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Chelation-assisted α and β C–H functionalization of aryl alkenes with alkynes and alkenes 芳基烯烃与炔烃和烯烃的α和β C-H 官能化螯合作用
IF 5.4 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2024-07-18 DOI: 10.1039/d4qo00325j
Cheng Zhang, Yu Lin, Yuhang Zhu, Chengxing Peng, Binbin Lv, Li Zhao, Guofu Zhong, Jinfeng Wei, Jian Zhang
The α C–H alkenylation of trans- and cis aryl alkenes through hydroalkenylation of alkynes was demonstrated to be proceeded by the formation of a six-membered exo-palladacycle, affording a wide range of conjugated dienes with an excellent E/Z ratio selectivity. Moreover, the oxidative β C–H alkenylation of dienes using alkenes was investigated to produce conjugated trienes through a seven-membered endo-palladacycle. The chemical derivation and photophysical properties of polyene products were also investigated.
通过炔烃的加氢烯化作用对反式和顺式芳基烯烃进行 α C-H 烯化反应的过程中形成了一个六元外向钯环,从而以优异的 E/Z 比选择性生成了多种共轭二烯。此外,还研究了二烯与烯的氧化 β C-H 烯化反应,通过一个七元内向帕拉二环生成共轭三烯。此外,还研究了多烯产品的化学衍生和光物理性质。
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引用次数: 0
Photoinduced Regioselective Trifluoroalkylation of Ketene Dithioacetals with CF3SO2Na 用 CF3SO2Na 进行光诱导的烯酮二硫代乙醛的区域选择性三氟烷基化反应
IF 5.4 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2024-07-17 DOI: 10.1039/d4qo01203h
Xiaoxiao Yang, Xinyue Ma, Pan Zhou, Shuaiqi Lu, Yongxin Zhang, Chao Shu
Fluoroorganic chemistry continues to fascinate various areas of the pharmaceuticals, agrochemicals, and materials. The incorporation of trifluoromethyl functional groups can provoke remarkable alterations on the chemical stability, metabolic stability and liposolubility of functional molecules. The development of efficient methods to synthesize trifluoromethyl compounds is of significant importance and radical trifluoromethylation of alkenes is a highly attractive strategy in the synthesis of trifluoromethylated compounds. In this study, regioselective hydro trifluoromethylation of ketene dithioacetals with CF3SO2Na was achieved via a visible-light promoted radical-polar process under mild and operationally simple conditions, using an inexpensive organic photocatalyst. The protocol features a low-cost catalyst, good functional group tolerance, a relatively broad range of substrate scope, and good to excellent yields. Gram-scale preparation and synthetic applications demonstrate opportunities to rapidly construct molecular complexity. Mechanistic studies indicated that the transformation involve a regioselective radical addition/radical-polar crossover process.
氟有机化学继续吸引着制药、农用化学品和材料等各个领域。加入三氟甲基官能团可显著改变功能分子的化学稳定性、代谢稳定性和脂溶性。开发合成三氟甲基化合物的高效方法具有重要意义,而烯的自由基三氟甲基化是合成三氟甲基化合物的一种极具吸引力的策略。在本研究中,利用一种廉价的有机光催化剂,在温和且操作简单的条件下,通过可见光促进的自由基-极性过程,用 CF3SO2Na 实现了烯酮二硫代乙醛的区域选择性氢三氟甲基化反应。该方案的特点是催化剂成本低、官能团耐受性好、底物范围相对较广、产率高到极好。克级制备和合成应用为快速构建复杂分子提供了机会。机理研究表明,该转化涉及一个区域选择性自由基加成/自由基-极性交叉过程。
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引用次数: 0
Acyl radicals generated from aldehydes with NHPI as electrocatalyst: aldehydes and alcohols as carbon-centered radical precursors 以 NHPI 为电催化剂从醛生成酰基:以醛和醇为碳中心自由基前体
IF 5.4 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2024-07-17 DOI: 10.1039/d4qo01067a
Rodrigo G. Enríquez, Juan S. Dato-Santiago, Roberto del Río-Rodríguez, José Alemán, Jose A. Fernández-Salas
In this work, we describe how N-hydroxyphthalimide (NHPI) promotes hydrogen atom transfer from aldehydes under electrocatalytic chemical conditions. This involves the generation of phthalimide-N-oxyl (PINO), which abstracts an acyl hydrogen to produce acyl radicals from aldehydes. These acyl radicals then react with oximes or another PINO radical to form redox-active esters (RAEs). Additionally, we detail a Giese-type reaction with electron-deficient alkenes via electrochemical reduction of the generated RAE derivatives. This process produces sp3-carbon centered radicals from aldehydes. We also extend this method to aliphatic alcohols, involving a multi-step electrochemical process to form carbon-centered radicals from readily available alcohols.
