Biomimetic synthesis refers to organic synthesis using strategies that mimic biosynthetic pathways to prepare natural products. It draws inspiration from nature's efficiency in constructing organic compounds, often enabling mild conditions and efficient routes. Natural products constitute an enduring source of leads for drug discovery, and this approach has been used to successfully synthesise many medicinally important compounds. The prevalence of topologically complex carbocyclic ring systems in many secondary metabolites and particularly terpenes makes their preparation challenging and highlights the need for increased synthetic efficiency in carbocyclisation reactions. Here, we briefly review recent advances in our understanding of sesquiterpene cyclases and then present six case studies comparing biomimetic vs. non‐biomimetic approaches to the key ring‐forming reactions in this context. Examples have been selected to exemplify some of the classic ring systems that characterise this iconic natural product family.
{"title":"Ring Formation in Sesquiterpene Synthesis: Biomimetic vs. Non‐Biomimetic Strategies","authors":"Bohan Lin, Chen Dai, Alan C. Spivey","doi":"10.1002/ejoc.202500816","DOIUrl":"https://doi.org/10.1002/ejoc.202500816","url":null,"abstract":"Biomimetic synthesis refers to organic synthesis using strategies that mimic biosynthetic pathways to prepare natural products. It draws inspiration from nature's efficiency in constructing organic compounds, often enabling mild conditions and efficient routes. Natural products constitute an enduring source of leads for drug discovery, and this approach has been used to successfully synthesise many medicinally important compounds. The prevalence of topologically complex carbocyclic ring systems in many secondary metabolites and particularly terpenes makes their preparation challenging and highlights the need for increased synthetic efficiency in carbocyclisation reactions. Here, we briefly review recent advances in our understanding of sesquiterpene cyclases and then present six case studies comparing biomimetic vs. non‐biomimetic approaches to the key ring‐forming reactions in this context. Examples have been selected to exemplify some of the classic ring systems that characterise this iconic natural product family.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"51 1","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145807644","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}
Shammy Suraj, Tulsi R. Patel, Sudheesh T. Sivanandan, Bishwajit Ganguly, Irishi N. N. Namboothiri
Synthesis of C–N axially chiral and N , N ‐bis‐tosylated 2‐aminoindole‐based triarylmethanes via 1,6‐conjugate addition of tosyliminoindoles to p ‐quinone methides (PQM) followed by in situ N ‐protection is reported here. The exceptional C–N configurational stability, with rotational barriers in the range 27.5–40.9 kcal/mol, exhibited by these triarylmethanes, is supported by density functional theory (DFT) calculations and corroborated by experimental evidence. While the 1,6‐conjugate addition takes place in DMF at room temperature under base/catalyst‐free conditions, the diaryliminoindolylmethanes are amenable for in situ N ‐protection via alkylation, acylation, and sulfonylation under mild basic conditions. This methodology provides convenient access to a diverse array of 2‐aminoindole and di‐ t ‐butyl phenol‐based triarylmethanes exhibiting C–N atropisomerism, in good to excellent yields.
本文报道了通过在对醌类化合物（PQM）上1,6偶联添加tosyliminindoole，然后进行原位N保护，合成C-N轴手性和N， N -二甲基化2 -氨基吲哚基三芳基甲烷。密度泛函理论（DFT）证实了三芳基甲烷在27.5 ~ 40.9 kcal/mol范围内具有优异的C-N构型稳定性，并得到了实验证据的证实。虽然1,6 -共轭加成发生在DMF中，在室温下无碱/无催化剂的条件下，在温和的碱性条件下，二芳酰亚胺甲基甲烷可以通过烷基化、酰化和磺化进行原位N -保护。这种方法提供了方便的途径，以多种多样的2 -氨基吲哚和二- t -丁基苯酚为基础的三芳基甲烷具有C-N反异构性，收率很高。
{"title":"Synthesis and Evaluation of Indole‐Based C – N Axially Chiral Triarylmethanes","authors":"Shammy Suraj, Tulsi R. Patel, Sudheesh T. Sivanandan, Bishwajit Ganguly, Irishi N. N. Namboothiri","doi":"10.1002/ejoc.202500932","DOIUrl":"https://doi.org/10.1002/ejoc.202500932","url":null,"abstract":"Synthesis of <jats:italic>C–N</jats:italic> axially chiral and <jats:italic>N</jats:italic> , <jats:italic>N</jats:italic> ‐bis‐tosylated 2‐aminoindole‐based triarylmethanes via 1,6‐conjugate addition of tosyliminoindoles to <jats:italic>p</jats:italic> ‐quinone methides (PQM) followed by in situ <jats:italic>N</jats:italic> ‐protection is reported here. The exceptional <jats:italic>C–N</jats:italic> configurational stability, with rotational barriers in the range 27.5–40.9 kcal/mol, exhibited by these triarylmethanes, is supported by density functional theory (DFT) calculations and corroborated by experimental evidence. While the 1,6‐conjugate addition takes place in DMF at room temperature under base/catalyst‐free conditions, the diaryliminoindolylmethanes are amenable for in situ <jats:italic>N</jats:italic> ‐protection via alkylation, acylation, and sulfonylation under mild basic conditions. This methodology provides convenient access to a diverse array of 2‐aminoindole and di‐ <jats:italic>t</jats:italic> ‐butyl phenol‐based triarylmethanes exhibiting <jats:italic>C–N</jats:italic> atropisomerism, in good to excellent yields.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"41 1","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-12-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145801134","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}
