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Recent developments in thiochromene chemistry. 硫铬化学的最新发展。
IF 2.9 3区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2024-07-19 DOI: 10.1039/d4ob00690a
Solai Murugappan, Pranali Vijaykumar Kuthe, Kondapalli Venkata Gowri Chandra Sekhar, Murugesan Sankaranarayanan

Thiochromenes are versatile sulfur-containing heterocyclic compounds that have received considerable interest in drug discovery because of their ability to act as crucial building blocks for synthesizing bioactive compounds. In particular, these scaffolds have found utility in the design of anticancer, anti-HIV, antioxidant, and antimicrobial agents, among others. Despite their pharmacological potential, the synthesis of these scaffolds is less explored in contrast to their oxygen-containing counterparts. This review classifies the synthetic processes into Michael addition, cycloaddition, ring-opening, coupling, cyclization and Diels-Alder reactions, and others. Reaction mechanisms, circumstances, and important instances are thoroughly discussed in each area. For instance, chiral catalysts and substrates like mercaptobenzaldehyde and cinnamaldehyde are used in Michael addition processes to achieve excellent enantioselectivity. In cycloaddition reactions, readily available substrates such as thioisatins and alkynes achieve regioselectivity and product production. Thiochromenes are also synthesized by ring-opening reactions with epoxides or aziridines. These reactions demonstrate the importance of catalysts and solvents in reaction control, particularly palladium catalysts for aryl halides and thiol coupling processes. Another major class discussed is cyclization reactions with alkynyl thiols and alkynes under regulated temperature and pressure conditions to efficiently synthesize thiochromenes. With the use of chiral substrates and catalysts, Diels-Alder processes increase yields and selectivity and enhance the variety of thiochromene compounds. This review emphasizes the versatility of thiochromenes in drug discovery and consolidates the existing literature on thiochromenes, scrutinizing the gaps and opportunities for synthesizing novel thiochromene-containing lead molecules.

硫代苯并吡喃是一种用途广泛的含硫杂环化合物,因其可作为合成生物活性化合物的关键构件而在药物发现领域受到广泛关注。特别是,这些支架在设计抗癌、抗艾滋病毒、抗氧化和抗菌剂等方面发挥了作用。尽管这些支架具有药理潜力,但与含氧支架相比,这些支架的合成研究较少。本综述将合成过程分为迈克尔加成反应、环加成反应、开环反应、偶联反应、环化反应和 Diels-Alder 反应等。每个领域都对反应机制、环境和重要实例进行了深入讨论。例如,巯基苯甲醛和肉桂醛等手性催化剂和底物可用于迈克尔加成反应过程,以实现出色的对映选择性。在环加成反应中,硫代异烷烃和炔烃等易于获得的底物可实现区域选择性和产品生产。硫代苯并可通过与环氧化物或氮丙啶的开环反应合成。这些反应显示了催化剂和溶剂在反应控制中的重要性,尤其是用于芳基卤化物和硫醇偶联过程的钯催化剂。讨论的另一个主要类别是在调节温度和压力条件下与炔硫醇和炔烃的环化反应,以高效合成硫代苯并吡喃。通过使用手性底物和催化剂,Diels-Alder 工艺提高了产率和选择性,并增加了硫代色烯化合物的种类。本综述强调了硫代苯并吡喃在药物发现中的多功能性,并整合了现有的硫代苯并吡喃文献,仔细研究了合成新型含硫代苯并吡喃先导分子的差距和机遇。
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引用次数: 0
Unexpected diselenide metathesis in selenocysteine-substituted biologically active peptides. 硒代半胱氨酸取代的具有生物活性的肽中的意外二硒化偏析。
IF 2.9 3区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2024-07-19 DOI: 10.1039/d4ob00921e
Ying He, Toshiki Takei, Luis Moroder, Hironobu Hojo

Substitution of disulfide bonds with a diselenide bonds in peptides and proteins is an often-used strategy to increase the stability of naturally occurring peptides and proteins. In this paper, diselenide metathesis between model diselenide dimer peptides, as well as that in diselenide(s)-substituted biologically active peptides, were analyzed. Surprisingly, depending on the tertiary structure of the peptides, we observed that the metathesis reaction occurs under physiological conditions even in the absence of reducing agents, light and heating.

