{"title":"Unlocking nature's antioxidants: a novel method for synthesising plasmalogens.","authors":"Jay Tromans, Bian Zhang, Bernard T Golding","doi":"10.1039/d4ob01233j","DOIUrl":"https://doi.org/10.1039/d4ob01233j","url":null,"abstract":"<p><p>Plasmalogens are glycerophospholipids distinguished by their <i>O</i>-(<i>Z</i>)-vinyl ether at the <i>sn</i>-1 position. These lipids are implicated in several disease states requiring analytical, diagnostic and therapeutic interventions, which demand synthetic availability for a variety of structural types. By deploying the new <i>O</i>-protecting group 1,4-dimethoxynaphthyl-2-methyl ('DIMON') and a new stereospecific method for accessing <i>Z</i>-vinyl ethers, a reproducible, versatile synthetic route to plasmalogens [plasmenyl phosphocholines] has been developed. A key intermediate is (<i>S</i>,<i>Z</i>)-1-((1,4-dimethoxynaphthalen-2-yl)methoxy)-3-(hexadec-1-en-1-yloxy)propan-2-ol, which in principle, permits plasmalogen synthesis 'à la carte' at scale. The methodology compares favourably with all previous synthetic routes by virtue of the very high configurational (>99% <i>Z</i>) and optical purity (>99% <i>ee</i>), including the ability to incorporate polyunsaturated fatty acyl chains (<i>e.g.</i> all <i>Z</i> docosahexaenoic acid) reliably at the <i>sn</i>-2 position.</p>","PeriodicalId":96,"journal":{"name":"Organic & Biomolecular Chemistry","volume":null,"pages":null},"PeriodicalIF":2.9,"publicationDate":"2024-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142131249","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}
{"title":"Visible light-mediated radical addition cascade cyclization of aryl isocyanides with tricarbonyls: rapid access to substituted phenanthridines and isoquinolines.","authors":"Sabyasachi Manna, Rahul Halanuru Sreedhara, Kandikere Ramaiah Prabhu","doi":"10.1039/d4ob01405g","DOIUrl":"https://doi.org/10.1039/d4ob01405g","url":null,"abstract":"<p><p>A visible light-mediated synthesis of substituted phenanthridines and isoquinolines from <i>ortho</i>-substituted aryl isocyanides and tricarbonyl compounds is unveiled <i>via</i> the radical addition cascade cyclization (RACC) strategy. This acid/base-free method involves an oxidant (a persulphate salt) and a Ru-photocatalyst. This protocol avoids the use of halogenated compounds as pre-functionalized carbonyl precursors. The products can be easily post-modified to other important small molecules. The functional group tolerance of the reaction and the yields of the products are good without any scalability issues. The mechanistic investigation suggested the presence of a radical pathway during the reaction.</p>","PeriodicalId":96,"journal":{"name":"Organic & Biomolecular Chemistry","volume":null,"pages":null},"PeriodicalIF":2.9,"publicationDate":"2024-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142131250","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}
Justin B Diccianni, Bo Hao, Wei Liu, Iulia I Strambeanu
{"title":"High-throughput optimization of the C-H arylation of oxetanes <i>via</i> Ni/aldehyde photocatalysis.","authors":"Justin B Diccianni, Bo Hao, Wei Liu, Iulia I Strambeanu","doi":"10.1039/d4ob01271b","DOIUrl":"https://doi.org/10.1039/d4ob01271b","url":null,"abstract":"<p><p>Oxetanes are under-explored in medicinal chemistry, despite their favorable physicochemical properties, in part, because of the challenges associated with their syntheses. High-throughput experimentation (HTE) enables the rapid screening of reaction variables, accelerating the reaction development process. Herein we report the use of HTE in the optimization of a mild C-H arylation reaction of oxetanes, and other ethers, using <i>p</i>-cyanobenzaldehyde as a cheap and effective photoexcited hydrogen-atom transfer catalyst, in conjunction with a Ni catalyst. Our optimized conditions enable the use of a modern, reproducible light source as well as sub-solvent quantity oxetane, while eliminating the need for toxic co-solvents and dangerous sources of UV light.</p>","PeriodicalId":96,"journal":{"name":"Organic & Biomolecular Chemistry","volume":null,"pages":null},"PeriodicalIF":2.9,"publicationDate":"2024-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142131247","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}