Neelam Sen, Garima Pravin Pandey, Ajaya K. Singh, Sunita Sanwaria, Sónia A. C. Carabineiro
Herein, the oxidative degradation of amoxicillin (AMX) by water‐soluble colloidal MnO 2 is investigated spectrophotometrically at 298 K in both uncatalyzed and nonionic micellar‐catalyzed media (Triton X‐100 and Brij‐35). A 1:1 stoichiometric ratio between AMX and MnO 2 in acidic medium is observed, and two primary oxidation products are identified and characterized by gas chromatography–mass spectrometry analysis. The reaction exhibits first‐order kinetics with respect to the concentration of AMX in aqueous media, and a fractional‐order dependence in micellar media. Similarly, first‐order and fractional‐order dependences are observed with respect to the concentrations of MnO 2 and H 2 SO 4 , respectively, in both phases. The effects of experimental parameters, including ionic strength, dielectric constant, and the concentrations of Mn(II), KBr, KCl, and Na 2 SO 4 , are thoroughly investigated. Significant catalytic effects are observed for the nonionic surfactants Triton X‐100 and Brij‐35, which are explained using an appropriate mathematical model. A reaction mechanism and corresponding rate law consistent with the experimental data are proposed for both uncatalyzed and micellar‐catalyzed systems, and the thermodynamic activation parameters are evaluated using the Arrhenius equation.
{"title":"Study of Uncatalyzed and Micellar‐Catalyzed Oxidative Degradation of Amoxicillin by Colloidal MnO 2 : Experimental Optimization and Mechanistic Aspects","authors":"Neelam Sen, Garima Pravin Pandey, Ajaya K. Singh, Sunita Sanwaria, Sónia A. C. Carabineiro","doi":"10.1002/ejoc.202500142","DOIUrl":"https://doi.org/10.1002/ejoc.202500142","url":null,"abstract":"Herein, the oxidative degradation of amoxicillin (AMX) by water‐soluble colloidal MnO <jats:sub>2</jats:sub> is investigated spectrophotometrically at 298 K in both uncatalyzed and nonionic micellar‐catalyzed media (Triton X‐100 and Brij‐35). A 1:1 stoichiometric ratio between AMX and MnO <jats:sub>2</jats:sub> in acidic medium is observed, and two primary oxidation products are identified and characterized by gas chromatography–mass spectrometry analysis. The reaction exhibits first‐order kinetics with respect to the concentration of AMX in aqueous media, and a fractional‐order dependence in micellar media. Similarly, first‐order and fractional‐order dependences are observed with respect to the concentrations of MnO <jats:sub>2</jats:sub> and H <jats:sub>2</jats:sub> SO <jats:sub>4</jats:sub> , respectively, in both phases. The effects of experimental parameters, including ionic strength, dielectric constant, and the concentrations of Mn(II), KBr, KCl, and Na <jats:sub>2</jats:sub> SO <jats:sub>4</jats:sub> , are thoroughly investigated. Significant catalytic effects are observed for the nonionic surfactants Triton X‐100 and Brij‐35, which are explained using an appropriate mathematical model. A reaction mechanism and corresponding rate law consistent with the experimental data are proposed for both uncatalyzed and micellar‐catalyzed systems, and the thermodynamic activation parameters are evaluated using the Arrhenius equation.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"173 1","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-12-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145801135","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}
Denis S. Baranov, Mikhail N. Uvarov, Alexey A. Dmitriev, Leonid V. Kulik
The concise one‐pot synthesis of pyrrolonaphthalimides from 3‐amino‐4‐iodonaphthalimide and terminal alkynes has been developed. Copper‐catalyzed transformation of 3‐amino‐4‐iodonaphthalimide with alkynes proceeds via the formation of an alkyne substrate, which then undergoes 5‐ endo ‐dig cyclization to pyrrolonaphthalimides. The approach demonstrates good tolerance for functional groups. The bathochromic shift of the absorption maximum of the UV–vis spectrum of the solution of pyrrolo‐NIs in toluene achieved 76 nm for the pyrrolo‐NI containing 4‐(dimethylamino)phenyl moieties. The highest photoluminescence quantum yield (78%) in toluene is observed for the phenyl‐substituted pyrrolo‐NI.
