Martin Lepeintre, Paul Couderc, Haron Harbi, Alexia Dussart, Roy Lavendomme, Nikolay Tumanov, Johan Wouters, Benoit Colasson, Ivan Jabin
The alternate O-methylation of p-tBu-calix[6]arene is a well-known method leading to the C3v-symmetrical 1,3,5-tris-O-Me-p-tBu-calix[6]arene, a key compound for the development of platforms for supramolecular studies and in particular for the access to receptors in host–guest chemistry. The alternate O-methylation of the parent de-tert-butylated calix[6]arene remained elusive, precluding the development of similar C3v-symmetrical 1,3,5-tris-O-methylated receptors with an open cavity devoid of bulky tBu groups at the large rim. In this work, we developed an efficient method for the synthesis of 1,3,5-tris-O-Me-calix[6]arene. This platform was further selectively derivatized on the small and large rims, producing notably a tris-imidazole calix[6]arene-based ligand forming a biomimetic funnel complex upon coordinating Zn2+, with an open cavity suitable for the inclusion of a bulky dopamine derivative.
对- tbu -杯[6]芳烃的交替o -甲基化是一种众所周知的方法，导致c3v对称1,3,5-三- o -me -p- tbu -杯[6]芳烃，这是开发超分子研究平台的关键化合物，特别是在主-客体化学中获得受体的关键化合物。亲本去叔丁基杯[6]芳烃的交替o -甲基化仍然是难以捉摸的，这阻碍了类似的c3v对称1,3,5-三- o -甲基化受体的发育，这些受体具有开放的腔，在大边缘没有大的tBu基团。在本工作中，我们开发了一种合成1,3,5-三- o - me杯[6]芳烃的高效方法。该平台进一步在小环和大环上选择性衍生化，特别是产生三咪唑杯[6]芳烃基配体，在配位Zn2+后形成仿生漏斗复合物，具有适合包含大体积多巴胺衍生物的开放腔。
{"title":"Synthesis of C3v-Symmetrical 1,3,5-Tris-O-Me-Calix[6]arene: New Perspectives","authors":"Martin Lepeintre, Paul Couderc, Haron Harbi, Alexia Dussart, Roy Lavendomme, Nikolay Tumanov, Johan Wouters, Benoit Colasson, Ivan Jabin","doi":"10.1002/ejoc.202500947","DOIUrl":"https://doi.org/10.1002/ejoc.202500947","url":null,"abstract":"The alternate <i>O</i>-methylation of <i>p</i>-<i>t</i>Bu-calix[6]arene is a well-known method leading to the <i>C</i><sub>3v</sub>-symmetrical 1,3,5-tris-<i>O</i>-Me-<i>p</i>-<i>t</i>Bu-calix[6]arene, a key compound for the development of platforms for supramolecular studies and in particular for the access to receptors in host–guest chemistry. The alternate <i>O</i>-methylation of the parent de-<i>tert</i>-butylated calix[6]arene remained elusive, precluding the development of similar <i>C</i><sub>3v</sub>-symmetrical 1,3,5-tris-<i>O</i>-methylated receptors with an open cavity devoid of bulky <i>t</i>Bu groups at the large rim. In this work, we developed an efficient method for the synthesis of 1,3,5-tris-<i>O</i>-Me-calix[6]arene. This platform was further selectively derivatized on the small and large rims, producing notably a tris-imidazole calix[6]arene-based ligand forming a biomimetic funnel complex upon coordinating Zn<sup>2+</sup><sub>,</sub> with an open cavity suitable for the inclusion of a bulky dopamine derivative.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"15 1","pages":""},"PeriodicalIF":2.8,"publicationDate":"2026-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145962204","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}
Karolina Paszek, Tomasz Siodła, Maciej Janicki, Agnieszka Ludwików, Henryk Koroniak, Katarzyna Koroniak-Szejn
The Front Cover shows mirrors reflecting the central dipeptide as synthesized trifluoromethylated amino acid derivatives that mimic the biological activity of cathepsin C inhibitors. The mirrored images symbolize peptidomimetics. More information can be found in the Research Article by K. Koroniak-Szejn and co-workers (DOI: 10.1002/ejoc.202500773).