在肽和蛋白质中用二硒化键取代二硫键是一种常用的策略,可以提高天然肽和蛋白质的稳定性。本文分析了二硒二聚体模型肽之间的二硒化作用,以及二硒取代的生物活性肽的二硒化作用。令人惊讶的是,根据肽的三级结构,我们观察到在生理条件下,即使没有还原剂、光照和加热,也会发生偏合成反应。
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引用次数: 0
Chromone-deferiprone hybrids as novel MAO-B inhibitors and iron chelators for the treatment of Alzheimer's disease. 作为新型 MAO-B 抑制剂和铁螯合剂治疗阿尔茨海默病的色酮-去铁酮混合物。
IF 2.9 3区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2024-07-19 DOI: 10.1039/d4ob00919c
Da-Jiang Zou, Ren-Zheng Liu, Yang-Jing Lv, Jia-Nan Guo, Miao-Liang Fan, Chang-Jun Zhang, Yuan-Yuan Xie

A series of chromone-deferiprone hybrids were designed, synthesized, and evaluated as inhibitors of human monoamine oxidase B (hMAO-B) with iron-chelating activity for the treatment of Alzheimer's disease (AD). The majority exhibited moderate inhibitory activity towards hMAO-B and potent iron-chelating properties. Particularly, compound 25c demonstrated remarkable selectivity against hMAO-B with an IC50 value of 1.58 μM and potent iron-chelating ability (pFe3+ = 18.79) comparable to that of deferiprone (pFe3+ = 17.90). Molecular modeling and kinetic studies showed that 25c functions as a non-competitive hMAO-B inhibitor. According to the predicted results, compound 25c can penetrate the blood-brain barrier (BBB). Additionally, it has been proved to display significant antioxidant activity and the ability to inhibit neuronal ferroptosis. More importantly, compound 25c reduced the cognitive impairment induced by scopolamine and showed significant non-toxicity in short-term toxicity assays. In summary, compound 25c was identified as a potential anti-AD agent with hMAO-B inhibitory, iron-chelating and anti-ferroptosis activities.

研究人员设计、合成并评估了一系列色酮-去铁酮杂交化合物,将其作为具有铁螯合活性的人单胺氧化酶 B (hMAO-B) 抑制剂,用于治疗阿尔茨海默病(AD)。大多数化合物对 hMAO-B 具有中等程度的抑制活性和强效的铁螯合特性。特别是化合物 25c 对 hMAO-B 具有显著的选择性,其 IC50 值为 1.58 μM,并且具有与去铁酮(pFe3+ = 17.90)相当的强效铁螯合能力(pFe3+ = 18.79)。分子建模和动力学研究表明,25c 是一种非竞争性 hMAO-B 抑制剂。根据预测结果,化合物 25c 可以穿透血脑屏障(BBB)。此外,它还被证明具有显著的抗氧化活性和抑制神经元铁突变的能力。更重要的是,化合物 25c 减少了东莨菪碱引起的认知障碍,并在短期毒性实验中显示出明显的无毒性。总之,化合物 25c 被鉴定为一种潜在的抗反式脂肪酸药物,具有抑制 hMAO-B、螯合铁和抗铁突变的活性。
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引用次数: 0
Visible-light induced selenocyclization of 2-ethynylanilines under ambient conditions: simple FeBr3 as a dual-functional catalyst. 环境条件下可见光诱导的 2-乙炔基苯胺硒环化反应:作为双功能催化剂的简单 FeBr3。
IF 2.9 3区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2024-07-19 DOI: 10.1039/d4ob01062k
Binbin Huang, Xinye Tang, Jiawei Yuan, Mingyu Zhang, Zhenyu Luo, Junlei Wang, Caicai Lu

We report herein a visible-light induced, Fe-catalyzed selenocyclization of 2-ethynylanilines with diselenides under ambient conditions, employing ethyl acetate as a benign solvent with no stoichiometric additive required. The simple iron salt FeBr3 serves as both a photo-induced LMCT (Ligand-to-Metal Charge Transfer) catalyst and a Lewis acid catalyst to promote the desired transformation in a sustainable manner, enabling the facile synthesis of diverse 3-selenylindoles with extended substitution patterns. Moreover, gram-scale reactions and late-stage functionalization of bioactive molecules further highlight the synthetic practicality of this method.