{"title":"One‐Pot Synthesis, Optical, and Photoluminescent Properties of Pyrrolonaphthalimides","authors":"Denis S. Baranov, Mikhail N. Uvarov, Alexey A. Dmitriev, Leonid V. Kulik","doi":"10.1002/ejoc.202500935","DOIUrl":"https://doi.org/10.1002/ejoc.202500935","url":null,"abstract":"The concise one‐pot synthesis of pyrrolonaphthalimides from 3‐amino‐4‐iodonaphthalimide and terminal alkynes has been developed. Copper‐catalyzed transformation of 3‐amino‐4‐iodonaphthalimide with alkynes proceeds via the formation of an alkyne substrate, which then undergoes 5‐ <jats:italic>endo</jats:italic> ‐dig cyclization to pyrrolonaphthalimides. The approach demonstrates good tolerance for functional groups. The bathochromic shift of the absorption maximum of the UV–vis spectrum of the solution of pyrrolo‐NIs in toluene achieved 76 nm for the pyrrolo‐NI containing 4‐(dimethylamino)phenyl moieties. The highest photoluminescence quantum yield (78%) in toluene is observed for the phenyl‐substituted pyrrolo‐NI.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"17 1","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145786055","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}
Tatyana V. Gryaznova, Maxim V. Tarasov, Robert R. Fayzullin, Vladimir I. Morozov, Yulia H. Budnikova
A one-step, one-pot method for the preparation of dihydroacridine bisphosphonates at room temperature by Fc/Fc+-mediated electrochemical synthesis using (RO)3P (R=alkyl) and acridines in good yields at room temperature is proposed. This is the first example of twofold C–P formation via synchronous aromatic C–H phosphorylation. 9,10-Dihydroacridine derivatives are commonly found as privileged structural motifs in OLEDs, bioactive substances, photocatalysts, and various materials for useful applications. However, synthesis of these compounds from starting materials usually involves multiple stages. To date, no examples have been reported of the formation of geminal bisphosphonates on a single carbon atom through the phosphorylation of a C(sp2)–H aromatic fragment. The proposed method is also applicable for xanthene and acridine orange derivatives, but the yields of the bisphosphonates are lower. The products were characterized using X-ray crystallography. Their redox properties were determined through cyclic voltammetry. Paramagnetic compounds formed under oxidation conditions were analyzed using the electron paramagnetic resonance method.
{"title":"Electrochemical C(sp2)-H Diphosphorylation With a Redox Mediator: Access to Gem-Bisphosphonates","authors":"Tatyana V. Gryaznova, Maxim V. Tarasov, Robert R. Fayzullin, Vladimir I. Morozov, Yulia H. Budnikova","doi":"10.1002/ejoc.202500983","DOIUrl":"10.1002/ejoc.202500983","url":null,"abstract":"<p>A one-step, one-pot method for the preparation of dihydroacridine bisphosphonates at room temperature by Fc/Fc<sup>+</sup>-mediated electrochemical synthesis using (RO)<sub>3</sub>P (R=alkyl) and acridines in good yields at room temperature is proposed. This is the first example of twofold C–P formation via synchronous aromatic C–H phosphorylation. 9,10-Dihydroacridine derivatives are commonly found as privileged structural motifs in OLEDs, bioactive substances, photocatalysts, and various materials for useful applications. However, synthesis of these compounds from starting materials usually involves multiple stages. To date, no examples have been reported of the formation of geminal bisphosphonates on a single carbon atom through the phosphorylation of a C(sp<sup>2</sup>)–H aromatic fragment. The proposed method is also applicable for xanthene and acridine orange derivatives, but the yields of the bisphosphonates are lower. The products were characterized using X-ray crystallography. Their redox properties were determined through cyclic voltammetry. Paramagnetic compounds formed under oxidation conditions were analyzed using the electron paramagnetic resonance method.</p>","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"29 3","pages":""},"PeriodicalIF":2.7,"publicationDate":"2025-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145785977","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}