{"title":"Outstanding Reviewers for Organic & Biomolecular Chemistry in 2023","authors":"","doi":"10.1039/D4OB90098G","DOIUrl":"10.1039/D4OB90098G","url":null,"abstract":"<p >We would like to take this opportunity to thank all of <em>Organic & Biomolecular Chemistry</em>'s reviewers for helping to preserve quality and integrity in chemical science literature. We would also particularly like to highlight the Outstanding Reviewers for <em>Organic & Biomolecular Chemistry</em> in 2023.</p>","PeriodicalId":96,"journal":{"name":"Organic & Biomolecular Chemistry","volume":null,"pages":null},"PeriodicalIF":2.9,"publicationDate":"2024-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142131248","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}
Ekaterina A Zhigileva, Victoria E Opryshko, Artur V Eshtukov-Shcheglov, Dmitrii S Ivanov, Daniil I Rudik, Andrey A Mikhaylov, Igor A Ivanov, Alexander Yu Smirnov, Mikhail S Baranov
{"title":"Photochemistry of 2-(2-formylphenyloxy)acetic acid derivatives: synthesis of hydroxychromanones and benzofuranones.","authors":"Ekaterina A Zhigileva, Victoria E Opryshko, Artur V Eshtukov-Shcheglov, Dmitrii S Ivanov, Daniil I Rudik, Andrey A Mikhaylov, Igor A Ivanov, Alexander Yu Smirnov, Mikhail S Baranov","doi":"10.1039/d4ob01194e","DOIUrl":"https://doi.org/10.1039/d4ob01194e","url":null,"abstract":"<p><p>Photochemical transformations of small molecules, such as <i>ortho</i>-substituted benzaldehydes, in the absence of a photocatalyst are significantly underexplored and may reveal unexpected outcomes. In the present paper, we showed that 2-(2-formylphenoxy)acetic acid and its esters undergo photocyclization into chromanone and benzofuranone derivatives under 365 nm irradiation. The reaction occurs exclusively in dimethyl sulfoxide and can be used to efficiently obtain hydroxychromanones in good yields (27-91%). A detailed mechanistic study revealed the clue of the divergent phototransformation with various products.</p>","PeriodicalId":96,"journal":{"name":"Organic & Biomolecular Chemistry","volume":null,"pages":null},"PeriodicalIF":2.9,"publicationDate":"2024-09-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142124273","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}
Haixing Zhang, Chaoyue Sun, Xuan Zhang, Xuan Cheng, Guiwen Guo, Wang Geng, Peiwei Gong, Shumiao Zhang, Mianran Chao, Duyi Shen
{"title":"C–N cleavage of secondary amide to access primary amide by a Co(II)/Oxone oxidation system","authors":"Haixing Zhang, Chaoyue Sun, Xuan Zhang, Xuan Cheng, Guiwen Guo, Wang Geng, Peiwei Gong, Shumiao Zhang, Mianran Chao, Duyi Shen","doi":"10.1039/d4ob00974f","DOIUrl":"https://doi.org/10.1039/d4ob00974f","url":null,"abstract":"Cleavage of the C–N bond of a secondary amide could provide alternative access to primary amides; however, this strategy remains challenging due to oxidation resistance of the amide. Herein, we employed the cobalt(<small>II</small>)/Oxone catalytic system, one of the advanced oxidation processes (AOPs), to make it available to break the strong C–N bond of various secondary (sulfon)amides, especially those bearing electron-poor or <em>ortho</em>-substituted <em>N</em>-arenes, <em>en route</em> to desirable primary (sulfon)amides. Control experiments showed that it was probably not the generally-considered persulfate anion radical in the cobalt/peroxymonosulfate (Co/PMS) system but the proposed high-valent cobalt-oxo intermediate that should