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Fluorine Chemistry: An Outlook to the Future 氟化学:展望未来
IF 4.4 2区 化学 Q2 CHEMISTRY, APPLIED Pub Date : 2024-08-28 DOI: 10.1002/adsc.202400881
Véronique Gouverneur

Véronique Gouverneur

  

  

Fluorine chemistry has had a long history with key milestones since the 16th century including the first use of fluorite in smelting, the synthesis of hydrogen fluoride first reported by Carl W. Scheele in 1771, and the production of elemental fluorine by Henri Moissan in 1886. Moissan was awarded the Nobel Prize in Chemistry twenty years later for this achievement. Considering the unique characteristics of fluorine atom and the hazardous nature of both HF and F2, chemists had to overcome considerable barriers to invent fluorinating reagents and processes for the synthesis of fluorochemicals. Intellectually, this is a fascinating field for research, and many groups in academia and industry have contributed great science over the past decades.

Fluorochemicals are produced in large quantities because they play a key role in pharmaceuticals, agrochemicals and materials including components of electric cars and electronics. Today, there are several challenges facing the (fluoro)chemical industry. These include the management of raw materials, transportation, complex supply chains and climate change pressure with a need for urgent decarbonisation and defossilization. These challenges represent new opportunities to develop processes that construct complex functional fluorochemicals “with less”. Regulations are also changing rapidly, not least in the light of the persistent nature of PFAS (per- and polyfluorinated alkyl substances), a situation that has revived the field of carbon-fluorine bond deconstruction. Inventive solutions are appearing fast both for PFAS recovery from waste stream and PFAS destruction.

As the world and the fluorochemical industry continue to change, we need to be able to adapt quickly. We all strive for a future circular fluorochemical industry which is cost effective, avoids the production and handling of dangerous chemicals, and minimises or eradicates waste. We need young scientists with brilliant minds to invent new solutions, and in the process, bring new knowledge on the reactivity of the most electronegative element of the periodic table. After all, the science hero Karl Barry Sharpless, reminded us in the foreword he wrote for the book titled “Efficient Preparations of Fluorine Compounds” edited by Herbert W. Roesky (Wiley 2013), that “A stand-in (e. g., C−Cl) for a C−F group might suffice in some applications but, wishful thinking aside, an honest surrogate for a C−F unit does not exist – nothing even comes close.”

Finally, and so importantly, I am very grateful to the authors for their contributions, and I hope that this Special Issue will inspire young generations of chemists to do research for the best of fluorine chemistry to serve humanity and preserve our beautiful “blue marble”, our home.

Véronique Gouverneur 氟化学历史悠久,自 16 世纪以来取得了许多里程碑式的重要成就,其中包括首次在冶炼中使用萤石、卡尔-W-舍勒(Carl W. Scheele)于 1771 年首次报道氟化氢的合成以及亨利-莫伊桑(Henri Moissan)于 1886 年生产元素氟。Scheele 在 1771 年首次报告了氟化氢的合成,以及 Henri Moissan 在 1886 年生产出元素氟。二十年后,莫瓦桑因此获得诺贝尔化学奖。考虑到氟原子的独特性以及 HF 和 F2 的危险性,化学家们必须克服重重困难,才能发明氟化试剂和氟化合物合成工艺。在过去的几十年里,学术界和工业界的许多团体都做出了巨大的科学贡献。氟化学品被大量生产,因为它们在医药、农用化学品和材料(包括电动汽车和电子产品的组件)中发挥着关键作用。如今,(氟)化学工业面临着一些挑战。这些挑战包括原材料管理、运输、复杂的供应链和气候变化压力,迫切需要去碳化和化石燃料化。这些挑战为开发 "以较少成本 "制造复杂功能性氟化学品的工艺提供了新机遇。法规也在迅速变化,尤其是全氟烷基和多氟烷基物质(PFAS)的持久性,这种情况使碳-氟键解构领域重新焕发生机。随着世界和氟化工行业的不断变化,我们必须能够快速适应。我们都在为未来的循环型氟化学工业而努力,它具有成本效益,避免了危险化学品的生产和处理,最大限度地减少或消除了废物。我们需要拥有聪明才智的年轻科学家来发明新的解决方案,并在这一过程中带来有关元素周期表中电负性最强的元素反应性的新知识。毕竟,科学英雄卡尔-巴里-夏普莱斯(Karl Barry Sharpless)在为赫伯特-W-罗斯基(Herbert W. Roesky)主编的《氟化合物的高效制备》(Wiley 2013)一书所写的前言中提醒我们:"C-F-Cl 的替身(如 C-Cl)是一种氟化合物、最后,也是最重要的一点,我非常感谢各位作者的贡献,希望本特刊能激励年轻一代的化学家从事氟化学研究,为人类服务,保护我们美丽的 "蓝色大理石"--我们的家园。