<p>Each author endeavors to carry out their research at the highest possible level, with a particular emphasis on addressing the main challenges of our present and future society. Organic chemistry stands out as a focal point in addressing these challenges, enabling a comprehensive understanding of the surrounding environment and providing innovative solutions for a wide range of issues, from health to energy.</p> <p>For many decades, the Division of Organic Chemistry of Società Chimica Italiana has demonstrated a dedicated commitment to formally and solemnly acknowledging, in front of the entire community, the noteworthy efforts and results attained each year by both junior and senior scientists across all major fields of organic chemistry. This commitment is consistently fulfilled, stressing the division's dedication to recognizing and celebrating outstanding contributions in organic chemistry.</p> <p>It fulfills this solemn commitment with the medals and the prizes of the Division of Organic Chemistry.</p> <p>The medals include: Gold Medal Adolfo Quilico (since 1984, intended for researchers in the field of bioorganic chemistry or chemistry of heterocyclic compounds), Gold Medal Angelo Mangini (since 1991, intended for researchers in the field of organic chemistry in mechanisms and theory), Gold Medal Giorgio Modena (since 2019, intended for researchers who have distinguished themselves for frontier research of highly interdisciplinary and innovative nature), and Silver Medal Giacomo Ciamician (since 1979, dedicated to researchers under the age of 40 and Ph.D. no longer than 7 years, who have distinguished themselves for notable research of high originality and interest).</p> <p>The prizes, established in 2001 and then renowned in 2016, include the following key macrosectors: environment, energy, and nanoscience; life sciences; methodological aspects; process and products in industry.</p> <p>Each year, the entire organic chemistry community is dedicated to analyzing and nominating the most deserving research in Italy within these fields. This annual process stands out as one of the most solemn moments for the organic chemistry community, as it acknowledges talent and solid dedication to the discipline and the community itself. The evaluation of candidacies and the final decision of the division's board follow a rigorous and meticulous procedure, especially considering the remarkably high scientific value of the proposed awardees. Each proposal originates from a division member and requires a solid endorsement from two or more distinguished scientists worldwide. Consequently, the ultimate decision reflects a careful and devoted process aimed at recognizing the most relevant achievements among the best researchers.</p> <p>This is confirmed by the fact that awarded chemists, including those in the early stages of their careers, consistently validate their talent both in Italy and internationally on numerous occasions.</p> <p>The scientists are ho
每个作者都努力在尽可能高的水平上开展他们的研究，特别强调解决我们现在和未来社会的主要挑战。有机化学作为解决这些挑战的焦点，使人们能够全面了解周围环境，并为从健康到能源的广泛问题提供创新的解决方案。几十年来，意大利化学学会有机化学部一直致力于在整个社会面前正式和庄严地承认每年在有机化学所有主要领域的初级和高级科学家所取得的显著努力和成果。这一承诺始终如一地履行，强调该部门致力于承认和庆祝有机化学领域的杰出贡献。它以有机化学学部的奖章和奖品来履行这一庄严的承诺。这些奖牌包括：金奖Adolfo Quilico（自1984年起，面向生物有机化学或杂环化合物化学领域的研究人员），金奖Angelo Mangini（自1991年起，面向有机化学机制和理论领域的研究人员），金奖Giorgio Modena（自2019年起，面向在高度跨学科和创新性质的前沿研究中脱颖而出的研究人员），银奖Giacomo Ciamician（自1979年起）。年龄在40岁以下，博士学位不超过7年，在独创性和趣味性方面有突出研究成果者)。该奖项成立于2001年，并于2016年成名，包括以下关键宏观领域：环境，能源和纳米科学；生命科学;方法论方面;工业过程和产品。每年，整个有机化学界都致力于分析和提名意大利在这些领域中最有价值的研究。这个一年一度的过程脱颖而出，成为有机化学界最庄严的时刻之一，因为它承认人才和对学科和社区本身的坚定奉献。对候选人的评估和部门董事会的最终决定遵循严格而细致的程序，特别是考虑到拟议的获奖者具有极高的科学价值。每项提案都是由一名部门成员提出的，并且需要得到两名或两名以上全球知名科学家的认可。因此，最终的决定反映了一个谨慎和专注的过程，旨在表彰最好的研究人员中最相关的成就。事实证明，获奖化学家，包括那些在职业生涯早期阶段的化学家，在意大利和国际上多次证明了他们的才能。在每年的有机化学部门年会期间举行的庄严仪式上，科学家们被授予奖章和奖品。这里介绍的2022年获奖作品如表1所示。颁奖仪式于2022年9月在意大利巴勒莫举行。表1。意大利化学学会有机化学分会2022年EurJOC获奖作品集。