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Electrochemical 1,2-hydrogen atom transfer functionalizations of N-(benzyloxy)phthalimides† N-(苄氧基)邻苯二甲酰亚胺的电化学 1,2-氢原子转移官能化
IF 4.6 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2024-10-05 DOI: 10.1039/D4QO01607F
Xin Fu, Tingting Ran and Jie Liu

We report a straightforward, catalyst-free method for the cathodic benzylic C–H hydroxyalkylation/arylation of N-(alkyloxy)phthalimides with ketones or cyanopyridines. The reaction is driven by an electrochemically induced 1,2-hydrogen atom transfer involving alkoxy radicals generated by O–N bond cleavage. This protocol provides an efficient approach for the synthesis of a wide range of valuable unsymmetrical 1,2-diols and diarylmethanols.

我们报告了一种直接、无催化剂的方法,用于 N-(烷氧基)邻苯二甲酰亚胺与酮或氰基吡啶的阴极苄基 C-H 羟烷基化/芳基化反应。该反应由电化学诱导的 1,2- 氢原子转移驱动,涉及 O-N 键裂解产生的烷氧基自由基。该方案为合成各种有价值的非对称 1,2-二醇和二芳基甲醇提供了一种有效的方法。
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引用次数: 0
Ir/XuPhos-catalyzed direct asymmetric reductive amination of ketones with secondary amines† Ir/XuPhos 催化的酮与仲胺的直接不对称还原胺化反应
IF 4.6 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2024-10-05 DOI: 10.1039/D4QO01495B
Zhou Luo, Tianxiang Fan, Jingyan Luo, Yuanyuan Liu and Junliang Zhang

A diverse array of bidentate P-containing ligands has been developed for Ir-catalyzed asymmetric hydrogenation, but chiral monodentate phosphine ligands have remained comparatively underexplored. We herein report a novel iridium catalyst with XuPhos as a chiral monodentate phosphine ligand for the direct asymmetric reductive amination of ketones with secondary amines. This catalytic system tolerates a wide range of substrates, providing a series of chiral tertiary amines efficiently with high enantioselectivities. The high catalytic activity is attributed to the presence of the aliphatic cyclohexyl group on the P-atom and the relative configuration of the ligand, which is crucial for XuPhos to act as a monodentate P-ligand for iridium.

目前已开发出多种双齿含 P 配体用于铱催化的不对称氢化反应,但对手性单齿膦配体的研究相对不足。我们在此报告了一种新型铱催化剂,该催化剂以 XuPhos 作为手性单齿膦配体,用于酮与仲胺的直接不对称还原胺化反应。该催化体系可耐受多种底物,能高效地提供一系列手性叔胺,并具有很高的对映选择性。高催化活性归功于 P 原子上脂肪族环己基的存在和配体的相对构型,这对于 XuPhos 作为铱的单位 P 配体至关重要。
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引用次数: 0
Shining light on sulfonium salts and sulfur ylides: recent advances in alkylation under photoredox catalysis 照亮锍盐和硫酰化物:光氧化催化下烷基化的最新进展
IF 4.6 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2024-10-03 DOI: 10.1039/D4QO01644K
Zhe Jin, Tingwei Yu, Hui Wang, Penghao Jia and You Huang

Organosulfur compounds, especially sulfur ylides and sulfonium salts, offer extraordinary potential in organic chemistry due to their distinctive structural properties and reactivities. In the past five years, tremendous progress has been made in sulfur ylide and sulfonium salt chemistry with the advent of photoredox catalysis. Increasing unprecedented reactivities and reactions of organosulfur compounds have been unearthed, which are distinguished from their conventional ionic reactivity. This review highlights the recent advances in alkylation procedures with sulfur ylides, sulfoxonium ylides, sulfonium salts and thianthrenium salts driven by photocatalysis—with emphases on reactions, mechanisms, and applications—aiming to provide guidance for the potential of sulfur-containing species in a wide range of reactions and to inspire further progress in organosulfur chemistry.