be the major active species for the initial N–H oxidation of <em>N</em>-aryl amides. In the case of <em>N</em>-alkylated secondary amides, the α-C–H bond, rather than the N–H bond, should be oxidized first by both the reactive radicals and high-valent cobalt-oxo species. This work not only establishes an efficient method for removing the <em>N</em>-substituents of secondary amides at low cost, with readily available and eco-friendly reagents, but also demonstrates further synthetic application and provides more insight into intermediates for metal-based AOPs in environmental remediation.","PeriodicalId":96,"journal":{"name":"Organic & Biomolecular Chemistry","volume":null,"pages":null},"PeriodicalIF":3.2,"publicationDate":"2024-09-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142249944","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}
{"title":"Synthesis and biological evaluation of natural Lachnophyllum methyl ester, Lachnophyllum lactone and their synthetic analogs","authors":"Kodjo Adande, Oudjaniyobi Simalou, Juline Ardanuy, Kodjo Eloh, Chérine Mehalla, Patricia Constant, Isabelle Fabing, Yves Génisson, Stéphanie Ballereau","doi":"10.1039/d4ob01224k","DOIUrl":"https://doi.org/10.1039/d4ob01224k","url":null,"abstract":"(2<em>Z</em>)-<em>Lachnophyllum</em> methyl ester and (4<em>Z</em>)-<em>Lachnophyllum</em> lactone were recently identified as major components in essential oils and extracts of <em>Conyza bonariensis</em> from Togo. Extended biological evaluation of these acetylenic compounds was however hampered by the reduced amounts isolated. A synthetic route was designed providing access to larger quantities of these two natural products as well as to original non-natural analogs with the prospect of exploring for the first time the structure–activity relationships in this series. Using LC/MS analysis, synthetic samples allowed confirming the presence of the two previously isolated natural products in plant extracts obtained by the accelerated solvent extraction technique. The nematocidal activity of the synthesized compounds confirmed the potency of the natural products, which remain the most active among all analogs tested. The synthesized compounds were also assessed against <em>Leishmania infantum</em> axenic amastigotes and the <em>Mycobacterium tuberculosis</em> H<small><sub>37</sub></small>Rv pathogenic strain. (2<em>Z</em>)-<em>Lachnophyllum</em> methyl ester, (4<em>Z</em>)-<em>Lachnophyllum</em> lactone and lactone analogs exhibited the strongest antileishmanial potency. As expected, a longer alkyl chain was necessary to observe significant antimycobacterial activity. The lactone analog bearing a C10 lipophilic appendage displayed the highest antimycobacterial potency. The notable activities of lactones, naturally occurring or analogs, either nematicidal, antileishmanial or antimycobacterial, were compared to their cytotoxicity for mammalian cells and revealed moderate selectivity index values. In this regard, the innocuous (2<em>Z</em>)-<em>Lachnophyllum</em> methyl ester and its analogs open up more promising perspectives for the discovery of bioactive agents to protect both agricultural crops and human health.","PeriodicalId":96,"journal":{"name":"Organic & Biomolecular Chemistry","volume":null,"pages":null},"PeriodicalIF":3.2,"publicationDate":"2024-09-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142202355","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}