Valerio fasano有机化学方法论方面的初级研究奖serena riel生命科学有机化学研究奖rocco Del regno博士环境，能源和纳米科学有机化学论文奖，cristina Di carlucciph . d生命科学有机化学论文奖（francesco calogerph . d）有机化学方法论论文奖得奖者简介及他们对本期特刊的贡献如下。在这篇题为“基于儿茶酚/胺相互作用的多功能涂料”的综述文章中，Alessandra Napolitano， Adolfo Quilico金奖获得者，和他的同事们分析了有关新型湿粘合剂自然启发涂料开发的文献数据。深入报道了起始前体的性质、加工条件和最终性能。奖章获得者Francesco Zinna博士发表的题为“有机化合物的磁圆极化发光”的综述，对MCPL在研究手性和非手性分子的光物理性质方面的原理和适用性提出了见解。 该系列的第三个观点，题为“含吡啶生物活性分子的后期功能化：最近的策略和观点”，由方法学方面初级奖获得者Valerio Fasano撰写，旨在为有机化学家提供实用指南，以解决含吡啶生物活性分子后期功能化的区域选择性问题。在方法论方面奖获得者Renzo Luisi的研究文章中，题为“通过连续流动光化学方法将硫醇和二硫化物添加到氮化丁环上，在氮化丁环上形成C - S键”，作者说明了在普利亚（意大利南部）的有机化学实验室中，有效地利用集成光化学连续流动方法在氮化丁环上形成C - S键。这种创新的合成策略说明了巯基自由基的产生及其随后与2-氮基的反应。光化学和连续流技术的集成在实现快速、弹性和可扩展的转化方面发挥着关键作用，从而促进了未知化学领域的进入。获得博士奖的Francesco Calogero在题为“直接获得α-乙烯基-β-羟基酯的双光氧化还原和cp2ticl2催化方法”的研究文章中也探讨了光催化在驱动新反应性方面的机会。在本研究中，采用双光氧化还原和钛催化的方案，在乙烯基重整型反应中获得α-乙烯基-β-羟基酯。清洁能源是获得能源纳米科学环境奖的Alessandro Mordini的研究文章的鼓舞人心的主题。这项名为“用于发光太阳能聚光器的绿光响应D-π-A-π-D喹啉发射器：潜在集成于农业光伏系统”的研究报告了对小型有机荧光染料库的模块化访问，其光物理性质似乎适合农业光伏技术的发展。在生命科学奖获得者Serena Riela的一篇题为“基于拉脱土和瓜脲的触变水凝胶用于输送亲脂性药物分子”的研究文章中，一种基于合成粘土材料与糖脲环低聚物组合的创新超分子水凝胶被实验和计算机的观点深入研究，用于亲脂性药物的皮肤输送。采用先进的核磁共振技术，结合分子对接和动态模拟，在分子水平上研究了两种合成抗原模拟物与新发现的免疫球蛋白样蛋白成员的结合。这篇题为“肿瘤碳水化合物相关抗原类似物作为siglece -7的潜在结合物”的研究论文由博士获得者Cristina Di Carluccio共同撰写。最近，博士学位获得者Rocco Del Regno发表了一篇题为《支化异丙基对异丙prism[6]芳烃构象和超分子性质的自填充效应的见解》的论文，报道了一类新的大环宿主化合物的合成和构象和络合行为的研究。总而言之，奖章和奖项不仅认可了有机化学家中最有价值的人才，而且向整个社区传达了一个关键信息。这一信息鼓励每个人在各种挑战中坚持不懈，努力发挥自己的最大潜力。这一承诺的最终目标是为世界上每个人的美好社会和受尊重的生活作出贡献。获奖者年复一年地担任大使，体现了我们最重要努力的主要目的。
{"title":"Division of Organic Chemistry – Società Chimica Italiana. Prizewinner Collection 2022. Editorial","authors":"Alessandro Abbotto, Maria Valeria D’Auria","doi":"10.1002/ejoc.202400684","DOIUrl":"https://doi.org/10.1002/ejoc.202400684","url":null,"abstract":"<p>Each author endeavors to carry out their research at the highest possible level, with a particular emphasis on addressing the main challenges of our present and future society. Organic chemistry stands out as a focal point in addressing these challenges, enabling a comprehensive understanding of the surrounding environment and providing innovative solutions for a wide range of issues, from health to energy.</p>\u0000<p>For many decades, the Division of Organic Chemistry of Società Chimica Italiana has demonstrated a dedicated commitment to formally and solemnly acknowledging, in front of the entire community, the noteworthy efforts and results attained each year by both junior and senior scientists across all major fields of organic chemistry. This commitment is consistently fulfilled, stressing the division's dedication to recognizing and celebrating outstanding contributions in organic chemistry.</p>\u0000<p>It fulfills this solemn commitment with the medals and the prizes of the Division of Organic Chemistry.</p>\u0000<p>The medals include: Gold Medal Adolfo Quilico (since 1984, intended for researchers in the field of bioorganic chemistry or chemistry of heterocyclic compounds), Gold Medal Angelo Mangini (since 1991, intended for researchers in the field of organic chemistry in mechanisms and theory), Gold Medal Giorgio Modena (since 2019, intended for researchers who have distinguished themselves for frontier research of highly interdisciplinary and innovative nature), and Silver Medal Giacomo Ciamician (since 1979, dedicated to researchers under the age of 40 and Ph.D. no longer than 7 years, who have distinguished themselves for notable research of high originality and interest).</p>\u0000<p>The prizes, established in 2001 and then renowned in 2016, include the following key macrosectors: environment, energy, and nanoscience; life sciences; methodological aspects; process and products in industry.