有机硫化合物,尤其是硫酰化物和锍盐,因其独特的结构性质和反应活性,在有机化学领域具有非凡的潜力。过去五年中,随着光氧化催化的出现,硫酰化物和锍盐化学取得了巨大进步。有机硫化合物前所未有的反应活性和反应不断增加,与传统的离子反应活性截然不同。本综述重点介绍了在光催化作用下,硫酰化物、硫氧鎓酰化物、锍盐和噻吩鎓盐的烷基化过程的最新进展,重点介绍了反应、机理和应用,旨在为含硫物质在各种反应中的潜力提供指导,并激励有机硫化学取得进一步进展。
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引用次数: 0
Recent developments in the ring-opening transformations of gem-difluorocyclopropanes 宝石-二氟环丙烷开环转化的最新进展
IF 4.6 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2024-10-03 DOI: 10.1039/D4QO01583E
Leiyang Lv, Junqi Su and Zhiping Li

gem-Difluorocyclopropanes (F2CPs), a unique class of cyclopropanes, have attracted particular interest of chemists due to their intrinsic reactivity. In this context, gem-F2CPs have been extensively studied as fluoroallylic synthons in transition metal-catalysed ring-opening/cross-coupling reactions for the preparation of linear/branched monofluoroalkenes via single C–F bond cleavage. In addition, various transformations of gem-F2CPs via double or no C–F bond cleavage have also been rapidly developed. This mini-review summarizes these advances and briefly discusses the design, selectivity, and reaction mechanism, with a particular focus on the last two years.

gem-二氟环丙烷(F2CPs)是一类独特的环丙烷,因其固有的反应活性而引起了化学家的特别兴趣。在此背景下,人们对 gem-F2CPs 作为过渡金属催化的开环/交叉偶联反应中的氟利昂合成物进行了广泛研究,以通过单个 C-F 键裂解制备线性/支链单氟烯。此外,通过双 C-F 键裂解或不通过 C-F 键裂解制备 gem-F2CPs 的各种转化反应也迅速兴起。这篇微型综述总结了这些进展,并简要讨论了其设计、选择性和反应机理,特别是最近两年的进展。
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引用次数: 0
A supramolecular dimer strategy for enhancing the selective generation of sulfides and sulfoxides by visible-light induced photoredox thiol–ene cross-coupling reactions of anthraquinone† 通过可见光诱导的蒽醌光氧化硫醚-烯交叉偶联反应提高硫化物和硫氧化物选择性生成的超分子二聚体策略
IF 4.6 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2024-10-03 DOI: 10.1039/D4QO01454E
Fa-Dong Wang, Kai-Kai Niu, Shengsheng Yu, Hui Liu and Ling-Bao Xing

Enhancing the photocatalytic efficiency of organic photocatalysts and increasing the generation capacity of reactive oxygen species (ROS) have consistently been substantial obstacles. In this study, we designed and synthesized a supramolecular dimer based on anthraquinone (Amvp-CB[8]) between the methylated vinylpyridinium substituted anthraquinone derivative (Amvp) and cucurbit[8]uril (CB[8]) through host–guest interactions in the aqueous solution. Compared to the monomer Amvp, the supramolecular dimer Amvp-CB[8] exhibited significantly enhanced fluorescence and demonstrated remarkable capabilities in generating singlet oxygen (1O2) and superoxide anion radicals (O2˙) in water. Importantly, Amvp-CB[8] displayed superior photocatalytic activity under visible light, facilitating efficient photoredox thiol–ene cross-coupling reactions between phenthiol and styrene, which selectively enabled rapid synthesis of sulfides within 0.5 h and sulfoxides within 12 h, showcasing high efficiency, low catalyst loading, and excellent functional group tolerance. This study introduces a novel supramolecular dimer strategy that enhances the design of efficient photocatalysts for organic conversions in photocatalysis.

