Organic chemistry frontiers : an international journal of organic chemistry最新文献

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A cross-shaped organic framework: a multi-functional template arranging chromophores† 十字形有机骨架；一种排列发色团的多功能模板

Organic chemistry frontiers : an international journal of organic chemistry

Pub Date : 2025-01-08 DOI: 10.1039/d4qo01808g

Camiel C. E. Kroonen , Adriano D'Addio , Allesandro Prescimone , Daniel Häussinger , Marcel Mayor

This work explores the use of a cross-shaped organic framework that is used as a template for the investigation of multi-functionalized chromophores. We report the design and synthesis of a universal cross-shaped building block bearing two bromines and two iodines on its peripheral positions. The template can be synthesized on a gram scale in a five-step reaction comprising an oxidative homo-coupling macro-cyclization. The formed scaffold was selectively functionalized via Suzuki cross-coupling reactions with methoxynaphthalene, naphthalimide and BODIPY derivatives, yielding a library of cross-shaped and chromophore-decorated model compounds, all of which were fully characterized. The formed racemic bis- and tetra-substituted crosses were resolved via chiral stationary phase HPLC, and assignment of the enantiomers was done via comparison of experimental and simulated electronic circular dichroism spectra as well as enantiomer single-crystal analysis. Additionally, the hybrid naphthalimide/BODIPY chromophore was found to be acting as an intramolecular Förster energy resonance transfer pair, which was investigated in more detail. With this easy-to-functionalize universal building block, we believe it might prove to be useful in the study of different sets of chromophores.

这项工作探索了十字形有机框架的使用，该框架被用作多功能发色团研究的模板。我们报道了一个通用的十字形状的建筑块的设计和合成承载两个溴和两个碘在其外围位置。该模板可以通过氧化-homo偶联大环化的五步反应在克级上合成。通过与甲氧基萘烯、萘酰亚胺和BODIPY衍生物的Suzuki-cross偶联反应，得到了一系列具有十字形状和发色团修饰的模型化合物，并对其进行了充分的表征。通过手性固定相高效液相色谱法对形成的外消旋双取代和四取代交叉进行了拆分，并通过实验和模拟电子圆二色光谱的比较以及对映体单晶分析对其进行了配位。此外，发现杂化萘酰亚胺/BODIPY发色团作为分子内的福斯特能量共振转移对，并对其进行了更详细的研究。有了这个易于功能化的通用构建块，我们相信它可能在研究发色团集方面是有用的。

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引用次数: 0

Modular synthesis of β-oxygen-containing sulfones from alkenes through hexatungstate-catalyzed cascade hydroxysulfenylation/selective oxidation† 六通酸催化级联羟基磺酰化/选择性氧化烯烃模块化合成β-含氧砜

Organic chemistry frontiers : an international journal of organic chemistry

Pub Date : 2025-01-08 DOI: 10.1039/d4qo02151g

Jiaoxiong Li , Zhibin Zhou , Xianghua Zeng , Yongge Wei

β-Oxygen-containing sulfones are versatile building blocks in pharmaceuticals and the chemical industry. Despite notable advances in the reported methods, a sustainable and general catalytic method for preparing β-oxygen-containing sulfones remains elusive, due to the inherent reactivity disparities and notorious metal-catalyst-poisoning capability of sulfur nucleophiles. Here, we present a distinct multifunctional hexatungstate catalytic strategy for the synthesis of β-hydroxy sulfones and β-keto sulfones through a sequential hydroxysulfenylation of alkenes/selective oxidation process, utilizing a commerically available thiol and green hydrogen peroxide as the ‘oxy-sulfonylation reagent’. This method not only offers a practical route for delivering functionalized sulfones from readily available chemicals but is also sufficiently versatile to achieve late-stage oxysulfonylation of complex substrates and concise syntheses of bioactive molecules. Moreover, this modular methodology features a new mechanism, water as the sole byproduct, and mild reaction conditions free of hydroperoxide reductant.

β-含氧砜是制药和化学工业中用途广泛的砌块。尽管已报道的方法取得了显著进展，但由于硫亲核物固有的反应性差异和臭名昭著的金属催化剂毒害能力，制备 β-含氧砜的可持续通用催化方法仍然遥遥无期。在此，我们提出了一种独特的多功能六钨酸盐催化策略，利用一种市售硫醇和绿色过氧化氢作为 "氧磺酰化试剂"，通过烯烃的顺序羟基磺酰化/选择性氧化过程合成β-羟基砜和β-酮砜。这种方法不仅提供了一条从现成化学品中获得功能化砜的实用途径，而且通过对复杂底物进行后期氧磺酰化和生物活性分子的简易合成，展示了其多功能性。此外，这种模块化方法不含过氧化氢还原剂，反应条件温和，水是唯一的副产物，而且机制新颖。