</p>\u0000<p>Each year, the entire organic chemistry community is dedicated to analyzing and nominating the most deserving research in Italy within these fields. This annual process stands out as one of the most solemn moments for the organic chemistry community, as it acknowledges talent and solid dedication to the discipline and the community itself. The evaluation of candidacies and the final decision of the division's board follow a rigorous and meticulous procedure, especially considering the remarkably high scientific value of the proposed awardees. Each proposal originates from a division member and requires a solid endorsement from two or more distinguished scientists worldwide. Consequently, the ultimate decision reflects a careful and devoted process aimed at recognizing the most relevant achievements among the best researchers.</p>\u0000<p>This is confirmed by the fact that awarded chemists, including those in the early stages of their careers, consistently validate their talent both in Italy and internationally on numerous occasions.</p>\u0000<p>The scientists are ho","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"1 1","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145777790","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}
The Front Cover depicts a relaxing spa treatment offered to a strained cyclopropanol client. The sunlight coming through the window symbolizes how visible light is essential for therapy, and photocatalysts (PC) and key intermediates engaged in the strain-release of cyclopropanol are depicted as spa therapists. The bottle of essential oil illustrates the use of DABSO as the essential source of SO2 gas. The PC therapist′s scissors chop off the radical from the dihydropyridine for SO2 capture and subsequent reaction with the acrylamide bed, eventually yielding SVI oxindoles. More information on this photoredox strategy can be found in the Research Article by T. Khan and co-workers (DOI: 10.1002/ejoc.202500726). Bhavik Parve is acknowledged for the graphic.
{"title":"Front Cover: 1,2-Sulfonylative-Arylation of Acrylamides via Strain-Release-/Aromaticity-Driven Radical Generation and SO2-Capture under Photoredox Catalysis to Access S(VI)-Oxindoles (Eur. J. Org. Chem. 47/2025)","authors":"Abhaykumar Vishwakarma, Tonish Kumar Sahu, Shanti Gopal Patra, Chhanda Paul, Somalisa Behera, Sanjeeb Sahoo, Tabrez Khan","doi":"10.1002/ejoc.70248","DOIUrl":"https://doi.org/10.1002/ejoc.70248","url":null,"abstract":"<p><b>The Front Cover</b> depicts a relaxing spa treatment offered to a strained cyclopropanol client. The sunlight coming through the window symbolizes how visible light is essential for therapy, and photocatalysts (PC) and key intermediates engaged in the strain-release of cyclopropanol are depicted as spa therapists. The bottle of essential oil illustrates the use of DABSO as the essential source of SO<sub>2</sub> gas. The PC therapist′s scissors chop off the radical from the dihydropyridine for SO<sub>2</sub> capture and subsequent reaction with the acrylamide bed, eventually yielding SVI oxindoles. More information on this photoredox strategy can be found in the Research Article by T. Khan and co-workers (DOI: 10.1002/ejoc.202500726). Bhavik Parve is acknowledged for the graphic.\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure>\u0000 </p>","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"28 47","pages":""},"PeriodicalIF":2.7,"publicationDate":"2025-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/ejoc.70248","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145754564","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
γ‐Keto sulfones, despite being a medicinally relevant building block, have never been integrated with the bioactive oxindole scaffold present in several alkaloid natural products. On the other hand, strategies involving SO2 capture in organic molecules to access value‐added products are gaining momentum. Therefore, a strategy en route to γ‐keto alkylsulfonylated oxindoles bearing a β‐all‐carbon quaternary center is disclosed. Toward this goal, the bisfunctionalization of N‐(hetero)arylacrylamides has been realized via the strain‐release driven ring‐scission of strained 3°‐cyclopropanols in the presence of DABSO under visible‐light photoredox catalysis to access a library of γ‐keto alkylsulfonylated oxindoles. Also, the