在这项工作中,我们描述了 N-羟基邻苯二甲酰亚胺(NHPI)如何在电催化化学条件下促进醛中氢原子的转移。这包括生成邻苯二甲酰亚胺-N-氧(PINO),PINO 从醛中抽取酰基氢生成酰基自由基。然后,这些酰基与肟或另一个 PINO 自由基反应,形成氧化还原活性酯 (RAE)。此外,我们还详细介绍了通过电化学还原生成的 RAE 衍生物与缺电子烯发生的盖斯型反应。这一过程可从醛中生成以 sp3 碳为中心的自由基。我们还将这一方法扩展到脂肪醇,涉及一个多步骤的电化学过程,从容易获得的醇中形成以碳为中心的自由基。
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引用次数: 0
Iron-catalyzed cascade cyclization of diaryldiyn-3-ones with P(O)H compounds: a rapid method for accessing 10-phosphorylated benzo[b]fluorenones 铁催化二芳基二炔-3-酮与 P(O)H 化合物的级联环化:获得 10-磷酸化苯并[b]芴酮的快速方法
IF 5.4 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2024-07-17 DOI: 10.1039/d4qo00703d
Yinwei Cao, Yue Ying, Jieyi Wu, Fushan Chen, Guo Tang, Yufen Zhao
A new inexpensive iron-catalyzed phosphination of diaryldiyn-3-ones under mild condition for the synthesis of 10-phosphorylated benzo[b]fluorenones is presented. The reaction is proposed to proceed via the generation of electrophilic phosphenium species (Ar2POTf) from secondary phosphine oxides in the presence of Tf2O and 2,6-lutidine, followed by cycloaddition with alkynes to form three-membered phosphirenium cation intermediates. Subsequently, a rapid intermolecular tandem cyclization occurs.
本文介绍了一种新的廉价铁催化二芳二炔-3-酮磷酸化反应,该反应在温和条件下合成 10-磷酸化苯并[b]芴酮。该反应是在 Tf2O 和 2,6-lutidine 的存在下,通过仲膦氧化物生成亲电磷铼物种 (Ar2POTf),然后与炔烃发生环化反应,形成三元磷铼阳离子中间体。随后,分子间迅速发生串联环化反应。
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引用次数: 0
Rational design of naphthoquinone-based antibacterial agents through iridium-catalyzed enantioselective β-allenylation of 2-hydroxynaphthoquinones 通过铱催化 2-hydroxynaphthoquinones 的对映体选择性 β-allenylation 合理设计萘醌类抗菌剂
IF 5.4 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2024-07-16 DOI: 10.1039/d4qo01134a
Aditya Chakrabarty, Komal Jaiswal, Mrinmoy De, Santanu Mukherjee
In the backdrop of established biological properties of 2-hydroxynaphthoquinone (lawsone) and related compounds, the rational design of chiral β-butyl lawsone derivatives as potential antibacterial agents, their enantioselective synthesis and investigation of antibacterial properties are described. The synthesis is accomplished through enantioselective β-allenylation of 2-hydroxynaphthoquinones with allenylic alcohols under cooperative catalysis of an Ir(I)/(phosphoramidite,olefin) complex and Lewis acidic La(OTf)3, followed by catalytic hydrogenation. In a rare example of the use of hydroxynapthoquinones in transition metal catalysis, β-allenylic lawsone derivatives are obtained generally in high yield with outstanding enantioselectivity (up to >99.9:0.1 er). The β-butyl lawsone derivatives, bearing a stereogenic center adjacent to the naphthoquinone core, showed high potency against gram-positive bacterial strain MRSA (methicillin-resistant Staphylococcus aureus) with minimum inhibitory concentration (MIC) as low as 1.5 μg/mL and low toxicity to mammalian cell lines such as HEK and HeLa. The bactericidal activity of these compounds is found to depend not just on the substituent at the stereocenter but also on their absolute configuration.