{"title":"Front Cover: Toward Novel Trifluoromethylated Peptidomimetics: A Case Study of Cathepsin C Inhibitors (Eur. J. Org. Chem. 1/2026)","authors":"Karolina Paszek, Tomasz Siodła, Maciej Janicki, Agnieszka Ludwików, Henryk Koroniak, Katarzyna Koroniak-Szejn","doi":"10.1002/ejoc.70293","DOIUrl":"10.1002/ejoc.70293","url":null,"abstract":"<p><b>The Front Cover</b> shows mirrors reflecting the central dipeptide as synthesized trifluoromethylated amino acid derivatives that mimic the biological activity of cathepsin C inhibitors. The mirrored images symbolize peptidomimetics. More information can be found in the Research Article by K. Koroniak-Szejn and co-workers (DOI: 10.1002/ejoc.202500773).\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure></p>","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"29 1","pages":""},"PeriodicalIF":2.7,"publicationDate":"2026-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/ejoc.70293","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145962324","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}
Electrophotochemical synthesis is emerging as a powerful and sustainable methodology in organic synthesis. This work describes the successful integration of photochemical and electrosynthesis to achieve an oxidation and carbene transfer cascade reaction for the synthesis of cyclopropane compounds. This strategy operates without stoichiometric oxidants or reductants, enabling efficient and highly selective redox transformations under mild conditions. Key to this process is the in situ electrochemical generation of diazo compounds from stable hydrazones, which subsequently undergo photolytic carbene formation and cyclopropanation with olefin derivatives in a single pot. This approach effectively mitigates the handling and stability issues associated with isolated diazo compounds. The reaction system was optimized, identifying acetonitrile as the optimal solvent with graphite and platinum electrodes in the presence of NH 4 OAc and KI, achieving high yields of various cyclopropane derivatives. This electrophotochemical method provides a practical, metal‐oxidant‐free, and environmentally friendly alternative for accessing valuable cyclopropane architectures.
{"title":"Electrophotochemical Oxidation and Carbene Transfer Cascade Reaction for the Synthesis of Cyclopropane Compounds","authors":"Ziyang Yu, Delin Si, Ziyi Lin, Yanmin Jiang, Lei Wang, Rui Zhao","doi":"10.1002/ejoc.202501111","DOIUrl":"https://doi.org/10.1002/ejoc.202501111","url":null,"abstract":"Electrophotochemical synthesis is emerging as a powerful and sustainable methodology in organic synthesis. This work describes the successful integration of photochemical and electrosynthesis to achieve an oxidation and carbene transfer cascade reaction for the synthesis of cyclopropane compounds. This strategy operates without stoichiometric oxidants or reductants, enabling efficient and highly selective redox transformations under mild conditions. Key to this process is the in situ electrochemical generation of diazo compounds from stable hydrazones, which subsequently undergo photolytic carbene formation and cyclopropanation with olefin derivatives in a single pot. This approach effectively mitigates the handling and stability issues associated with isolated diazo compounds. The reaction system was optimized, identifying acetonitrile as the optimal solvent with graphite and platinum electrodes in the presence of NH <jats:sub>4</jats:sub> OAc and KI, achieving high yields of various cyclopropane derivatives. This electrophotochemical method provides a practical, metal‐oxidant‐free, and environmentally friendly alternative for accessing valuable cyclopropane architectures.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"45 1","pages":""},"PeriodicalIF":2.8,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145955797","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}
Derek Mota-Hernández, Luis Antonio Vázquez-López, Alejandro Cordero-Vargas
An efficient, ATRA (Atom-Transfer Radical Addition)-based, Ru-photocatalyzed radical-polar crossover reaction for the preparation of monoprotected dicarbonyl compounds is reported. This procedure is based on the capture of a cationic intermediate, arising from the radical step, with diverse nucleophiles. Additionally, we have extended this methodology to the synthesis of 1,5-dicarbonyl compounds by using cyanide as the oxocarbenium-capturing nucleophile.