aromaticity‐driven bond‐scission in pro‐aromatics like 4‐alkyl‐1,4‐DHPs in the presence of Na2S2O5 under visible‐light photoredox catalysis has been exploited to trigger the alkylsulfonylative‐arylation of N‐(hetero)arylacrylamides to access a library of alkylsulfonylated oxindoles featuring a β‐all‐carbon quaternary center. Broad substrate scope is demonstrated, and the mechanistic probing studies have been complemented with DFT calculations. Also, moderate to potent cytotoxic activity is observed against the tested triple‐negative breast cancer cell lines for some of the synthesized sulfonylated oxindole derivatives. Further, evaluation of the mechanism of cell death for the most potent oxindole analog revealed that it induces apoptosis in a concentration‐dependent manner.
{"title":"1,2‐Sulfonylative‐Arylation of Acrylamides via Strain‐Release‐/Aromaticity‐Driven Radical Generation and SO2‐Capture under Photoredox Catalysis to Access S(VI)‐Oxindoles","authors":"Abhaykumar Vishwakarma , Tonish Kumar Sahu , Shanti Gopal Patra , Chhanda Paul , Somalisa Behera , Sanjeeb Sahoo , Tabrez Khan","doi":"10.1002/ejoc.202500726","DOIUrl":"10.1002/ejoc.202500726","url":null,"abstract":"<div><div>γ‐Keto sulfones, despite being a medicinally relevant building block, have never been integrated with the bioactive oxindole scaffold present in several alkaloid natural products. On the other hand, strategies involving SO<sub>2</sub> capture in organic molecules to access value‐added products are gaining momentum. Therefore, a strategy en route to γ‐keto alkylsulfonylated oxindoles bearing a <em>β</em>‐all‐carbon quaternary center is disclosed. Toward this goal, the bisfunctionalization of N‐(hetero)arylacrylamides has been realized via the strain‐release driven ring‐scission of strained 3°‐cyclopropanols in the presence of DABSO under visible‐light photoredox catalysis to access a library of γ‐keto alkylsulfonylated oxindoles. Also, the aromaticity‐driven bond‐scission in pro‐aromatics like 4‐alkyl‐1,4‐DHPs in the presence of Na<sub>2</sub>S<sub>2</sub>O<sub>5</sub> under visible‐light photoredox catalysis has been exploited to trigger the alkylsulfonylative‐arylation of N‐(hetero)arylacrylamides to access a library of alkylsulfonylated oxindoles featuring a β‐all‐carbon quaternary center. Broad substrate scope is demonstrated, and the mechanistic probing studies have been complemented with DFT calculations. Also, moderate to potent cytotoxic activity is observed against the tested triple‐negative breast cancer cell lines for some of the synthesized sulfonylated oxindole derivatives. Further, evaluation of the mechanism of cell death for the most potent oxindole analog revealed that it induces apoptosis in a concentration‐dependent manner.</div></div>","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"28 47","pages":"Article e202500726"},"PeriodicalIF":2.7,"publicationDate":"2025-12-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145235389","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}
Henrich Kabzan , Péter Kisszékelyi , Juraj Filo , Marek Cigáň , Erik Rakovský , Radovan Šebesta
Ferrocene thioamides are potential alternatives for classical oxoamide‐type ferrocene ligands with broad applications in metal‐catalyzed transformations as well as substrates for CH activations and applications in other fields. A reaction of ferrocenecarboxaldehyde with various amines and sulfur promoted by sodium sulfide furnishes a wide range of ferrocene thioamides via the Willgerodt–Kindler multicomponent reaction. The detailed solvent screening reveals that amide‐type solvents are highly beneficial for the reaction. The steric hindrance of bulky amine substrates limits the reaction. While secondary amines require only conventional heating, primary amines yield better results with microwave irradiation at higher temperatures. The mechanism is investigated using nuclear magnetic resonance kinetic measurements, which show that Na2S acts as a promoter, rather than a catalyst, of the reaction.