在 2-羟基萘醌(lawsone)及相关化合物的生物特性已得到证实的背景下,本研究介绍了作为潜在抗菌剂的手性 β-丁基 lawsone 衍生物的合理设计、对映选择性合成及其抗菌特性的研究。该合成是在 Ir(I)/(phosphoramidite,olefin) 复合物和路易斯酸性 La(OTf)3 的协同催化下,通过 2-羟基萘醌与别烯醇的对映体选择性β-别烯醇化反应完成的,随后进行催化氢化反应。在过渡金属催化中使用羟基萘醌的一个罕见实例中,β-烯丙基律酮衍生物的产率普遍较高,对映体选择性出色(高达 99.9:0.1er)。β-丁基律酮衍生物的立体中心与萘醌核心相邻,对革兰氏阳性细菌菌株 MRSA(耐甲氧西林金黄色葡萄球菌)具有很高的效力,最低抑菌浓度(MIC)低至 1.5 μg/mL,对哺乳动物细胞系(如 HEK 和 HeLa)的毒性很低。研究发现,这些化合物的杀菌活性不仅取决于立体中心的取代基,还取决于它们的绝对构型。
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引用次数: 0
Rh-Catalyzed Asymmetric Allylation of tert-Butanesulfinamide Rh 催化的叔丁基亚磺酰胺不对称烯丙基化反应
IF 5.4 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2024-07-16 DOI: 10.1039/d4qo00986j
Min Liu, Changkun Li
Chiral allylic tert-butanesulfinamides were developed as bidentate sulfur-olefin ligands for rhodium. Synthesis of such ligands is normally based on diastereoselective addition or reduction. The preparation of the diastereomer of allylic tert-butanesulfinamides is underdeveloped and the influence of the second chiral center is not fully examined. We report Rh-catalyzed asymmetric allylation of tert-butanesulfinamides to synthesize all four stereoisomers of allylic tert-butanesulfinamides. The application of cyclohexyl-substituted bisoxazolinephosphine ligand is the key to control the regioselectivity.
作为铑的双齿硫烯烃配体,开发了手性烯丙基叔丁基亚磺酰胺。此类配体的合成通常基于非对映选择性加成或还原。烯丙基叔丁基亚磺酰胺非对映异构体的制备方法尚不成熟,第二个手性中心的影响也未得到充分研究。我们报告了在 Rh 催化下叔丁烷亚磺酰胺的不对称烯丙基化反应,从而合成了烯丙基叔丁烷亚磺酰胺的所有四种立体异构体。环己基取代双噁唑啉膦配体的应用是控制区域选择性的关键。
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引用次数: 0
Facile synthesis of α-sulfonyl ketoximes from alkenes using sodium sulfinate and NaNO₂ in water 在水中使用亚硫酸钠和 NaNO₂以烯烃为原料轻松合成α-磺酰基酮肟
IF 5.4 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2024-07-16 DOI: 10.1039/d4qo01108b
Zhenlei Zhang, Ning Zhu, Tianheng Liu
A novel synthesis method for α-sulfonyl ketoximes from alkenes, sodium sulfinate, and NaNO₂ in water has been introduced. This intermolecular three-component approach facilitates the one-step formation of C-N and C-S bonds under mild conditions, offering a new, rapid, and straightforward route to α-sulfonyl ketoximes.
本研究介绍了一种在水中从烯、亚硫酸钠和 NaNO₂合成α-磺酰基酮肟的新方法。这种分子间三组分方法有利于在温和的条件下一步形成 C-N 和 C-S 键,为 α-磺酰基酮肟的合成提供了一条新的、快速而直接的途径。
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引用次数: 0
Nickel-Catalyzed Reductive Cross-Coupling of Monofluoroalkyl Triflates with Aryl Halides for Monofluoroalkylated Arenes 镍催化的一氟烷基三氟酸盐与芳基卤化物的还原交叉偶联反应制备一氟烷基化烯烃
IF 5.4 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2024-07-16 DOI: 10.1039/d4qo01033g
Zhi-Heng Li, Hao Peng, Panke Zhang, Yu-Ang Hu, Chao Pi, Cuiju Zhu, Hao Xu
Here, we report a nickel-catalyzed reductive C(sp3)−C(sp2) cross-coupling of monofluoroalkyl triflates with aryl halides, yielding a series of functionalized monofluoroalkylated arenes. This method demonstrates mild reaction conditions, a broad scope with excellent functional group compatibility respect to both readily availability substrates. Facile follow-up transformations highlight its utility as an appealing tool in the synthesis of pharmaceutical derivatives. Preliminary mechanistic studies indicate the involvement of a radical-chain mechanism in the reaction.