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引用次数: 0

Cation radicals, borenium cations, and a dication from the oxidation of B-tolyl BIII subporphyrins† b - toyl - BIII亚卟啉氧化的阳离子自由基，硼离子和指示

Organic chemistry frontiers : an international journal of organic chemistry

Pub Date : 2025-01-08 DOI: 10.1039/d4qo02291b

Zixuan Xie , Xiaoheng Ji , Xu Zeng , Daiki Shimizu , Takayuki Tanaka , Yutao Rao , Mingbo Zhou , Ling Xu , Atsuhiro Osuka , Jianxin Song

Oxidation of B-tolyl B^III 5,10,15-tritolylsubporphyrin with tris(4-bromophenyl)ammoniumyl hexachloroantimonate gave its cation radical instantaneously, which slowly dissociated to give B^III subporphyrin borenium hexachloroantimonate in 89% yield after stirring overnight. This is a much more convenient method for the synthesis of B^III borenium cations than the previous synthesis with [Et₃Si]⁺[CH₆B₁₁Br₆]⁻. Oxidants such as tris(4-bromophenyl)ammonium tetrakis(perfluorophenyl)borate and AgSbF₆ can be used for the synthesis of the borenium cation. Oxidation of B-tolyl B^III 5,10,15-trianisylsubporphyrin with AgSbF₆ gave a cation radical that was stable at room temperature but dissociated to give the corresponding borenium cation upon refluxing in CH₂Cl₂, while the B-tolyl B^III 5,10,15-tris(4-dibutylaminophenyl)subporphyrin was oxidized to give a cation radical that was easily oxidized to afford a quinonoidal dication. Oxidation of B-tolyl B^III β-hexaethyl-5,10,15-tri(4-diethylaminophenyl)subporphyrin with AgSbF₆ gave a borenium cation instantaneously. As such, the reactivities of the cation radicals depend on the peripheral substituents.

三（4-溴苯基）氨酰基六氯锑酸盐氧化b -甲基bii5,10,15-三硝基亚卟啉，瞬间产生阳离子自由基，搅拌过夜后，阳离子自由基以89%的速率缓慢解离生成bii5 -氨基六氯锑酸硼。这是一种更方便的BIII硼离子合成方法。三（4-溴苯基）四（全氟苯基）硼酸铵和AgSbF6等氧化剂可用于合成硼离子。与AgSbF6氧化b - toyl bii5,10,15 -三苯基亚卟啉得到一个在室温下稳定的阳离子自由基，但在CH2Cl2中回流时解离得到相应的硼离子，而b - toyl bii5,10,15 -三（4-二丁基氨基苯基）亚卟啉被氧化得到一个易于氧化的阳离子自由基，从而提供醌类药物。用AgSbF6氧化b -甲基bii β-六乙基-5,10,15-三（4-二乙基氨基苯基）亚卟啉，立即得到硼离子。因此，阳离子自由基的反应性取决于周围取代基。

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引用次数: 0

Ball-milling and piezoelectric materials enabled radical trifluoromethylation of enamides and acrylamides† 球磨和压电材料使酰胺和丙烯酰胺的自由基三氟甲基化成为可能

Organic chemistry frontiers : an international journal of organic chemistry

Pub Date : 2025-01-08 DOI: 10.1039/d4qo01911c

Vitalii Solomin , Matthias Liard , Philippe Jubault , Thomas Castanheiro

A mechanochemical radical direct C(sp²)–H trifluoromethylation of enamide derivatives was developed using Togni II reagent. Under mechanochemical compression, the use of 0.5 to 1.0 equivalents of piezoelectric materials enabled the solid-state formation of the key CF₃ radical intermediate in mild and sustainable conditions. The use of 0.5 equivalents of piezoelectric materials proved to be just as efficient. The protocol showed a general efficiency and tolerance to multiple functional groups, accessing trifluoromethylated enamides with yields of up to 88% and full stereoselectivity. The reaction conditions were applied to acrylamide substrates, enabling synthesis of trifluoromethylated oxindole derivatives through a radical cascade cyclization initiated from addition of CF₃ radical onto electron-poor C–C double bonds. Radical quenching experiments highlighted a radical mechanism, and control experiments showcased the crucial need to use of piezoelectric materials/ball-milling system.