{"title":"One‐Pot Synthesis of Ferrocene Thioamides from Ferrocenecarboxaldehyde via the Willgerodt–Kindler Reaction","authors":"Henrich Kabzan , Péter Kisszékelyi , Juraj Filo , Marek Cigáň , Erik Rakovský , Radovan Šebesta","doi":"10.1002/ejoc.202500956","DOIUrl":"10.1002/ejoc.202500956","url":null,"abstract":"<div><div>Ferrocene thioamides are potential alternatives for classical oxoamide‐type ferrocene ligands with broad applications in metal‐catalyzed transformations as well as substrates for CH activations and applications in other fields. A reaction of ferrocenecarboxaldehyde with various amines and sulfur promoted by sodium sulfide furnishes a wide range of ferrocene thioamides via the Willgerodt–Kindler multicomponent reaction. The detailed solvent screening reveals that amide‐type solvents are highly beneficial for the reaction. The steric hindrance of bulky amine substrates limits the reaction. While secondary amines require only conventional heating, primary amines yield better results with microwave irradiation at higher temperatures. The mechanism is investigated using nuclear magnetic resonance kinetic measurements, which show that Na<sub>2</sub>S acts as a promoter, rather than a catalyst, of the reaction.</div></div>","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"28 47","pages":"Article e202500956"},"PeriodicalIF":2.7,"publicationDate":"2025-12-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145427684","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}
Anjali Sharma , Smritilekha Bera , Dhananjoy Mondal
The total synthesis of anti‐inflammatory (‐)‐berkeleyamide A (with an overall yield of 40%) and its seven stereoisomers was accomplished from inexpensive Meldrum's acid. The reagent‐controlled KOtBu‐mediated syn‐aldol adduct (>76% yield and >90% diastereoselectivity) afforded the natural (10S, 11R,14S)‐(‐)‐berkeleyamide A. Notably, an exclusive anti‐aldol adduct, formed via LiHMDS/TMEDA‐mediated aldol reaction, produced (10S, 11S,14S)‐(‐)‐11‐epi‐berkeleyamide A as a single crystal. While the use of LDA and NaHMDS yielded both syn‐ and antiadducts, enabling access to all stereoisomers. The required aldol partners, chiral γ‐lactam and aliphatic aldehyde, were both produced from Meldrum's acid in 3‐ and 5‐step sequences, respectively, with high yields (each step >87%). The 2D NMR studies and single‐crystal X‐ray crystallographic data assisted in assigning the stereochemistry of all the stereoisomers.
{"title":"Reagent‐Controlled Total Synthesis of Natural Anti‐Inflammatory (‐)‐Berkeleyamide A and its Seven Stereoisomers","authors":"Anjali Sharma , Smritilekha Bera , Dhananjoy Mondal","doi":"10.1002/ejoc.202500926","DOIUrl":"10.1002/ejoc.202500926","url":null,"abstract":"<div><div>The total synthesis of anti‐inflammatory (‐)‐berkeleyamide A (with an overall yield of 40%) and its seven stereoisomers was accomplished from inexpensive Meldrum's acid. The reagent‐controlled KO<sup>t</sup>Bu‐mediated <em>syn</em>‐aldol adduct (>76% yield and >90% diastereoselectivity) afforded the natural (<em>10S</em>, <em>11R</em>,<em>14S</em>)‐(‐)‐berkeleyamide A. Notably, an exclusive anti‐aldol adduct, formed via LiHMDS/TMEDA‐mediated aldol reaction, produced (<em>10S</em>, <em>11S</em>,<em>14S</em>)‐(‐)‐11‐<em>epi</em>‐berkeleyamide A as a single crystal. While the use of LDA and NaHMDS yielded both <em>syn</em>‐ and antiadducts, enabling access to all stereoisomers. The required aldol partners, chiral γ‐lactam and aliphatic aldehyde, were both produced from Meldrum's acid in 3‐ and 5‐step sequences, respectively, with high yields (each ste<em>p</em> >87%). The 2D NMR studies and single‐crystal X‐ray crystallographic data assisted in assigning the stereochemistry of all the stereoisomers.</div></div>","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"28 47","pages":"Article e202500926"},"PeriodicalIF":2.7,"publicationDate":"2025-12-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145454704","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}
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