提高有机光催化剂的光催化效率和增加活性氧(ROS)的生成能力一直是一个巨大的障碍。在本研究中,我们设计并合成了一种基于蒽醌的超分子二聚体(Amvp-CB[8]),它是甲基化乙烯基吡啶取代蒽醌衍生物(Amvp)与葫芦[8]脲(CB[8])在水溶液中通过主客体相互作用而形成的。与单体 Amvp 相比,超分子二聚体 Amvp-CB[8] 的荧光明显增强,并在水中产生单线态氧(1O2)和超氧阴离子自由基(O2--)方面表现出卓越的能力。重要的是,Amvp-CB[8] 在可见光下显示出卓越的光催化活性,促进了苯硫酚与苯乙烯之间高效的光氧化硫酚-烯交叉偶联反应,在 0.5 小时内选择性地实现了硫化物的快速合成,在 12 小时内实现了硫氧化物的快速合成,显示出高效、低催化剂负载和优异的官能团耐受性。本研究介绍了一种新型超分子二聚体策略,有助于设计光催化有机转化的高效光催化剂。
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引用次数: 0
Mechanistic insights into the gold(i)-catalyzed [3,3]-sigmatropic rearrangement of sulfoniums for the formation of chiral 1,4-dicarbonyls or formal α-arylation of carbonyl compounds† 金(I)催化[3,3]-锍重排生成手性 1,4-二羰基或羰基化合物的正规 α-芳基化的机理透视
IF 4.6 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2024-10-03 DOI: 10.1039/D4QO01061B
Weiping Zhou, Ya-Qing Huang, Vincent Gandon and Arnaud Voituriez

Starting with vinyl sulfoxides and propargyl silane, the Au(I)-catalyzed asymmetric [3,3]-sigmatropic rearrangement of sulfonium intermediates furnished, after a protodemetallation step and hydrolysis of a thionium ion, the corresponding 4-oxo-2-aryl-2-alkyl-pentanal derivatives. From the fine analysis of crude mixtures representative of this transformation, formal α-arylated products of acetone (1-arylpropan-2-one derivatives) and aryl sulfanes were also isolated and characterized, depending on the substrates and reaction conditions used. Therefore, a tentative mechanistic explanation of the formation of these unexpected products was highlighted and DFT calculations have also streamlined the reactivity of these cationic gold(I)-catalyzed transformations.

从乙烯基硫醚和丙炔基硅烷开始,在 Au(I)催化下,锍中间体发生不对称 [3,3]-sigmatropic 重排,经过原脱硫步骤和硫离子水解,得到相应的 4-oxo-2-aryl-2-alkyl-pentanal 衍生物。通过对这一转化过程中具有代表性的粗混合物进行精细分析,还分离出了丙酮(1-芳基丙-2-酮衍生物)和芳基硫烷的α-芳基化产物,并根据所使用的底物和反应条件对其进行了表征。因此,这些意外产物形成的初步机理解释得到了强调,DFT 计算也简化了这些阳离子金(I)催化转化的反应性。
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引用次数: 0
Exploring N-centered umpolung reactivity in photoredox-catalyzed amidation with an α-iminoester† 探索光氧化催化α-氨基酯氨化反应中的 N-中心乌普隆反应活性
IF 4.6 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2024-10-03 DOI: 10.1039/D4QO01515K
Parag Mistry, Subhankar Das, Rik Patra and Indranil Chatterjee

The synthesis of amides and their derivatives has gained significant attention from the scientific community in recent decades due to the presence of amide moieties in many bioactive organic molecules. Pursuing sustainable chemistry using cost-effective starting materials under mild reaction conditions is intriguing and challenging. In this context, we present a method for the direct synthesis of amides from α-keto acids and α-iminoesters. This approach employs an Ir-based photocatalyst to enable redox-neutral C–N bond formation at room temperature through N-center umpolung chemistry. This straightforward protocol is compatible with a broad range of functional groups, allowing for the efficient production of amides from aromatic keto acids and imines as coupling partners in an atom-economical manner.

近几十年来,由于许多生物活性有机分子中存在酰胺分子,酰胺及其衍生物的合成在科学界获得了极大关注。在温和的反应条件下,利用具有成本效益的起始材料追求可持续化学是一件既有趣又具有挑战性的事情。在此背景下,我们提出了一种从 α-酮酸和 α-亚胺酯直接合成酰胺的方法。这种方法采用了一种基于 Ir 的光催化剂,通过 N 中心的umpolung 化学反应,在室温下形成氧化还原中性的 C-N 键。这种简单易行的方法与多种官能团兼容,能以原子经济的方式从芳香酮酸和亚胺作为偶联剂高效生产酰胺。
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引用次数: 0
Ion-pairing assemblies of anion-responsive helical PtII complexes† 阴离子响应螺旋 PtII 复合物的离子配对组装
IF 4.6 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2024-10-02 DOI: 10.1039/D4QO01697A
Yohei Haketa, Maho Kawami, Wataru Ota, Tohru Sato and Hiromitsu Maeda