我们在此报告了一种在可见光诱导下,由铁催化的 2-乙炔基苯胺与二硒化物的硒环化反应,该反应采用乙酸乙酯作为良性溶剂,无需化学添加剂。简单的铁盐 FeBr3 既是光诱导 LMCT(配体-金属电荷转移)催化剂,又是路易斯酸催化剂,能以可持续的方式促进所需的转化,从而轻松合成具有扩展取代模式的各种 3-硒基吲哚。此外,克级反应和生物活性分子的后期功能化进一步突出了该方法的合成实用性。
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引用次数: 0
N-Confused strapped calix[4]pyrrole: the missing member of calix[4]pyrrole chemistry. N-混淆的卡利克[4]吡咯:卡利克[4]吡咯化学中缺失的成员。
IF 2.9 3区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2024-07-18 DOI: 10.1039/d4ob00799a
Anik Roy, Dibakar Halder, Ashoke Kumar Patra, Antonio Frontera, Indrajit Saha

The first example of N-confused strapped calix[4]pyrrole 5 is presented. The structural integrity of 5 and its regular isomer 4 was unambiguously confirmed by single crystal X-ray diffraction analysis. Anion binding studies using 1H NMR titration carried out in CDCl3 revealed a small but detectable tendency of 5 to interact with an anion. Conversely, the isomeric regular strapped calix[4]pyrrole 4 displayed high selectivity for fluoride anions under similar experimental conditions. The high fluoride selectivity of 4 and unexpectedly low anion affinity of 5 were ascribed to the presence of intramolecular hydrogen bonds within strapping subunits.

本研究首次展示了 N-混淆杂环萼[4]吡咯 5 的实例。单晶 X 射线衍射分析明确证实了 5 及其常规异构体 4 的结构完整性。在 CDCl3 中使用 1H NMR 滴定法进行的阴离子结合研究表明,5 与阴离子相互作用的趋势很小,但可以检测到。相反,在类似的实验条件下,同分异构的正交萼[4]吡咯 4 对氟阴离子具有很高的选择性。4 的高氟选择性和 5 意外的低阴离子亲和性归因于捆绑亚基中分子内氢键的存在。
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引用次数: 0
Highly efficient esterification of carboxylic acids with O-H nucleophiles through acid/iodide cooperative catalysis. 通过酸/碘化物协同催化,实现羧酸与 O-H 亲核物的高效酯化反应。
IF 2.9 3区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2024-07-17 DOI: 10.1039/d4ob00910j
Dongxu Zuo, Xiong Xiao, Xinyue Ma, Peng Nie, Long Liu, Tieqiao Chen

The esterification of carboxylic acids is an important reaction for preparing esters which find wide applications in various research fields. In this manuscript, we report an acid/iodide cooperative catalytic method which enables highly efficient esterification of carboxylic acids with a wide range of equivalent O-H nucleophiles including both alcohols and weak nucleophilic phenols. Under the reaction conditions, both aromatic and aliphatic carboxylic acids including those bearing functional groups work well, furnishing the corresponding esters in good to high yields. Moreover, this reaction is scalable and applicable to the modification of bioactive molecules. These results demonstrate the synthetic value of this new reaction in organic synthesis.

羧酸酯化反应是制备酯类的重要反应,在各个研究领域都有广泛应用。在本手稿中,我们报告了一种酸/碘协同催化方法,该方法可使羧酸与多种等效 O-H 亲核物(包括醇和弱亲核酚)发生高效酯化反应。在该反应条件下,芳香族和脂肪族羧酸(包括那些带有官能团的羧酸)都能很好地发挥作用,以良好的收率或较高的收率生成相应的酯。此外,该反应具有可扩展性,适用于生物活性分子的改性。这些结果证明了这种新反应在有机合成中的合成价值。
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引用次数: 0
A general approach to construct selenopheno[3,2-b]indole-cored molecules using Fischer indolization. 利用费歇尔吲哚化构建硒吩并[3,2-b]吲哚芯分子的一般方法。
IF 2.9 3区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2024-07-17 DOI: 10.1039/d4ob00788c
Roman A Irgashev, Alexander S Steparuk

A wide series of various selenopheno[3,2-b]indole-based compounds, including 2-aryl-substituted selenopheno[3,2-b]indoles as well as derivatives of benzo[4,5]selenopheno[3,2-b]indole, pyrido[3',2':4,5]selenopheno[3,2-b]indole, pyrazino[2',3':4,5]selenopheno[3,2-b]indole and chromeno[3',4':4,5]selenopheno[3,2-b]indol-6-one, were prepared from the appropriate 3-aminoselenophen-2-carboxylates via a one-pot two-step procedure based on the Fischer indole synthesis. The present synthetic strategy includes the conversion of 3-aminoselenophen-2-carboxylates into 2-unsubstituted 3-aminoselenophenes, their C-2 protonation to form selenophen-3(2H)-iminium cations, and the reaction of these iminium intermediates with arylhydrazines to obtain arylhydrazones of selenophen-3(2H)-ones followed by their Fischer indolization affording selenopheno[3,2-b]indole molecules.