{"title":"A Photoredox Radical-Polar Crossover Reaction for the Preparation of Monoprotected Dicarbonyl Compounds","authors":"Derek Mota-Hernández, Luis Antonio Vázquez-López, Alejandro Cordero-Vargas","doi":"10.1002/ejoc.202501033","DOIUrl":"https://doi.org/10.1002/ejoc.202501033","url":null,"abstract":"An efficient, ATRA (Atom-Transfer Radical Addition)-based, Ru-photocatalyzed radical-polar crossover reaction for the preparation of monoprotected dicarbonyl compounds is reported. This procedure is based on the capture of a cationic intermediate, arising from the radical step, with diverse nucleophiles. Additionally, we have extended this methodology to the synthesis of 1,5-dicarbonyl compounds by using cyanide as the oxocarbenium-capturing nucleophile.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"82 1","pages":""},"PeriodicalIF":2.8,"publicationDate":"2026-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145938169","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}
Jinhui Xie, Karwan Abdulmajed Othman, Musher Ismael Salih, Abdalla Ali Amin, Khdir Ahmed Othman, Rebaz Anwar Omer, Hui Yao, Damir A. Safin
C ‐Glycosides represent a class of structurally robust and pharmacologically significant molecules due to their stable anomeric C–C bonds and diverse biological profiles. Herein, a novel series of stereodefined C ‐fucosides, specifically (2 S ,3 S ,6 R )‐2‐methyl‐6‐aryl/aryloxy‐3,6‐dihydro‐2 H ‐pyran‐3‐ols ( 1 – 8 ), was efficiently synthesized from 3,4‐ O ‐carbonate‐L‐fucal via palladium‐catalyzed cross‐coupling with diverse aryltrifluoroborates. The reactions proceeded under mild conditions with excellent stereoselectivity, delivering high yields (78%–94%). All α ‐ C ‐glycosides were thoroughly characterized by nuclear magnetic resonance, high‐resolution mass spectrometry, and optical rotation. To evaluate their therapeutic potential, an integrated in silico assessment was conducted. ADMET profiling using SwissADME, BOILED‐Egg, and ProTox‐II predicted favorable pharmacokinetics and acceptable toxicity, identifying compounds 3 , 6 , and 8 as low‐toxicity candidates (Class 5). Molecular docking against cyclooxygenase‐2 (COX‐2), a validated anti‐inflammatory target, revealed strong binding affinities. Notably, compounds 7 and 2 exhibited docking scores comparable or superior to the reference drug rofecoxib (Vioxx), with MM/GBSA binding energies of −31.99 and −35.26 kcal/mol, respectively. Compound 7 demonstrated a unique binding mode involving hydrogen bonding with TYR355 and π – π stacking with TYR385 and TRP387, whereas compound 2 formed the most distinctive electrostatic interaction among all tested ligands. These results underscore the successful synthesis, structural characterization, and promising computational profile of these pyran‐based C ‐fucosides as potential COX‐2 inhibitors.
