used as important amination reagents in C–N bond construction reactions; however, these reactions have exclusively focused on utilizing the amino group, with the benzoyloxy moiety often discarded as waste. Herein, we achieved the incorporation of both the NH2 and benzoyloxy fragments of O-benzoylhydroxylamines into indole scaffolds via dearomatization of 4-alkyl-2-alkynylanilines and subsequent treatment with single-electron transfer (SET) reagents. The resulting 4-amino-7-oxyindoles allow for further selective structural modifications at the C-4 and C-7 positions as needed, facilitating drug screening investigations.

邻苯甲酰羟胺作为重要的胺化试剂在C-N键构建反应中得到了广泛的应用;然而,这些反应只集中于利用氨基,而苯甲酰氧基部分通常作为废物丢弃。在本研究中,我们通过4-烷基-2-烷基苯胺的脱芳化和随后的单电子转移(SET)试剂处理,将o -苯甲酰羟胺的NH2和苯甲酰氧基片段结合到吲哚支架中。所得的4-氨基-7-氧吲哚允许根据需要在C-4和C-7位置进行进一步的选择性结构修饰,促进药物筛选研究。
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引用次数: 0
Rongalite as a mild reductant for solvent-assisted dechlorination of 3,3-dichlorooxindoles to 3-chloro-2-oxindoles and 2-oxindoles 溶铝酸盐作为温和还原剂用于3,3-二氯吲哚溶剂辅助脱氯制备3-氯-2-吲哚和2-吲哚。
IF 2.7 3区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2026-01-07 DOI: 10.1039/D5OB01526J
Jalagam Swathi, Hari Prasad Kokatla, Sivaparwathi Golla and Nagaraju Naddi

A mild, metal-free, and solvent-controlled reductive dechlorination method has been developed for synthesizing 3-chloro-2-oxindoles, and 2-oxindoles from 3,3-dichlorooxindoles. In this process, Rongalite serves as a mild reducing agent, achieving monodechlorination in polar protic, and complete dehalogenation in polar aprotic solvents, leading to the formation of 3-chloro-2-oxindoles, and oxindoles, respectively. This methodology features several advantages, including the use of inexpensive reagents, mild reaction conditions, simple operational procedures, high yields, and short reaction times.

建立了一种温和、无金属、溶剂控制的还原脱氯方法,用于合成3-氯-2-氧吲哚和由3,3-二氯氧吲哚合成2-氧吲哚。在此过程中,荣格莱特作为温和还原剂,在极性质子溶剂中实现单脱氯,在极性非质子溶剂中实现完全脱卤,分别生成3-氯-2-氧吲哚和氧吲哚。该方法具有几个优点,包括使用廉价试剂,反应条件温和,操作程序简单,收率高,反应时间短。
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引用次数: 0
Visible-light induced sustainable photochemical approach for the synthesis of spirocyclic compounds 可见光诱导可持续光化学方法合成螺环化合物。
IF 2.7 3区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2026-01-07 DOI: 10.1039/D5OB01654A
Praveen P. Singh, Surabhi Sinha, Pallavi Singh and Vishal Srivastava

The application of photocatalysis in organic synthesis has become essential because it enables mild, eco-friendly, and effective transformations to access essential molecular scaffolds. A sustainable and effective technique for generating spirocyclic compounds using photocatalysts is carried out via visible light-induced photochemical methods. This method enables the formation of intricate spirocyclic structures using easily accessible starting materials under moderate, eco-friendly conditions. Several visible light mediated spirocyclization reactions proceed via radical intermediates through a variety of processes, such as hydrogen atom transfer and single-electron transfer. The current developments in photocatalysed synthesis of spirocyclic compounds have been highlighted.