{"title":"Regioselective synthesis of 2-aminophenols from N-arylhydroxylamines","authors":"Zhiwei Gao, Zhiguo Hou, Hongyin Gao","doi":"10.1039/d4ob01281j","DOIUrl":"https://doi.org/10.1039/d4ob01281j","url":null,"abstract":"A novel strategy for the synthesis of 2-aminophenols in the absence of metals and oxidants was described. The 2-aminophenols were efficiently obtained through a cascade [3,3]-sigmatropic rearrangement and <em>in situ</em> hydrolysis process by using readily available <em>N</em>-arylhydroxylamines and the <em>in situ</em>-generated methyl chlorosulfonate from commercially available sulfuryl chloride and methanol under mild conditions. This method could be scaled up and has a wide substrate scope with great functional group tolerance and high regioselectivity. The 2-aminophenol products could be readily converted into structurally diverse functional molecules in good yields under various conditions.","PeriodicalId":96,"journal":{"name":"Organic & Biomolecular Chemistry","volume":null,"pages":null},"PeriodicalIF":3.2,"publicationDate":"2024-09-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142202353","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}
{"title":"Ternary deep eutectic solvents for esterification of 2-methylpropenoic acid with alcohols","authors":"Jiani Huang, Yanyan Li, Ruonan Zhang, Liran Wang, Ming Bao, Xiaoqiang Yu","doi":"10.1039/d4ob01180e","DOIUrl":"https://doi.org/10.1039/d4ob01180e","url":null,"abstract":"In this paper, a set of novel ternary deep eutectic solvents (T-DESs) is synthesized and applied in the esterification of 2-methylpropenoic acid with alcohols. T-DESs have multiple functions, serving as a catalyst, polymerization inhibitor, and solvent, and demonstrate excellent catalytic esterification reaction activity (up to 96% yield). The optimal T-DESs <strong>1</strong> can be recycled 14 times without any decrease in its catalytic activity, thus solving the problems of methacrylate product separation with a polymerization inhibitor, catalyst recovery, and organic solvent pollution.","PeriodicalId":96,"journal":{"name":"Organic & Biomolecular Chemistry","volume":null,"pages":null},"PeriodicalIF":3.2,"publicationDate":"2024-09-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142202354","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}
Alexey L. Nuzhdin, Marina V. Bukhtiyarova, Galina A. Bukhtiyarova
{"title":"Organic synthesis in flow mode by selective liquid-phase hydrogenation over heterogeneous non-noble metal catalysts","authors":"Alexey L. Nuzhdin, Marina V. Bukhtiyarova, Galina A. Bukhtiyarova","doi":"10.1039/d4ob00873a","DOIUrl":"https://doi.org/10.1039/d4ob00873a","url":null,"abstract":"Flow hydrogenation performed over heterogeneous catalysts makes organic synthesis more economical, safe and environmentally friendly. Over the past two decades, a significant amount of research with a major focus on noble metal catalysts has been carried out in this area. However, catalysts based on non-noble metals (Ni, Cu, Co, <em>etc</em>.) are more promising for practical use due to their low cost and high availability. This review article discusses the use of supported and bulk non-noble metal catalysts for the liquid-phase hydrogenation of bi- and polyfunctional organic compounds in flow mode. The main attention is paid to the selective reduction of one functional group (NO<small><sub>2</sub></small>, C<img alt=\"[double bond, length as m-dash]\" border=\"0\" src=\"https://www.rsc.org/images/entities/char_e001.gif\">C, C<img alt=\"[triple bond, length as m-dash]\" border=\"0\" src=\"https://www.rsc.org/images/entities/char_e002.gif\">N, C<img alt=\"[double bond, length as m-dash]\" border=\"0\" src=\"https://www.rsc.org/images/entities/char_e001.gif\">O, and C<img alt=\"[double bond, length as m-dash]\" border=\"0\" src=\"https://www.rsc.org/images/entities/char_e001.gif\">N) in the presence of other substituents. In addition, cascade synthetic protocols involving hydrogenation are presented.</img></img></img></img>","PeriodicalId":96,"journal":{"name":"Organic & Biomolecular Chemistry","volume":null,"pages":null},"PeriodicalIF":3.2,"publicationDate":"2024-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142202210","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}