由于其稳定的C - C键和多样的生物学特征，C‐糖苷代表了一类结构坚固且具有药理意义的分子。本文通过钯催化的三氟硼酸芳基交叉偶联，从3,4 - O -碳酸盐- L - fucal中高效合成了一系列新型立体定向的C - focusides，特别是(2s, 3s, 6r) - 2 -甲基- 6 -芳基/芳氧基- 3,6 -二氢- 2 H - pyran - 3 - ol（1 - 8）。反应在温和的条件下进行，具有良好的立体选择性，收率高（78%-94%）。所有的α‐C‐糖苷都通过核磁共振、高分辨率质谱和旋光度进行了彻底的表征。为了评估它们的治疗潜力，进行了综合的计算机评估。使用SwissADME、煮鸡蛋和ProTox - II进行ADMET分析预测了有利的药代动力学和可接受的毒性，确定化合物3、6和8为低毒性候选物（5类）。分子对接环氧化酶- 2 (COX - 2)，一个有效的抗炎靶标，显示出很强的结合亲和力。值得注意的是，化合物7和2的对接分数与参比药物罗非昔布（Vioxx）相当或更高，MM/GBSA结合能分别为- 31.99和- 35.26 kcal/mol。化合物7与TYR355形成了氢键结合，与TYR385和TRP387形成了π - π堆叠，而化合物2形成了最独特的静电相互作用。这些结果强调了这些pyran - based C - focusides作为潜在的COX - 2抑制剂的成功合成，结构表征和有前途的计算轮廓。
{"title":"Design, Stereoselective Synthesis, and in Silico Evaluation of Novel Pyran‐Based C ‐Fucosides as Potential COX‐2 Inhibitors","authors":"Jinhui Xie, Karwan Abdulmajed Othman, Musher Ismael Salih, Abdalla Ali Amin, Khdir Ahmed Othman, Rebaz Anwar Omer, Hui Yao, Damir A. Safin","doi":"10.1002/ejoc.202501095","DOIUrl":"https://doi.org/10.1002/ejoc.202501095","url":null,"abstract":"<jats:italic>C</jats:italic> ‐Glycosides represent a class of structurally robust and pharmacologically significant molecules due to their stable anomeric C–C bonds and diverse biological profiles. Herein, a novel series of stereodefined <jats:italic>C</jats:italic> ‐fucosides, specifically (2 <jats:italic>S</jats:italic> ,3 <jats:italic>S</jats:italic> ,6 <jats:italic>R</jats:italic> )‐2‐methyl‐6‐aryl/aryloxy‐3,6‐dihydro‐2 <jats:italic>H</jats:italic> ‐pyran‐3‐ols ( 1 – 8 ), was efficiently synthesized from 3,4‐ <jats:italic>O</jats:italic> ‐carbonate‐L‐fucal via palladium‐catalyzed cross‐coupling with diverse aryltrifluoroborates. The reactions proceeded under mild conditions with excellent stereoselectivity, delivering high yields (78%–94%). All <jats:italic>α</jats:italic> ‐ <jats:italic>C</jats:italic> ‐glycosides were thoroughly characterized by nuclear magnetic resonance, high‐resolution mass spectrometry, and optical rotation. To evaluate their therapeutic potential, an integrated in silico assessment was conducted. ADMET profiling using SwissADME, BOILED‐Egg, and ProTox‐II predicted favorable pharmacokinetics and acceptable toxicity, identifying compounds 3 , 6 , and 8 as low‐toxicity candidates (Class 5). Molecular docking against cyclooxygenase‐2 (COX‐2), a validated anti‐inflammatory target, revealed strong binding affinities. Notably, compounds 7 and 2 exhibited docking scores comparable or superior to the reference drug rofecoxib (Vioxx), with MM/GBSA binding energies of −31.99 and −35.26 kcal/mol, respectively. Compound 7 demonstrated a unique binding mode involving hydrogen bonding with TYR355 and <jats:italic>π</jats:italic> – <jats:italic>π</jats:italic> stacking with TYR385 and TRP387, whereas compound 2 formed the most distinctive electrostatic interaction among all tested ligands. These results underscore the successful synthesis, structural characterization, and promising computational profile of these pyran‐based <jats:italic>C</jats:italic> ‐fucosides as potential COX‐2 inhibitors.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"07 1","pages":""},"PeriodicalIF":2.8,"publicationDate":"2026-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145908146","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}
We developed a metal‐free and solvent‐controlled protocol for the bromo‐lactonization of ( E )‐ N ‐substituted ortho ‐styryl benzamides using N ‐bromosuccinimide (NBS) as the sole reagent under ambient conditions. The reaction proceeded through an NBS‐derived bromine radical that evolved into a bromonium‐ion intermediate, enabling a trans ‐selective intramolecular cyclization exclusively through the amide oxygen. The reaction outcome depended strongly on the solvent: acetonitrile furnished bromo‐imino‐lactones, whereas wet methanol promoted oxime hydrolysis in the final step to afford 3,4‐dihydroisocoumarins. This NBS‐driven and solvent‐directed strategy therefore expanded the synthetic utility of prefunctionalized amides and provided a sustainable approach to oxygen‐containing heterocycles.