光催化在有机合成中的应用已经变得至关重要,因为它可以实现温和、环保和有效的转化,以获得必需的分子支架。通过可见光诱导光化学方法,实现了一种可持续有效的利用光催化剂合成螺环化合物的技术。这种方法可以在温和、环保的条件下使用容易获得的起始材料形成复杂的螺旋环结构。几种可见光介导的螺旋环化反应通过自由基中间体进行,如氢原子转移和单电子转移。重点介绍了光催化合成螺环化合物的最新进展。
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引用次数: 0
Iron-catalyzed oxidative cleavage of C–N bonds of tertiary amines: syntheses of unsymmetrical ureas from isocyanates 铁催化叔胺C-N键的氧化裂解:异氰酸酯合成不对称脲。
IF 2.7 3区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2026-01-06 DOI: 10.1039/D5OB01697E
Bumairemu Aizezi, Bulunuer Yusan, Pinchang Sun and Abudureheman Wusiman

An iron-catalyzed protocol has been developed for the synthesis of unsymmetrical ureas via a cascade of oxidative C–N bond cleavage of tertiary amines and hydroamination of isocyanates. This strategy employs inexpensive FeCl3 as the catalyst and aqueous TBHP as a benign oxidant in acetonitrile, enabling tertiary anilines to react with various isocyanates at room temperature. The protocol features a broad substrate scope and excellent functional group tolerance, while being operationally simple and scalable. It thus offers a practical and sustainable alternative for the synthesis of ureas.

通过叔胺的C-N键氧化裂解和异氰酸酯的氢胺化反应,建立了一种铁催化合成不对称尿素的方案。该策略采用廉价的FeCl3作为催化剂,在乙腈中采用三必和二必作为良性氧化剂,使叔苯胺在室温下与各种异氰酸酯反应。该协议具有广泛的基板范围和出色的功能组容忍度,同时操作简单且可扩展。因此,它为尿素的合成提供了一种实用和可持续的替代方法。
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引用次数: 0
Basic importance: mechanistic molecular modeling of the ent-copalyl diphosphate synthase from Arabidopsis thaliana (AtCPS) 基本重要性:拟南芥(AtCPS)中对-共聚二磷酸合成酶的机制分子模型。
IF 2.7 3区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2026-01-06 DOI: 10.1039/D5OB01857A
Ian S. Torrence, Reuben J. Peters, Justin B. Siegel and Dean J. Tantillo

Terpene synthases/cyclases catalyze the formation of complex polycyclic natural products via mechanisms proceeding through carbocation intermediates. Their active sites are generally lined with aliphatic and aromatic residues that prevent untoward termination of the reaction via carbocation deprotonation or addition of water, enabling use of the relevant catalytic base, whose positioning is then crucial to product outcome. This has been emphasized by studies with the ent-copalyl pyrophosphate synthase from Arabidopsis thaliana (AtCPS), representative of plant class II diterpene cyclases more generally, as displacement of its (conserved) catalytic base leads to such alternative product outcomes. Here we characterize the mechanistic basis for the profound effects of these disruptions in AtCPS using the TerDockin computational approach, combining quantum chemical electronic structure calculations and docking of the relevant carbocation intermediates, to provide insight into the underlying enzymatic structure–function relationships. Our predictions help identify important bases in the wild type and mutant systems of AtCPS, which include trapped water and the conjugate base of the catalytic acid that initiates terpene cyclization.

萜烯合成酶/环化酶通过碳正离子中间体催化形成复杂的多环天然产物。它们的活性位点通常与脂肪族和芳香族残基相连,以防止通过碳正离子去质子化或加水而导致反应的不幸终止,从而允许使用相关的催化碱,其定位对产物结果至关重要。拟南芥(Arabidopsis thaliana, AtCPS)的对-共聚焦磷酸合成酶(t-copalyl焦磷酸合成酶)的研究已经强调了这一点,AtCPS是植物II类二萜环化酶的代表,因为其(保守的)催化碱的移位导致了这种替代产物的结果。在这里,我们使用TerDockin计算方法,结合量子化学电子结构计算和相关碳正离子中间体的对接,描述了这些破坏对AtCPS产生深远影响的机制基础,以深入了解潜在的酶结构-功能关系。我们的预测有助于识别野生型和突变型AtCPS系统中的重要碱基,其中包括捕获的水和引发萜烯环化的催化酸的共轭碱。
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引用次数: 0
BF3·Et2O-catalyzed dearomative spirocyclization of ynones for the synthesis of spirolactams and spirolactones BF3·et20催化炔酮的脱芳螺环化反应合成螺内酯和螺内酯。
IF 2.7 3区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2026-01-06 DOI: 10.1039/D5OB01826A
Yu Zhao, Jingfu Zhu, Quanye Liu, Kangyi Li, Shu Chen, Yu Cheng, Wei Li and Di Wu

This study presents a BF3·Et2O catalyzed intramolecular cyclization reaction of ynones, enabling the efficient synthesis of spiro-heterocyclic compounds, such as spiro-γ-lactams and spiro-γ-lactones. This reaction enables the synthesis of diverse spirocyclic compounds under metal-free and mild conditions, exhibiting broad substrate compatibility and excellent yields.