在此,我们报告了在镍催化下,三氟甲酸单氟烷基酯与芳基卤化物发生还原性 C(sp3)-C(sp2)交叉偶联反应,生成一系列官能化的单氟烷基化烷烃。该方法反应条件温和,适用范围广泛,对两种容易获得的底物都具有极好的官能团兼容性。简便的后续转化突出了它在合成药物衍生物方面的实用性。初步的机理研究表明,该反应涉及自由基链机制。
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引用次数: 0
Recent advancements in Ni/photoredox dual catalysis for the Csp3-Csp3 cross-coupling reactions 用于 Csp3-Csp3 交叉偶联反应的 Ni/photoredox 双催化的最新进展
IF 5.4 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2024-07-16 DOI: 10.1039/d4qo00887a
Qi-Yun Huang, Min Shi
For the construction of Csp3-Csp3 bonds, the cross-coupling reactions in Ni/photoredox dual catalysis have recently achieved significant progress than those of traditional ones. In the past five years, a variety of free radical precursors have been developed to participate in the cross-coupling reactions via a dual photoredox/Ni-catalytic process. In this minireview, we mainly focus on the recent advancements (from 2019 to 2023) in Ni/photoredox dual catalysis for the Csp3-Csp3 cross-coupling reactions.
对于 Csp3-Csp3 键的构建,镍/光氧双重催化中的交叉偶联反应最近比传统反应取得了重大进展。在过去的五年中,人们开发了多种自由基前驱体,通过光氧/镍双催化过程参与交叉偶联反应。在本小视图中,我们主要关注用于 Csp3-Csp3 交叉偶联反应的 Ni/photoredox 双催化的最新进展(从 2019 年到 2023 年)。
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引用次数: 0
Remote C(sp3)−H heteroarylation of N-fluoroarylsulfonamides via a silyl radical process under visible light irradiation 在可见光辐照下通过硅自由基过程实现 N-氟芳酰胺的远程 C(sp3)-H 杂芳基化反应
IF 5.4 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2024-07-16 DOI: 10.1039/d4qo00888j
Ya-Jian Hu, Jin-Chang Liu, Guang-Yi Zhang, Ting-Ting Yuan, Shan Wang, Xiao-Xia Liang, Ping Lan, Ren-Wang Jiang, Martin G Banwell, Yu-Tao He
An efficient method for heteroarylation of unactivated, aliphatic C(sp3)−H bonds has been developed using a novel, visible light-promoted radical-relay sequence. The overall process likely occurs via hydrogen atom transfer between an in situ generated methoxy radical and a silane Si-H bond. The ensuing silicon-centered radical then abstracts the fluorine from N-fluorosulfonamides to produce N-centered radicals that themselves undergo 1,5-hydrogen atom transfer to furnish carbon-centered radicals. The radical-chain process involves the formation of electron donor–acceptor complexes between electron-deficient N-methoxyheteroarenium salts and the fluoride ion that leads to remote δ-C(sp3)−H heteroarylation. Certain product structures were confirmed by X-ray analysis using a single, pre-crystalline coating method. Such outcomes provide new insights into radical relay processes as well as access to a range of new molecular scaffolds.
利用一种新颖的可见光促进自由基中继序列,开发出了一种对未活化的脂肪族 C(sp3)-H 键进行杂芳基化的高效方法。整个过程可能是通过原位生成的甲氧基自由基和硅烷 Si-H 键之间的氢原子转移来实现的。随后产生的硅中心自由基从 N-氟磺酰胺中抽取氟,生成 N-中心自由基,N-中心自由基本身经过 1,5 氢原子转移生成碳中心自由基。自由基链过程包括在缺电子的 N-甲氧基杂硒盐和氟离子之间形成电子供体-受体复合物,从而导致远程 δ-C(sp3)-H 杂芳基化。通过使用单一预结晶涂层方法进行 X 射线分析,确认了某些产品结构。这些成果提供了对自由基中继过程的新见解,以及获得一系列新分子支架的途径。
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引用次数: 0
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Organic Chemistry Frontiers
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