采用Togni试剂制备了一种机械化学自由基直接C(sp2)-H三氟甲基化酰胺衍生物。在机械化学压缩条件下，施加0.5 ~ 1.0等效压电材料使关键的CF3自由基中间体在温和和可持续的条件下形成固态。压电材料的催化量被证明是同样有效的。该方案显示出一般的效率和对多个官能团的耐受性，获得三氟甲基化酰胺的收率高达88%，具有完全的立体选择性。将该反应条件应用于丙烯酰胺底物，通过在电子贫的C-C双键上由CF3自由基加成引发的自由基级联环化反应合成了三氟甲基化的氧吲哚衍生物。自由基淬火实验强调了自由基机理，而控制实验则表明了压电材料/球磨系统的迫切需要。

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引用次数: 0

Electromagnetic milling promoted mechanochemical copper-catalyzed C–O coupling reaction for diaryl ether formation† 电磁铣削促进铜催化的机械化学C-O偶联反应生成二芳基醚

Organic chemistry frontiers : an international journal of organic chemistry

Pub Date : 2025-01-08 DOI: 10.1039/d4qo01909a

Zhaoxuan Zeng , Zhe Tian , Zhihan Zhang , Hongzhen Sun , Qing Liu , Lizhi Zhang , Fachao Yan , Zengdian Zhao , Hui Liu

A novel copper-catalyzed C–O coupling reaction promoted by electromagnetic milling (EMM) has been reported for the mild and efficient synthesis of various diaryl ethers. This transformation could be realized without solvent and additional heating in a short reaction time, and features a wide substrate scope, good functional group tolerance, and efficient gram-scale synthesis. A ligand derived from oxalic diamide was synthesized and utilized in the solid-state coupling, which exhibited excellent activity towards C–O bond formation under solid state conditions. Additionally, it opens up extensive possibilities for chemical bond activation and construction under multi-energy field coupling conditions.

本文报道了一种新的铜催化的电磁铣削（EMM）催化C-O偶联反应，该反应温和而高效地合成了多种二芳醚。该转化无需溶剂，无需额外加热，反应时间短，具有底物范围广，官能团耐受性好，克级合成效率高的特点。合成了一种由草酸二胺衍生的配体，并将其用于固态偶联中，该配体在固态下对C-O键的形成具有良好的活性。红外光谱控制实验表明，在磁场中高速旋转的电磁棒可能形成Cu(I)-O中间体。此外，它还为多能场耦合下化学键的激活和构建开辟了广阔的可能性。

引用次数: 0

Metal-free synthesis of carboxamides via the Lossen rearrangement† 通过Lossen重排法无金属合成羧酰胺

Organic chemistry frontiers : an international journal of organic chemistry

Pub Date : 2025-01-08 DOI: 10.1039/d4qo02155j

Chong Li , Yi-Fei Liu , Wei Yang , Lian-Jie Zhao , Lin-Yuan Song , Yu-Shuang Deng , Ke-Yu Mou , Jing-Wen Wang , Sheng Cao , Feng Li

A novel and efficient method for synthesizing carboxamides has been developed, utilizing a base-promoted Lossen rearrangement of hydroxylamine derivatives. In these reactions, the hydroxylamine derivatives are bench-top stable and easy to handle, allowing them to smoothly replace highly toxic isocyanate reagents by generating isocyanates in situ. This approach facilitates the straightforward formation of C–P, C–C, or C–N bonds. Furthermore, the mild reaction conditions, straightforward operational procedure, and broad substrate scope render this protocol highly practical and attractive.

利用碱促进羟胺衍生物的Lossen重排，提出了一种新的合成羧胺的高效方法。在这个反应中，羟胺衍生物是稳定的，易于处理，使它们能够通过原位生成异氰酸酯来顺利取代剧毒的异氰酸酯试剂。这种方法使得C-P键和C-C键都能直接形成。此外，温和的反应条件、简单的操作程序和广泛的底物范围使该方案具有很高的实用性和吸引力。

引用次数: 0

Intermolecular amination of ethyl benzo ylacetate via photocatalytic nitrene transfer reactions† 光催化硝基转移反应中乙酸苯乙酯的分子间胺化反应

Organic chemistry frontiers : an international journal of organic chemistry

Pub Date : 2025-01-08 DOI: 10.1039/d4qo02194k

Yujing Guo , Yifan Guo , Luyao Ding , Linlin Shi , Xinqi Hao , Rene M. Koenigs

In this study, we report on a C–H functionalization of 1,3-dicarbonyl compounds via a photocatalytic nitrene transfer reaction. A wide range of 1,3-dicarbonyl substrates and iodinanes were found compatible with the reaction conditions to directly afford the C–H functionalization products without the need of preformation of nucleophilic enolate equivalents. Additionally, a comprehensive series of synthetic applications and control experiments were conducted, thereby further extending the practical utility of this approach.