我们开发了一种在环境条件下以N -溴代琥珀酰亚胺（NBS）为唯一试剂的无金属溶剂控制的(E) - N -取代的邻苯甲酰基苯酰胺的溴内酯化反应方案。该反应通过NBS衍生的溴自由基演变成溴离子中间体，使分子内的反式选择性环化完全通过酰胺氧进行。反应结果很大程度上取决于溶剂：乙腈生成溴亚胺内酯，而湿甲醇在最后一步促进肟水解生成3,4 -二氢异香豆素。因此，这种NBS驱动和溶剂导向的策略扩大了预官能化酰胺的合成用途，并为含氧杂环化合物的合成提供了一种可持续的方法。
{"title":"Solvent Controlled NBS‐Driven Divergent Bromo‐Lactonization of Ortho ‐Styryl Benzamides","authors":"Pravat Nayek, Ramendranath Guchait, Tanmay Narendra Deshpande, Bappaditya Debnath, Rosalin Bhanja, Prasenjit Mal","doi":"10.1002/ejoc.202501176","DOIUrl":"https://doi.org/10.1002/ejoc.202501176","url":null,"abstract":"We developed a metal‐free and solvent‐controlled protocol for the bromo‐lactonization of ( <jats:italic>E</jats:italic> )‐ <jats:italic>N</jats:italic> ‐substituted <jats:italic>ortho</jats:italic> ‐styryl benzamides using <jats:italic>N</jats:italic> ‐bromosuccinimide (NBS) as the sole reagent under ambient conditions. The reaction proceeded through an NBS‐derived bromine radical that evolved into a bromonium‐ion intermediate, enabling a <jats:italic>trans</jats:italic> ‐selective intramolecular cyclization exclusively through the amide oxygen. The reaction outcome depended strongly on the solvent: acetonitrile furnished bromo‐imino‐lactones, whereas wet methanol promoted oxime hydrolysis in the final step to afford 3,4‐dihydroisocoumarins. This NBS‐driven and solvent‐directed strategy therefore expanded the synthetic utility of prefunctionalized amides and provided a sustainable approach to oxygen‐containing heterocycles.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"14 1","pages":""},"PeriodicalIF":2.8,"publicationDate":"2026-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145908147","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}
Owing to their unique properties, the synthesis of α ‐methylenelactams has long been a research hotspot in synthetic chemistry. In this article, a Pd‐catalyzed intramolecular dihalogenative cyclization reaction of amide‐fused 1,6‐enynes was developed, which successfully afforded a series of α ‐methylenelactam compounds. This reaction exhibits advantages including good yields, excellent stereoselectivity, and favorable functional group tolerance. In addition, the synthetic application of the products showed that the halogens reserved in the products can further undergo reactions such as cross‐coupling reactions and substitution reactions.