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引用次数: 0
Light-Induced Direct Decarboxylative Functionalization of Aromatic Carboxylic Acids 光诱导芳香族羧酸直接脱羧功能化
IF 5.4 2区 化学 Q2 CHEMISTRY, APPLIED Pub Date : 2024-08-27 DOI: 10.1002/adsc.202400573
Jia-Lin Tu, Shen Zhengjia, Binbin Huang
Aryl radicals are important intermediates in organic synthesis. The generation of these reactive species via direct decarboxylation of inexpensive and readily available aromatic carboxylic acids is an attractive goal. However, such a process intrinsically exhibits high energy barriers to overcome, which in consequence usually require precious metal catalysis, stoichiometric oxidants and harsh conditions, suffering from limitations such as poor functional group tolerance and low atom economy. In recent years, visible-light-induced photochemical reactions have provided new approaches to address this challenge. Three major strategies have been introduced in this emerging field: 1) one-pot in-situ activation of benzoic acids to generate intermediates such as benzoyl hypobromites or hypoiodites; 2) the use of specialized photocatalysts like biphenyl/1,4-dicyanobenzene to promote decarboxylation through photo-induced electron transfer or charge transfer processes; 3) photo-induced LMCT (Ligand-to-Metal Charge Transfer) strategy where copper or iron salts coordinate to the carboxylate anion and generate aromatic radicals upon visible light excitation. On the basis of these three strategies, this review will systematically summarize the development of visible-light-induced direct decarboxylative functionalization of aromatic carboxylic acids, focusing on the reaction mechanism and substrate scope, and discuss their prospects in organic synthesis.
芳基自由基是有机合成的重要中间体。通过直接对廉价易得的芳香族羧酸进行脱羧反应生成这些活性物质是一个极具吸引力的目标。然而,这一过程本质上需要克服高能量障碍,因此通常需要贵金属催化、符合一定比例的氧化剂和苛刻的条件,并受到官能团耐受性差和原子经济性低等限制。近年来,可见光诱导的光化学反应为解决这一难题提供了新方法。在这一新兴领域,已经引入了三种主要策略:1) 苯甲酸的一锅原位活化,生成苯甲酰基次溴化物或次碘化物等中间产物;2) 使用联苯/1,4-二氰基苯等专用光催化剂,通过光诱导电子转移或电荷转移过程促进脱羧反应;3) 光诱导 LMCT(配体-金属电荷转移)策略,铜盐或铁盐与羧酸阴离子配位,在可见光激发下生成芳香自由基。在这三种策略的基础上,本综述将系统地总结可见光诱导芳香族羧酸直接脱羧官能化的发展,重点讨论反应机理和底物范围,并探讨其在有机合成中的应用前景。
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引用次数: 0
Cu-promoted Access to 1,4-Diazine-fused Isoindoles Through Concomitant Csp3-N and Csp2-N Bonds Formation Starting from Constrained N,O-acetals 从受约束的 N,O-乙醛开始,通过同时形成 Csp3-N 和 Csp2-N 键,以铜为促进剂获得 1,4-重氮融合的异吲哚
IF 5.4 2区 化学 Q2 CHEMISTRY, APPLIED Pub Date : 2024-08-27 DOI: 10.1002/adsc.202400343
Christine Safi, Mohamed Othman, Ata Martin Lawson, Jan Moncol, Hassan Oulyadi, Sergiu Shova, Christophe Waterlot, Alina Ghinet, Adam Daïch
Scarce dihydro-1,4-diazinoisoindole framework bearing two points of diversity was prepared through interesting cascade process based on concomitant Csp3-N and Csp2-N bonds formation. This approach consists on amidation in basic medium of tosyl group by nucleophilic substitution followed by Cu-mediated Goldberg reaction in same operation. The required β-bromoenamide bearing a tosyl group was obtained by tosylation of fused brominated N,O-acetals for the first time in acidic medium using submolar amounts of PTSA. The obtained piperazines act as a powerful reaction intersection as illustrated by the formation of N-heterocyclic system via the intramolecular interception of enamide function.