Naphthylisoquinoline-appended dipyrrolyldiketone PtII complexes as helical π-electronic systems were synthesized. The PtII complexes, showing chiroptical properties in solution, exhibited anion-binding behaviour, resulting in the formation of anion complexes as pseudo π-electronic anions. In combination with the π-electronic cation, the receptor–anion complexes formed charge-by-charge ion-pairing assemblies, with the narcissistic self-sorting columnar structures comprising either of the enantiomers, in the crystal state.

研究人员合成了萘基异构喹啉添加的二吡咯烷酮铂Ⅱ配合物螺旋π电子系统。这些铂Ⅱ配合物在溶液中显示出旋光特性,并表现出阴离子结合行为,从而形成了作为伪π电子阴离子的阴离子配合物。在与π-电子阳离子结合时,受体-阴离子配合物形成了逐电荷离子配对组合,在晶体状态下,自恋式自排序柱状结构由两种对映体中的任何一种组成。
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引用次数: 0
Strongly fluorescent indolizine-based coumarin analogs† 基于吲哚利嗪的强荧光香豆素类似物
IF 4.6 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2024-10-02 DOI: 10.1039/D4QO01216J
Jaqueline S. A. Badaro, Antoni Wrzosek, Olaf Morawski, Adam Szewczyk, Irena Deperasińska and Daniel T. Gryko

It is now possible to prepare 2-oxo-2H-pyrano[2,3-b]indolizine-3-carboxylates with an ordered arrangement of various substituents directly from pyridinium salts and diethyl 2-(ethoxymethylene)malonate, allowing for refined control of their photophysical properties. Facile entry into some previously unknown derivatives is disclosed to demonstrate the potential of this method. The use of substituted picolinium salts, as well as further functionalization of the pyrrole ring, permitted easy introduction of new moieties upon the dye, which enabled fine-tuning of the photophysical properties. The obtained dyes possess absorption and emission spectrum in the blue–green region and fluorescence quantum yields reaching 92%. The parent 2-oxo-pyrano[2,3-b]indolizine-3-carboxylate turned out to be an electron-deficient system with a low-lying LUMO, an electronic transition energy of 2.7 eV and possessing a large oscillator strength. Almost complete overlap of the HOMO and LUMO in the 2-oxo-pyrano[2,3-b]indolizine core is responsible for the large fluorescence quantum yields for almost all prepared derivatives. The reason for maintaining the large emission intensity in polar solvents is that the increase in the dipole moment is accompanied with a significant change in its orientation in space. Fluorescence imaging studies have proven that 2-oxo-pyrano[2,3-b]indolizines penetrate the membrane of living cells. A positively charged analog was synthesized and used to stain intracellular organelles in the H9c2 cell line. This compound did not penetrate the cell membrane, however after permeabilization, it specifically stained the nucleus.

现在有可能直接从吡啶鎓盐和 2-(乙氧基亚甲基)丙二酸二乙酯制备出各种取代基有序排列的 2-氧代-2H-吡喃并[2,3-b]吲嗪-3-羧酸盐,从而对其光物理性质进行精细控制。本研究披露了一些以前未知的衍生物的简易进入方法,以证明这种方法的潜力。通过使用取代的吡啶鎓盐以及吡咯环的进一步官能化,可以很容易地在染料中引入新的分子,从而实现对光物理性质的微调。获得的染料具有蓝绿区域的吸收和发射光谱,荧光量子产率达到 92%。母体 2-氧代吡喃并[2,3-b]吲嗪-3-羧酸盐是一个缺电子系统,具有低洼的 LUMO,电子转变能为 2.7 eV,并具有较大的振荡器强度。2-oxo-pyrano[2,3-b]indolizine 内核的 HOMO 和 LUMO 几乎完全重叠,这也是几乎所有制备的衍生物都能产生较大荧光量子产率的原因。之所以能在极性溶剂中保持较大的发射强度,是因为偶极矩的增加伴随着其空间取向的显著变化。荧光成像研究证明,2-氧代吡喃并[2,3-b]吲嗪类化合物能穿透活细胞膜。我们合成了一种带正电荷的类似物,并将其用于染色 H9c2 细胞系中的细胞器。这种化合物不能穿透细胞膜,但在渗透后能对细胞核产生特异性染色。
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引用次数: 0
Hypervalent iodide(iii)-mediated thiofluorination of alkenes and alkynes from thioureas/thiocarbamoyl fluorides with water and a nucleophilic fluoride source† 高价碘化物(III)介导的硫脲类/硫代氨基甲酰氟与水和亲核氟化源的烯烃和炔烃硫氟化反应
IF 4.6 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2024-10-01 DOI: 10.1039/D4QO01569J
Junyi Zhou, Xiang Wang, Wenjun Tang and Liqin Jiang