一系列广泛的硒并[3,2-b]吲哚类化合物,包括 2-芳基取代的硒并[3,2-b]吲哚以及苯并[4,5]硒并[3,2-b]吲哚、吡啶并[3',2':4,5]硒并[3,2-b]吲哚、吡嗪并[2',3':在费歇尔吲哚合成法的基础上,通过一步法两步法,从适当的 3-氨基硒酚-2-甲酸酯制备了吡啶并[3',2':4,5]硒并[3,2-b]吲哚和色烯并[3',4':4,5]硒并[3,2-b]吲哚-6-酮。本合成策略包括将 3-aminoselenophen-2-boxylates 转化为 2-unsubstituted 3-aminoselenophenes, 将其 C-2 质子化形成硒酚-3(2H)-亚氨阳离子,再将这些亚氨中间体与芳基肼反应,得到硒酚-3(2H)-酮的芳基肼,然后将其费歇尔吲哚化,得到硒吩并[3,2-b]吲哚分子。
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引用次数: 0
Preparative scale Achmatowicz and aza-Achmatowicz rearrangements catalyzed by Agrocybe aegerita unspecific peroxygenase. Agrocybe aegerita 非特异性过氧酶催化的制备规模 Achmatowicz 和 aza-Achmatowicz 重排。
IF 2.9 3区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2024-07-16 DOI: 10.1039/d4ob00939h
Balázs Pogrányi, Tamara Mielke, Alba Díaz Rodríguez, Jared Cartwright, William P Unsworth, Gideon Grogan

The unspecific peroxygenase (UPO) from Agrocybe aegerita (rAaeUPO-PaDa-I-H) is an effective and practical biocatalyst for the oxidative expansion of furfuryl alcohols/amines on a preparative scale, using the Achmatowicz and aza-Achmatowicz reaction. The high activity and stability of the enzyme, which can be produced on a large scale as an air-stable lyophilised powder, renders it a versatile and scalable biocatalyst for the preparation of synthetically valuable 6-hydroxypyranones and dihydropiperidinones. In several cases, the biotransformation out-performed the analogous chemo-catalysed process, and operates under milder and greener reaction conditions.

来自 Agrocybe aegerita 的非特异性过氧化物酶(UPO)(rAaeUPO-PaDa-I-H)是一种高效实用的生物催化剂,可利用 Achmatowicz 和 aza-Achmatowicz 反应制备规模的糠醇/胺氧化扩展。该酶具有高活性和稳定性,可作为空气稳定的冻干粉末大规模生产,因此是制备具有合成价值的 6-羟基吡喃酮和二氢哌啶酮的多功能、可扩展的生物催化剂。在一些情况下,生物转化的效果优于类似的化学催化过程,而且反应条件更温和、更环保。
{"title":"Preparative scale Achmatowicz and aza-Achmatowicz rearrangements catalyzed by <i>Agrocybe aegerita</i> unspecific peroxygenase.","authors":"Balázs Pogrányi, Tamara Mielke, Alba Díaz Rodríguez, Jared Cartwright, William P Unsworth, Gideon Grogan","doi":"10.1039/d4ob00939h","DOIUrl":"https://doi.org/10.1039/d4ob00939h","url":null,"abstract":"<p><p>The unspecific peroxygenase (UPO) from <i>Agrocybe aegerita</i> (r<i>Aae</i>UPO-PaDa-I-H) is an effective and practical biocatalyst for the oxidative expansion of furfuryl alcohols/amines on a preparative scale, using the Achmatowicz and aza-Achmatowicz reaction. The high activity and stability of the enzyme, which can be produced on a large scale as an air-stable lyophilised powder, renders it a versatile and scalable biocatalyst for the preparation of synthetically valuable 6-hydroxypyranones and dihydropiperidinones. In several cases, the biotransformation out-performed the analogous chemo-catalysed process, and operates under milder and greener reaction conditions.</p>","PeriodicalId":96,"journal":{"name":"Organic & Biomolecular Chemistry","volume":null,"pages":null},"PeriodicalIF":2.9,"publicationDate":"2024-07-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141618625","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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
Electrochemical selenylative ipso-annulation of N-benzylacrylamides to construct seleno-azaspiro[4.5]decadienones. 通过电化学硒化作用异annulation N-苄基丙烯酰胺来构建硒氮杂螺[4.5]癸二烯酮。
IF 2.9 3区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2024-07-16 DOI: 10.1039/d4ob00805g
Chada Raji Reddy, Jannatul Islam, Thallamapuram Nagendraprasad, Uprety Ajaykumar

Herein, we present the electrochemical synthesis of selenylated azaspiro[4.5]decadienones through domino selenylation/ipso-annulation of N-benzylacrylamides with diselenides. The method showed a wide substrate scope under mild and external oxidant-free reaction conditions, involving the construction of C-Se and C-C bonds. Gram-scale synthesis and further functional group conversion of the product are also demonstrated.