{"title":"Palladium‐Catalyzed Dihalogenative Cyclization of Amide‐Fused 1,6‐Enynes for the Synthesis of Lactams","authors":"Shan Zhong, Xiang Li, Hai Huang, Luning Tang","doi":"10.1002/ejoc.202501151","DOIUrl":"https://doi.org/10.1002/ejoc.202501151","url":null,"abstract":"Owing to their unique properties, the synthesis of <jats:italic>α</jats:italic> ‐methylenelactams has long been a research hotspot in synthetic chemistry. In this article, a Pd‐catalyzed intramolecular dihalogenative cyclization reaction of amide‐fused 1,6‐enynes was developed, which successfully afforded a series of <jats:italic>α</jats:italic> ‐methylenelactam compounds. This reaction exhibits advantages including good yields, excellent stereoselectivity, and favorable functional group tolerance. In addition, the synthetic application of the products showed that the halogens reserved in the products can further undergo reactions such as cross‐coupling reactions and substitution reactions.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"39 1","pages":""},"PeriodicalIF":2.8,"publicationDate":"2026-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145908148","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}
Jianwu Lv, Lihong Gou, Richard R. Schmidt, Peng Peng, Tianlu Li
Leishmaniasis remains an ignored tropical disease with urgent need for safe and effective vaccines. The lipophosphoglycans (LPGs) of Leishmania parasites is a key virulence factor, and its terminal cap tetrasaccharide represents a structurally conserved antigen suitable for vaccine development. Herein, we report a concise and practical route to synthesize the cap tetrasaccharide. This synthesis strategy highlights (i) regioselective axial benzoylation of mannosyl units via the “cyanide effect,” providing quick and orthogonally protected building blocks in large scale, and (ii) highly stereoselective glycosidation under AuCl 3 – t BuCN cooperative catalysis, which ensures efficient formation of challenging β ‐(1,4)‐galactosidic linkages without neighboring participation. These protocols are operationally simple, minimize protecting group manipulations, and are highly reproducible, thus enabling in‐depth biological studies and translational implementation.
利什曼病仍然是一种被忽视的热带病，迫切需要安全有效的疫苗。利什曼原虫的脂磷聚糖（LPGs）是一个关键的毒力因子，其端帽四糖是一种结构保守的抗原，适合于疫苗的开发。本文报道了一种简单实用的合成帽四糖的方法。该合成策略突出了(i)通过“氰化物效应”对甘露糖基单元进行区域选择性轴向苯甲酰化，提供了大规模的快速且正交保护的构建单元；（ii）在AuCl - 3 - t BuCN协同催化下进行高度立体选择性糖苷化，确保在没有邻近参与的情况下有效形成具有挑战性的β -(1,4) -半乳糖苷键。这些协议操作简单，最大限度地减少了保护群体操作，并且具有高度可重复性，因此可以进行深入的生物学研究和转化实施。
{"title":"Expedient Synthesis of the Cap Tetrasaccharide of Leishmania Lipophosphoglycan","authors":"Jianwu Lv, Lihong Gou, Richard R. Schmidt, Peng Peng, Tianlu Li","doi":"10.1002/ejoc.202501052","DOIUrl":"https://doi.org/10.1002/ejoc.202501052","url":null,"abstract":"Leishmaniasis remains an ignored tropical disease with urgent need for safe and effective vaccines. The lipophosphoglycans (LPGs) of <jats:italic>Leishmania</jats:italic> parasites is a key virulence factor, and its terminal cap tetrasaccharide represents a structurally conserved antigen suitable for vaccine development. Herein, we report a concise and practical route to synthesize the cap tetrasaccharide. This synthesis strategy highlights (i) regioselective axial benzoylation of mannosyl units via the “cyanide effect,” providing quick and orthogonally protected building blocks in large scale, and (ii) highly stereoselective glycosidation under AuCl <jats:sub>3</jats:sub> – <jats:italic>t</jats:italic> BuCN cooperative catalysis, which ensures efficient formation of challenging <jats:italic>β</jats:italic> ‐(1,4)‐galactosidic linkages without neighboring participation. These protocols are operationally simple, minimize protecting group manipulations, and are highly reproducible, thus enabling in‐depth biological studies and translational implementation.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"4 1","pages":""},"PeriodicalIF":2.8,"publicationDate":"2026-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145908079","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 total synthesis of eighteen structurally complex pallavicinia diterpenoids with three distinct carbon skeletons was accomplished from the second‐generation common intermediate 19 employing our bioinspired skeletal diversification strategy. Among these, (±)‐pallavicinolide D ( 4 ), (±)‐pallambins G/H ( 11 / 12 ), (±)‐pallaviambin C ( 13 ), (±)‐pallasubcin A ( 16 ), and (±)‐pallavisubin B ( 44b ) were synthesized prior to the reports of their isolation. The structures of (±)‐pallavicinolide D ( 4 ) and (±)‐pallasubcin A ( 16 ) were revised based on the X‐ray crystallographic and Nuclear Magnetic Resonance (NMR) analyses. The total synthesis of (±)‐pallavicinin A ( 17 ) was achieved for the first time. The synthetic route of (±)‐pallavicinolide A ( 1 ) was the shortest.