在本研究中，我们通过光催化硝基转移反应报道了1,3-二羰基化合物的C-H功能化。广泛的1,3-二羰基底物和碘类与反应条件相适应，可以直接产生C-H功能化产物，而不需要预先形成亲核烯酸酯等价物。此外，还进行了一系列综合应用和控制实验，从而进一步扩展了该方法的实际应用。

引用次数: 0

Recent advances in enantioselective construction of C–N bonds involving radical intermediates 含自由基中间体的C-N键对映选择性构建研究进展

Organic chemistry frontiers : an international journal of organic chemistry

Pub Date : 2025-01-08 DOI: 10.1039/d4qo02268h

Jiaqiong Sun , Guangfan Zheng , Ge Zhang , Yan Li , Qian Zhang

This review offers a comprehensive overview of recent advancements in the asymmetric construction of C–N bonds involving radical intermediates. Enantioselective radical amination strategies have proven to be highly effective for synthesizing chiral amines and nitrogen-containing heterocycles. Significant progress has been made in the enantioselective installation of N-containing groups into halogenated alkanes, olefins, and dienes with the asymmetric formation of C–N bonds as the key step via diverse pathways including reductive elimination, radical-polar crossover, amino group substitution, radical–radical cross-coupling, etc. This review highlights these recent developments and the mechanistic insights that drive these transformations.

本综述全面概述了涉及自由基中间体的 C-N 键不对称构建的最新进展。事实证明，对映选择性自由基胺化策略在合成手性胺和含氮杂环方面非常有效。通过还原消除、自由基-极性交叉、氨基取代和自由基-自由基交叉偶联等多种途径，以不对称形成 C-N 键为关键步骤，将含 N 基团对映选择性地安装到卤代烷、烷烃、烯烃和二烯中的研究取得了重大进展。本综述重点介绍了这些最新进展以及驱动这些转化的机理见解。

引用次数: 0

Multichromophoric perylene–iridium triad as a homogeneous photocatalyst for the efficient synthesis of tetrahydroquinoline derivatives† 四氢喹啉衍生物高效合成的多色苝铱三元均相光催化剂

Organic chemistry frontiers : an international journal of organic chemistry

Pub Date : 2025-01-08 DOI: 10.1039/d4qo02269f

Anita Kumari , Sanchita Sengupta

This study presents the design and synthesis of a multichromophoric catalyst system, namely, , which incorporates a perylene monoimide (PMI) as the central chromophore, with naphthalimide (NMI) positioned at its 1- and 7-bay positions, and the catalyst features an iridium (Ir) metal ion coordinated with a cyclopentadienyl (Cp*) unit, a chloride ligand and a cyclometalating ligand attached to PMI. Following photophysical and electrochemical characterization, was utilized as a homogeneous photocatalyst to efficiently synthesize tetrahydroquinolines from N,N-dimethylanilines and maleimides under an aerobic atmosphere. The reaction involves direct cyclization via an sp³ C–H bond functionalization, yielding products in high yields from a diverse range of substrates, with up to 82–83% yields under blue LED (450 nm) irradiation.

本研究设计并合成了一种多显色催化剂体系，即Ir-triad 1，该体系以苝单亚胺（PMI）为中心显色团，萘酰亚胺（NMI）位于其1-和7-位，催化剂的特征是铱（Ir）金属离子与环pentadienyl （Cp*）配位，氯配体和环金属配体附着在PMI上。在进行了光物理和电化学表征之后，利用Ir-triad 1作为均相光催化剂，在好氧气氛下由N， N-二甲苯胺和马来酰亚胺高效合成四氢喹啉。该反应涉及通过sp³C−H键功能化直接环化，从各种底物中获得高收率的产物，在蓝色LED （450 nm）照射下收率高达82-83%。

引用次数: 0

Cobalt-catalyzed regioselective diazidation of 1-aryl-1,3-dienes enabled by a single electron transfer/radical addition/group transfer relay process† 通过单电子转移/自由基加成/基团转移接力过程实现钴催化1 -芳基-1,3-二烯的区域选择性重氮化

Organic chemistry frontiers : an international journal of organic chemistry

Pub Date : 2025-01-08 DOI: 10.1039/d4qo02180k

Chi-Fan Zhu , Jun-Ju Mai , Xiao-Jing Li , Mingyuan Shi , Xiasen Dong , Huinan Fu , Mei-Hua Shen , Hua-Dong Xu

A novel cobalt-catalyzed 1,2-diazidation of 1-aryl-1,3-dienes by using TMSN₃ as an azide source has been reported. A series of vicinal diazides containing unsaturated bonds that are amenable to further functionalization were synthesised with excellent regioselectivity and stereoselectivity under mild conditions. Preliminary mechanistic studies suggest that the reaction proceeds via a single electron transfer/radical addition/group transfer relay process.

报道了以TMSN3为叠氮化物源，钴催化1 -芳基-1,3-二烯的1,2-二氮化反应。在温和的条件下，合成了一系列含有可进一步功能化的不饱和键的邻二叠氮化合物，具有良好的区域选择性和立体选择性。初步机理研究表明，该反应是通过单电子转移/自由基加成/基团转移接力过程进行的。

引用次数: 0

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