在此,我们介绍了通过 N-苄基丙烯酰胺与二硒化物的多米诺硒化/异annulation,电化学合成硒化氮杂螺[4.5]癸二烯酮的方法。该方法在温和、外部无氧化剂的反应条件下,涉及 C-Se 和 C-C 键的构建,显示出广泛的底物范围。此外,还展示了该产品的克级合成和进一步的官能团转换。
{"title":"Electrochemical selenylative <i>ipso</i>-annulation of <i>N</i>-benzylacrylamides to construct seleno-azaspiro[4.5]decadienones.","authors":"Chada Raji Reddy, Jannatul Islam, Thallamapuram Nagendraprasad, Uprety Ajaykumar","doi":"10.1039/d4ob00805g","DOIUrl":"https://doi.org/10.1039/d4ob00805g","url":null,"abstract":"<p><p>Herein, we present the electrochemical synthesis of selenylated azaspiro[4.5]decadienones through domino selenylation/<i>ipso</i>-annulation of <i>N</i>-benzylacrylamides with diselenides. The method showed a wide substrate scope under mild and external oxidant-free reaction conditions, involving the construction of C-Se and C-C bonds. Gram-scale synthesis and further functional group conversion of the product are also demonstrated.</p>","PeriodicalId":96,"journal":{"name":"Organic & Biomolecular Chemistry","volume":null,"pages":null},"PeriodicalIF":2.9,"publicationDate":"2024-07-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141618623","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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
Light-induced ligand-to-metal charge transfer of Fe(III)-OR species in organic synthesis. 有机合成中 Fe(III)-OR 物种的光诱导配体-金属电荷转移。
IF 2.9 3区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2024-07-16 DOI: 10.1039/d4ob00876f
Jie Qin, Hong Lei, Chuanhua Gao, Yuewen Zheng, Yating Zhao, Wujiong Xia

Light-induced ligand-to-metal charge transfer (LMCT) has been utilized as a powerful strategy in various organic reactions. First-row transition metals, especially iron complexes, show good applications in this process. Fe(III)-Cl and Fe(III)-OR species are two key intermediates involved in the LMCT of iron complexes. This review highlights studies on LMCT of Fe(III)-OR species, including carboxylate-iron and alkoxy-iron species, in organic transformations. Reaction conditions, substrate scope and related mechanisms are discussed.

在各种有机反应中,光诱导配体-金属电荷转移(LMCT)已被用作一种强有力的策略。第一排过渡金属,尤其是铁络合物,在这一过程中显示出良好的应用前景。Fe(III)-Cl 和 Fe(III)-OR 物种是参与铁络合物 LMCT 的两个关键中间体。本综述重点介绍了有机转化过程中 Fe(III)-OR 物种(包括羧基铁和烷氧基铁)的 LMCT 研究。文中讨论了反应条件、底物范围和相关机理。
{"title":"Light-induced ligand-to-metal charge transfer of Fe(III)-OR species in organic synthesis.","authors":"Jie Qin, Hong Lei, Chuanhua Gao, Yuewen Zheng, Yating Zhao, Wujiong Xia","doi":"10.1039/d4ob00876f","DOIUrl":"https://doi.org/10.1039/d4ob00876f","url":null,"abstract":"<p><p>Light-induced ligand-to-metal charge transfer (LMCT) has been utilized as a powerful strategy in various organic reactions. First-row transition metals, especially iron complexes, show good applications in this process. Fe(III)-Cl and Fe(III)-OR species are two key intermediates involved in the LMCT of iron complexes. This review highlights studies on LMCT of Fe(III)-OR species, including carboxylate-iron and alkoxy-iron species, in organic transformations. Reaction conditions, substrate scope and related mechanisms are discussed.</p>","PeriodicalId":96,"journal":{"name":"Organic & Biomolecular Chemistry","volume":null,"pages":null},"PeriodicalIF":2.9,"publicationDate":"2024-07-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141618624","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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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Organic & Biomolecular Chemistry
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