本研究提出了一种由BF3·Et2O催化的炔酮分子内环化反应,可以高效合成螺-γ-内酰胺和螺-γ-内酯等螺-杂环化合物。该反应可以在无金属和温和的条件下合成多种螺环化合物,具有广泛的底物相容性和优异的产率。
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引用次数: 0
Diastereoselective construction of spiro-cyclopropyl-pyrazoles via a [2 + 1] annulation reaction of iminoindoline-derived alkenes and 4-bromo-pyrazolones 亚胺吲哚衍生烯烃与4-溴吡唑酮[2 + 1]环反应制备螺环丙基吡唑的非对映选择性结构。
IF 2.7 3区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2026-01-06 DOI: 10.1039/D5OB01841B
Dan Hu, Heng Yin, Fuyu Li, Jiao He, Chenlong Deng, Lixia Liu, Wen Xia, Yulong Li and Chenyi Li

A base-promoted [2 + 1] annulation reaction between iminoindoline-derived alkenes and 4-bromo-pyrazolones has been disclosed, affording a series of novel, pharmaceutically interesting spiro-cyclopropyl pyrazolones containing indolines in good to excellent yields with moderate to good diastereoselectivities. This protocol features broad functional group compatibility, simple operation, and mild reaction conditions.

在亚胺吲哚衍生的烯烃和4-溴吡唑啉酮之间进行了碱促进的[2 + 1]环化反应,得到了一系列新颖的、药学上有趣的含吲哚啉的螺环丙基吡唑啉酮,收率高至高,非对映选择性中等至良好。该方案具有官能团相容性广、操作简单、反应条件温和等特点。
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引用次数: 0
PyBroP/base-promoted one-pot three-component sequential decarboxylative addition reaction of β-keto acids, isatylidene malononitriles and pyridine N-oxides PyBroP/base促进了β-酮酸、异亚基丙二腈和吡啶n -氧化物的一锅三组分顺序脱羧加成反应。
IF 2.7 3区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2026-01-06 DOI: 10.1039/D5OB01772F
Fuzhong Han, Yingdong Na, Lina Jia and Xiangping Hu

A PyBroP/base-promoted three-component sequential decarboxylative nucleophilic addition protocol has been developed. Under the optimized conditions, a wide array of β-keto acids, isatylidene malononitriles and pyridine N-oxides couple efficiently to deliver the desired 3,3-disubstituted oxindole-fused pyridine derivatives in moderate to excellent yields. This method features good functional group tolerance, high positional selectivity, mild reaction conditions, and a one-pot procedure. The methodology can be scaled up to the gram scale, and the synthetic utility of the product was further validated. Control experiments have also been carried out to elucidate the plausible mechanistic pathway.

开发了一种PyBroP/碱基促进的三组分顺序脱羧亲核加成协议。在优化的条件下,大量β-酮酸、异丙二烯丙二腈和吡啶n -氧化物有效偶联,以中等至优异的收率获得所需的3,3-二取代氧吲哚-吡啶衍生物。该方法具有官能团耐受性好、位置选择性高、反应条件温和、一锅反应等特点。该方法可扩展到克级,进一步验证了产物的合成效用。控制实验也进行了阐明合理的机制途径。
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引用次数: 0
Four-component assembly of polysubstituted pyrimidines via dual C(sp3)–H functionalization of primary aliphatic amines 伯脂肪胺的双C(sp3)-H官能化聚取代嘧啶的四组分组装。
IF 2.7 3区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2026-01-06 DOI: 10.1039/D5OB01866H
Kang Liu, Jiaoling Li, Sichen Xu, Xi Zhang, Xue Peng, Yao-Fu Zeng, Xinping Liu, Ying Peng, Zhen Wang and Jinjin Chen

An efficient iodine-promoted four-component reaction has been developed for the synthesis of diverse polysubstituted pyrimidines from simple and readily available starting materials under metal-free conditions. The multicomponent strategy innovatively utilizes primary aliphatic amines as C–C–N synthons, aromatic aldehydes as C1 synthons and ammonium iodide as an environmentally benign nitrogen source, achieving α-C(sp3)–H and β-C(sp3)–H bond functionalization of primary aliphatic amines in one pot. This method offers a valuable alternative for synthesizing structurally diverse pyrimidines.