通过基于 Csp3-N 和 Csp2-N 键同时形成的有趣级联过程,制备出了具有两个多样性点的稀缺二氢-1,4-二氮杂吲哚框架。这种方法包括在碱性介质中通过亲核取代对甲苯基进行酰胺化,然后在同一操作过程中进行铜介导的戈德堡反应。通过使用亚摩尔量的 PTSA 在酸性介质中首次对融合溴化 N,O-乙醛进行对甲苯基反应,获得了所需的带有对甲苯基的 β-溴烯酰胺。通过烯酰胺官能团的分子内截取作用形成的 N-杂环系统表明,所获得的哌嗪类化合物具有强大的反应交集作用。
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引用次数: 0
Iron-Catalyzed Regioselective Borobenzylation of Vinyl Arenes 铁催化的乙烯基烯酮的区域选择性硼苄化反应
IF 5.4 2区 化学 Q2 CHEMISTRY, APPLIED Pub Date : 2024-08-26 DOI: 10.1002/adsc.202400807
Deyuan Meng, Jaesook Yun
Herein, catalytic difunctionalization of vinyl arenes is reported using iron salt as a catalyst without ligands. A series of substituted alkylboronic acid esters was obtained as a single regioisomer from vinyl arenes at 50 °C. This multicomponent protocol enabled the formation of C–C and C–B bonds to produce boroalkylated products in a single process. A non-radical pathway is proposed for the reaction in contrast to the radical pathways of iron-catalyzed hydroalkylation reactions. The organoboron compounds generated from this reaction were further utilized for diverse functional group conversions.
本文报告了以铁盐为催化剂(不含配体)催化乙烯基炔的双官能化过程。在 50 °C的温度下,乙烯基炔以单一异构体的形式获得了一系列取代的烷基硼酸酯。这种多组分方案能够形成 C-C 和 C-B 键,从而在单一过程中生成硼烷化产物。与铁催化的氢烷基化反应的自由基途径不同,该反应采用的是一种非自由基途径。该反应生成的有机硼化合物可进一步用于各种官能团的转化。
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引用次数: 0
Visible-Light-Initiated Uranyl-Catalyzed Hydrosilylation and Hydrosulfonylation of Alkenes and Alkynes 可见光引发的铀催化烯烃和炔烃的氢硅烷化和氢磺酰化反应
IF 5.4 2区 化学 Q2 CHEMISTRY, APPLIED Pub Date : 2024-08-26 DOI: 10.1002/adsc.202400745
Xingxing Gong, Qianyi Zhao, Congqing Zhu
This study investigates the visible-light-initiated uranyl(VI)-catalyzed activation of Si-H bonds through direct hydrogen atom transfer, which facilitates the formation of silyl radicals from silanes. The silyl radical can abstract a chlorine atom from the sulfonyl chloride, leading to the generation of sulfonyl radicals. These silyl radicals and sulfonyl radicals could react with alkenes and alkynes, achieving the first example of uranyl-catalyzed hydrosilylation and hydrosulfonylation of unsaturated C-C bonds. This method features mild reaction conditions and a broad substrate scope, and exhibiting exceptional functional-group tolerance. Consequently, it is suitable for the late-stage functionalization of drug derivatives.