The hypervalent iodine(III) mediated oxo/aza/carbon/difluorination of alkenes has made significant progress, although the corresponding fluorination of alkynes cannot be accomplished. However, hypervalent iodine(III) mediated thiofluorination of both alkenes and alkynes has never been achieved before. Herein, three-component alkenyl thiocarbamoyl fluorides, water, and Et3N·3HF or two-component alkenyl thioureas and Et3N·3HF proceeded through cascade hydrolysis/thiofluorination or thiofluorination of terminal/internal unactivated/activated alkenes upon phenyliodine(III)bis(pivalate) in toluene at room temperature, providing access to diversified monofluorinated 1,3-thiazolidin-2-ones, 1,3-thiazinan-2-ones, 2-imino-thiazolidines and 1,3-thiazinan-2-imines with a broad substrate scope, excellent functional group tolerance and excellent regioselectivity. Configurations of some products were found to be opposite to those expected from the traditional mechanism of olefin activation by hypervalent iodines(III). Based on mechanistic studies and product configurations, another mechanism involving a cyclic sulfonium ion intermediate was proposed. This inspired us to further discover that phenyliodine(III)bis(pivalate) with dioxane as solvent enabled thiofuorination of alkynes from alkynyl thioureas and Et3N·3HF, furnishing 2-imino-thiazolidines bearing an exocyclicfluoromethylene as tetrasubstituted fluorinated alkenes with remarkable regio-, chemo- and stereoselectivity (absolute E-isomer). These transformations represent the unprecedented thiofluorination of alkenes/alkynes in one operation directly from nucleophilic sulfur reagents and nucleophilic fluorine reagents.

由高价碘(III)介导的烯烃氧化/氮/碳/二氟化反应取得了重大进展,但炔烃的相应氟化反应却未能实现。然而,高价碘(III)介导的烯烃和炔烃的硫氟化反应还从未实现过。在这里,三组分烯基硫代氨基甲酰氟、水和 Et3N-3HF 或双组分烯基硫脲和 Et3N-3HF,在室温下,通过在甲苯中的苯基碘(III)双(特戊酸酯)对末端/内部未活化/活化的烯烃进行级联水解/硫氟化或硫氟化、提供了获得多样化的单氟 1,3-噻唑烷-2-酮、1,3-噻唑烷-2-酮、2-亚氨基噻唑烷和 1,3-噻唑烷-2-亚胺的途径,具有广泛的底物范围、优异的官能团耐受性和出色的区域选择性。研究发现,一些产物的构型与超价碘(III)活化烯烃的传统机理预期相反。根据机理研究和产物构型,我们提出了另一种涉及环状锍离子中间体的机理。受此启发,我们进一步发现,以二氧六环为溶剂,苯基碘(III)双特戊酸酯可以使炔基硫脲和 Et3N-3HF 发生硫代炔化反应,生成带有外环氟亚甲基的 2-亚氨基噻唑烷,作为四取代氟化烯,具有显著的区域、化学和立体选择性(绝对 E 异构体)。这些转化代表了前所未有的直接从亲核硫试剂和亲核氟试剂通过一次操作对烯/炔进行硫代氟化的过程。
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引用次数: 0
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Organic Chemistry Frontiers
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