在无金属条件下,以简单易得的原料为原料,采用碘促进的四组分反应合成了多种多取代嘧啶。该多组分策略创新地利用伯脂肪胺作为C-C-N合子,芳香醛作为C1合子,碘化铵作为环保氮源,在一锅中实现了伯脂肪胺的α-C(sp3)-H和β-C(sp3)-H键功能化。该方法为合成结构多样的嘧啶提供了有价值的替代方法。
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引用次数: 0
A computational investigation of the thermal elimination chemistry of β-borylated sulfoxides. Sulfenic acid vs. boryl sulfenate elimination β-硼化亚砜热消除化学的计算研究。亚硫酸与亚硫酸硼的消除。
IF 2.7 3区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2026-01-05 DOI: 10.1039/D5OB01455G
Eric A. Nicol and Adrian L. Schwan

Electronic structure calculations were performed to assess how a β-boryl substituent modulates barriers for the classical Ei elimination of sulfoxides. Four main boron substituents were investigated: H, Me, F and OMe. Across the series, methanesulfenic-acid elimination exhibits reduced activation free energies and enthalpies as the boron functionality accepts electron density from the Cβ–H bond, promoting a more asynchronous transition state with advanced Cβ–H cleavage and O–H formation and correspondingly less S–Cα bond rupture relative to the benchmark ethyl methyl sulfoxide transition state. Nevertheless, β-boryl substrates of the 1B family access lower-energy minima that lead preferentially to boryl sulfenate elimination: the corresponding ΔG values are 9.5–15.5 kcal mol−1 lower than for the competing proton-transfer (sulfenic-acid) pathway. Replacing methyl with vinyl or phenyl lowers ΔG by 1.9–4.9 kcal mol−1 through enhanced stabilization of developing electron density at sulfur. A comparison of common boronic esters (catechol, pinacol, BMIDA) for both proton-transfer and boronic-ester-transfer pathways shows catechol (Bcat) gives the lowest barriers, whereas BMIDA is distinctive in that its methanesulfenic acid elimination resembles that of methyl ethyl sulfoxide, and boryl-sulfenate elimination is disfavoured owing to loss of intramolecular N → B coordination. Collectively, β-boryl substitution lowers Ei barriers via electron-acceptor stabilization and biases reaction manifolds toward boryl sulfenate elimination, with the extent governed by conjugation patterns and ester identity.

通过电子结构计算来评估β-硼基取代基如何调节经典的Ei消除亚砜的势垒。研究了四种主要的硼取代基:H、Me、F和OMe。在整个系列中,由于硼官能团接受来自Cβ-H键的电子密度,甲烷磺酸消去表现出更低的激活自由能和焓,与基准乙基甲基亚砜过渡态相比,促进了更异步的过渡态,Cβ-H裂解和O-H形成更早,相应的s - c- α键断裂更少。然而,1B家族的β-硼酸基底物获得更低的能量最小值,优先导致硼酸盐的消除:相应的ΔG‡值比竞争性质子转移(硫酸)途径低9.5-15.5 kcal mol-1。用乙烯基或苯基取代甲基,通过增强在硫上显像电子密度的稳定性,可降低ΔG‡1.9-4.9 kcal mol-1。对质子转移途径和硼酯转移途径的常见硼酯(儿茶酚、品酚、BMIDA)进行比较表明,儿茶酚(Bcat)具有最低的屏障,而BMIDA的独特之处在于其甲磺酸的消除类似于甲基乙基亚砜,而由于分子内N→B配位的丧失,硼磺酸的消除不利。总的来说,β-硼基取代通过电子受体稳定降低了Ei势垒,并使反应流形偏向于消除亚硫酸硼基,其程度受共轭模式和酯同一性的支配。
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引用次数: 0
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Organic & Biomolecular Chemistry
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