本研究探讨了可见光引发的铀酰(VI)催化活化 Si-H 键的过程,该过程通过直接氢原子转移促进硅烷中硅烷基的形成。硅烷基可从磺酰氯中抽取一个氯原子,从而生成磺酰基。这些硅基和磺酰基可与烯烃和炔烃发生反应,首次实现了铀酰催化的不饱和 C-C 键的氢硅化和氢磺化反应。这种方法的特点是反应条件温和,底物范围广泛,对官能团的耐受性极强。因此,它适用于药物衍生物的后期官能化。
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引用次数: 0
Divergent Synthesis of Multisubstituted Hydroindole Derivatives via [3 + 2] Annulations of p-Quinamines with Nitroalkenes 通过对喹胺与硝基烯的 [3 + 2] 嵌合分歧合成多取代吲哚衍生物
IF 5.4 2区 化学 Q2 CHEMISTRY, APPLIED Pub Date : 2024-08-26 DOI: 10.1002/adsc.202400647
Zengwei Lai, Hao Qin, Didi Liu, Bingrui Wan, Zhe Liu, Yan Ding, Haonan Zong, Yi Huang, Lianghua Zou
The synthesis of two stereoisomers of hydroindole derivatives was achieved through [3 + 2] annulations of p-quinamines with nitroalkenes. Catalyst-free or in the presence of DMAP, the annulation reactions were employed to produce the target products containing four contiguous stereogenic centers. This method enables efficient assessment of multisubstituted and functionalized hydroindole derivatives using readily accessible building blocks and reagents. Furthermore, the anti-inflammatory activity of some resulting hydroindoles was evaluated, with three derivative products showing effective inhibition of NLRP3 inflammasome activation.
通过对喹胺与硝基烯的[3 + 2]环化反应,合成了氢吲哚衍生物的两种立体异构体。在无催化剂或有 DMAP 存在的情况下,环化反应生成了含有四个连续立体中心的目标产物。通过这种方法,可以利用容易获得的构筑基块和试剂,有效地评估多取代和功能化吲哚衍生物。此外,还评估了一些氢吲哚衍生物的抗炎活性,其中三种衍生物能有效抑制 NLRP3 炎性体的激活。
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引用次数: 0
Photocatalyst-Free Wavelength-Dependant Sequential Ring Transformations of Pyrazolo[1,2-a]pyrazolones 吡唑并[1,2-a]吡唑酮的无光催化剂波长依赖性序环转化
IF 5.4 2区 化学 Q2 CHEMISTRY, APPLIED Pub Date : 2024-08-26 DOI: 10.1002/adsc.202400684
Ines Kulašić, Nejc Petek, Helena Brodnik, Uroš Grošelj, Jurij Svete, Bogdan Štefane
We report new sequential wavelength-selective photochemical transformations of 1-alkenylpyrazolo[1,2-a]pyrazolones to pyrazolo[1,2-a][1,2]diazepines or cyclobuta[c]pyrazolo[1,2-a]pyrazolones. Irradiation of 1-alkenylpyrazolo[1,2-a]pyrazolones with visible-light (blue LED, 457 nm) induced selective ‘ring switching’ transformation into pyrazolo[1,2-a][1,2]diazepines, which, upon irradiation with UV A light (black LED, 365 nm) underwent electrocyclisation into cyclobuta[c]pyrazolo[1,2-a]pyrazolones. Due to the very narrow irradiation wavelength now available from OLED sources, the selective formation of either 5,7-bicyclic or 5,5,4-tricyclic ring systems from the 5,5-bicyclic starting material is possible simply by changing the wavelength of the irradiation source. The transformations took place under mild conditions in the absence of additives or photocatalysts. Mechanistic studies indicate that these transformations proceed through the formation of an excited triplet state of the substrate, followed by selective homolytic C(1)–N(8) bond cleavage, intersystem crossing, and cyclization of the zwitterionic intermediate on the ground potential energy surface. Subsequent photoinduced disrotatory stereospecific 4-π-electrocyclization of the 5,7-bicyclic systems leads to 3D-rich 5,5,4-tricyclic products.