{"title":"Bioinspired Total Synthesis of Eighteen Pallavicinia Diterpenoids with Three Distinct Skeletons","authors":"Lijun Chen, Yuan Wang, Peng Chen, Yanxing Jia","doi":"10.1002/ejoc.202501157","DOIUrl":"https://doi.org/10.1002/ejoc.202501157","url":null,"abstract":"The total synthesis of eighteen structurally complex <jats:italic>pallavicinia</jats:italic> diterpenoids with three distinct carbon skeletons was accomplished from the second‐generation common intermediate 19 employing our bioinspired skeletal diversification strategy. Among these, (±)‐pallavicinolide D ( 4 ), (±)‐pallambins G/H ( 11 / 12 ), (±)‐pallaviambin C ( 13 ), (±)‐pallasubcin A ( 16 ), and (±)‐pallavisubin B ( 44b ) were synthesized prior to the reports of their isolation. The structures of (±)‐pallavicinolide D ( 4 ) and (±)‐pallasubcin A ( 16 ) were revised based on the X‐ray crystallographic and Nuclear Magnetic Resonance (NMR) analyses. The total synthesis of (±)‐pallavicinin A ( 17 ) was achieved for the first time. The synthetic route of (±)‐pallavicinolide A ( 1 ) was the shortest.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"11 1","pages":""},"PeriodicalIF":2.8,"publicationDate":"2026-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145903309","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}
Guihua Nie, Chengjiang Fang, Mei Chen, Qianqian Guo, Jun Sun, Renfeng Zhang, Yuguo Zheng
N‐heterocyclic carbenes (NHCs) have emerged as efficient catalysts for promoting umpolung reactions of aldehydes and enals. Recently, the NHCs have been successfully used for catalyzing the umpolung reactions of aldimines through the formation of aza‐Breslow intermediates. This article provides a systematic review of the research progress in the polarity reversal of imines and related reactions catalyzed by NHCs, along with a detailed discussion and summary of the underlying reaction mechanisms. The review is organized and categorized according to the types of NHC‐catalyzed reactions involving imines.
N -杂环羰基（NHCs）已成为促进醛类和醛类合成反应的有效催化剂。最近，NHCs已被成功地用于通过形成aza - Breslow中间体来催化醛胺的混合反应。本文系统综述了NHCs催化亚胺极性反转及相关反应的研究进展，并对其反应机理进行了详细的讨论和总结。根据NHC催化的涉及亚胺的反应类型对综述进行组织和分类。
{"title":"N‐Heterocyclic Carbene‐Catalyzed Umpolung Reactions of Imines Proceeding Through Aza‐Breslow Intermediates","authors":"Guihua Nie, Chengjiang Fang, Mei Chen, Qianqian Guo, Jun Sun, Renfeng Zhang, Yuguo Zheng","doi":"10.1002/ejoc.202501171","DOIUrl":"https://doi.org/10.1002/ejoc.202501171","url":null,"abstract":"N‐heterocyclic carbenes (NHCs) have emerged as efficient catalysts for promoting umpolung reactions of aldehydes and enals. Recently, the NHCs have been successfully used for catalyzing the umpolung reactions of aldimines through the formation of aza‐Breslow intermediates. This article provides a systematic review of the research progress in the polarity reversal of imines and related reactions catalyzed by NHCs, along with a detailed discussion and summary of the underlying reaction mechanisms. The review is organized and categorized according to the types of NHC‐catalyzed reactions involving imines.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"166 1","pages":""},"PeriodicalIF":2.8,"publicationDate":"2026-01-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145897200","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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