我们报告了 1-烯基吡唑并[1,2-a]吡唑啉酮到吡唑并[1,2-a][1,2]二氮杂卓或环丁并[c]吡唑并[1,2-a]吡唑啉酮的新型顺序波长选择性光化学转化。用可见光(蓝色发光二极管,457 纳米)照射 1-烯基吡唑并[1,2-a]吡唑啉酮,可诱导其选择性 "换环 "转化为吡唑并[1,2-a][1,2]二氮杂卓,而在用紫外线 A 光(黑色发光二极管,365 纳米)照射后,这些吡唑并[1,2-a]二氮杂卓又会发生电环化反应,转化为环丁并[c]吡唑并[1,2-a]吡唑啉酮。由于 OLED 光源的照射波长非常窄,因此只需改变照射光源的波长,就能从 5,5 双环起始材料中选择性地形成 5,7 双环或 5,5,4 三环系统。在没有添加剂或光催化剂的情况下,转化在温和的条件下进行。机理研究表明,这些转化是通过底物的激发三重态形成,然后选择性地发生 C(1)-N(8) 键的同源裂解、系统间交叉以及齐聚物中间体在地面势能面上的环化而进行的。随后,5,7-双环体系在光诱导下发生脱旋立体特异性 4-π 电环化反应,生成富含三维的 5,5,4-三环产物。
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引用次数: 0
Visible Light-Induced Cyanomethyl Radical Triggered Cascade Cyclization of Phenyl-Linked 1,6-Enynes with a-Halogenated Acetonitriles 可见光诱导的氰甲基自由基引发的苯基连接的 1,6-炔与 a-卤代乙腈的级联环化反应
IF 5.4 2区 化学 Q2 CHEMISTRY, APPLIED Pub Date : 2024-08-26 DOI: 10.1002/adsc.202400878
Xiao Hu, Bo-Xin Chen, Xiang-Lin Bo, Qing-Fang Zhang, Lin-Ping Hu, Ming-Yu Teng, Guo-Li Huang, Bo Liu
Photo-promoted cyanomethyl radical procedures for the preparation of 2,3-dihydro-1H-indenes and 2,8-dihydrocyclopenta[a]indenes from phenyl-linked 1,6-enynes with α-halogenated acetonitriles are reported. The iodocyanomethylation/cyclization is performed via an atom-transfer radical addition (ATRA) strategy under photocatalyst- and oxidant-free conditions. In particular, the photoinduced cyanomethylative cascade bicyclization is carried out under the fac-Ir(ppy)3/Na2CO3 catalystic symtem and visible light irradiation. These methods offer a one-step and atom-economical access to diverse cyano-group containing five-membered rings with broad substrate scope and high selectivity. A plausible reaction mechanism is also proposed.
本研究报告采用光促进的氰甲基自由基程序,从苯基连接的 1,6-enynes 与 α 卤代乙腈制备 2,3- 二氢-1H-茚和 2,8- 二氢环戊并[a]茚。碘氰基甲基化/环化是在光催化剂和无氧化剂条件下通过原子转移自由基加成(ATRA)策略进行的。特别是,在 fac-Ir(ppy)3/Na2CO3 催化剂结构和可见光照射下,进行了光诱导氰甲基化级联双环化反应。这些方法提供了一种一步到位、原子经济的方法来获得多种含有氰基的五元环,具有广泛的底物范围和高选择性。此外,还提出了一种合理的反应机理。
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引用次数: 0
Construction of Spirocyclic Compounds via Electrochemical Intramolecular Dearomatization of Benzene Derivatives 通过电化学分子内苯衍生物脱芳烃作用构建螺环化合物
IF 5.4 2区 化学 Q2 CHEMISTRY, APPLIED Pub Date : 2024-08-26 DOI: 10.1002/adsc.202400700
Wen-Yun Zhang, Long-Hao Zhu, Yuan-Zheng Cheng, Shu-Li You
The spirocyclic framework is found in many natural products, some of which are biologically active. However, It remains a challenge to develop environmentally friendly and atom-economic synthetic methods. Herein, we report an intramolecular dearomatization reaction of benzene derivatives enabled by electrochemistry-mediated two successive single-electron-transfer (SET) processes, providing an alternative method for the rapid construction of spirocyclic skeletons without using sacrificial reagents. A series of cyclohexadiene products were obtained in 25-81% yields. Furthermore, a proposed mechanism involving a sequential electron transfer event was supported by cyclic voltammetry experiments. This strategy features transition-metal-free conditions and easy handling, which will greatly enhance its practical utility.
螺环框架存在于许多天然产物中,其中一些具有生物活性。然而,开发环境友好且原子经济的合成方法仍是一项挑战。在此,我们报告了通过电化学介导的两个连续单电子转移(SET)过程实现的苯衍生物分子内脱芳反应,为不使用牺牲试剂快速构建螺环骨架提供了另一种方法。一系列环己二烯产品的产率为 25-81%。此外,循环伏安法实验也支持了所提出的涉及电子顺序转移事件的机理。该方法不需要过渡金属,操作简便,大大提高了其实用性。
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引用次数: 0
Palladium‐Catalyzed Cross‐Coupling between Alkylidenecyclopropanes and Boronic Acids 钯催化亚烷基环丙烷与硼酸的交叉偶联反应
IF 5.4 2区 化学 Q2 CHEMISTRY, APPLIED Pub Date : 2024-08-22 DOI: 10.1002/adsc.202400657
Ricardo Rodiño, Fernando Mardones, Krishna Paredes, Claudio A. Jiménez, Ronald Nelson, Jose Mascareñas, Fernando Lopez, Felipe Verdugo
The combination of a Pd(0) source and a phosphoramidite ligand promotes a formal allylic cross‐coupling between alkylidenecyclopropanes (ACPs) and boronic acids to yield synthetically appealing 1,1‐disubstituted alkenes. Remarkably, the reaction proceeds both under neutral and basic conditions, and works with both aryl‐ and alkenylboronic acids. DFT calculations suggest that the reaction entails a C‐C activation/protonation mechanism instead of a hydropalladation pathway, such as has been proposed for other metal‐promoted hydrofunctionalizations of ACPs.
钯(0)源与磷酰胺配体的结合促进了亚烷基环丙烷(ACPs)与硼酸之间的正式烯丙基交叉偶联反应,从而生成合成上极具吸引力的 1,1 二取代烯烃。值得注意的是,该反应既可在中性条件下进行,也可在碱性条件下进行,而且对芳基硼酸和烯基硼酸都有效。DFT 计算表明,该反应涉及一种 C-C 活化/质子化机制,而不是水钯化途径,如其他金属促进的 ACPs 加氢官能化反应。
{"title":"Palladium‐Catalyzed Cross‐Coupling between Alkylidenecyclopropanes and Boronic Acids","authors":"Ricardo Rodiño, Fernando Mardones, Krishna Paredes, Claudio A. Jiménez, Ronald Nelson, Jose Mascareñas, Fernando Lopez, Felipe Verdugo","doi":"10.1002/adsc.202400657","DOIUrl":"https://doi.org/10.1002/adsc.202400657","url":null,"abstract":"The combination of a Pd(0) source and a phosphoramidite ligand promotes a formal allylic cross‐coupling between alkylidenecyclopropanes (ACPs) and boronic acids to yield synthetically appealing 1,1‐disubstituted alkenes. Remarkably, the reaction proceeds both under neutral and basic conditions, and works with both aryl‐ and alkenylboronic acids. DFT calculations suggest that the reaction entails a C‐C activation/protonation mechanism instead of a hydropalladation pathway, such as has been proposed for other metal‐promoted hydrofunctionalizations of ACPs.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":null,"pages":null},"PeriodicalIF":5.4,"publicationDate":"2024-08-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142042558","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
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