Huimei Zhong, Zijing Xing, Zi Yang, Huaixin Wei, Mingming Yu, Jinhui Cai
{"title":"Facile Synthesis of 1,2-Dicarbonyls From Alkynes Enabling by Oxone/PhSeSePh Under Mild Conditions","authors":"Huimei Zhong, Zijing Xing, Zi Yang, Huaixin Wei, Mingming Yu, Jinhui Cai","doi":"10.1002/ajoc.70345","DOIUrl":"10.1002/ajoc.70345","url":null,"abstract":"<div>\u0000 \u0000 <p>A robust, mild, and straightforward strategy for the efficient synthesis of structurally valuable 1,2-dicarbonyls from alkynes under the cooperative work of Oxone/diselenide was reported. This method proceeded with high efficiency under mild conditions, accommodating various symmetric and unsymmetric alkynes, which yielded the corresponding 1,2-diketones in 40%–96% yields. The control experiments indicated that both Oxone and diphenyl diselenide were crucial to this transformation. Furthermore, the preliminary mechanistic investigations revealed that a radical pathway was possibly involved in this reaction.</p>\u0000 </div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"15 3","pages":""},"PeriodicalIF":2.7,"publicationDate":"2026-02-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147570158","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Sofia O. Strekalova, Alexander I. Kononov, Maria A. Khvorova, Radel R. Mingazov, Vladimir I. Morozov, Ekaterina S. Bashirova, Olga B. Babaeva, Kamil A. Ivshin, Guzel R. Strekalova, Yulia H. Budnikova
{"title":"Metal-Free Electrosynthesis and Photoelectrosynthesis of N-Aryl Phenothiazines via C–H Amination","authors":"Sofia O. Strekalova, Alexander I. Kononov, Maria A. Khvorova, Radel R. Mingazov, Vladimir I. Morozov, Ekaterina S. Bashirova, Olga B. Babaeva, Kamil A. Ivshin, Guzel R. Strekalova, Yulia H. Budnikova","doi":"10.1002/ajoc.70339","DOIUrl":"https://doi.org/10.1002/ajoc.70339","url":null,"abstract":"<div>\u0000 \u0000 <p>N-Aryl phenothiazines are privileged scaffolds in materials science and medicinal chemistry, yet their synthesis often relies on transition metals or stoichiometric oxidants. Herein, we report a sustainable, metal-free electrochemical (EC) method for the C–H amination of phenols and anilines with phenothiazines. This protocol employs stable platinum electrodes under mild, oxidant-free conditions, enabling the late-stage functionalization of pharmaceuticals and natural products with high efficiency (up to 97% yield) and excellent regioselectivity. Furthermore, we introduce a complementary photoelectrochemical (PEC) strategy that, for a subset of substrates, provides superior yields, including several near-quantitative transformations. Mechanistic studies via cyclic voltammetry and EPR spectroscopy confirm the generation of a persistent phenothiazine radical cation (PTZ•<sup>+</sup>) as the key electrophilic intermediate. The efficiency of both EC and PEC pathways is rationalized by the stability of these radical cations, which is tunable by substituent effects.</p>\u0000 </div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"15 3","pages":""},"PeriodicalIF":2.7,"publicationDate":"2026-02-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147570160","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Sofia O. Strekalova, Alexander I. Kononov, Maria A. Khvorova, Radel R. Mingazov, Vladimir I. Morozov, Ekaterina S. Bashirova, Olga B. Babaeva, Kamil A. Ivshin, Guzel R. Strekalova, Yulia H. Budnikova
{"title":"Metal-Free Electrosynthesis and Photoelectrosynthesis of N-Aryl Phenothiazines via C–H Amination","authors":"Sofia O. Strekalova, Alexander I. Kononov, Maria A. Khvorova, Radel R. Mingazov, Vladimir I. Morozov, Ekaterina S. Bashirova, Olga B. Babaeva, Kamil A. Ivshin, Guzel R. Strekalova, Yulia H. Budnikova","doi":"10.1002/ajoc.70339","DOIUrl":"10.1002/ajoc.70339","url":null,"abstract":"<div>\u0000 \u0000 <p>N-Aryl phenothiazines are privileged scaffolds in materials science and medicinal chemistry, yet their synthesis often relies on transition metals or stoichiometric oxidants. Herein, we report a sustainable, metal-free electrochemical (EC) method for the C–H amination of phenols and anilines with phenothiazines. This protocol employs stable platinum electrodes under mild, oxidant-free conditions, enabling the late-stage functionalization of pharmaceuticals and natural products with high efficiency (up to 97% yield) and excellent regioselectivity. Furthermore, we introduce a complementary photoelectrochemical (PEC) strategy that, for a subset of substrates, provides superior yields, including several near-quantitative transformations. Mechanistic studies via cyclic voltammetry and EPR spectroscopy confirm the generation of a persistent phenothiazine radical cation (PTZ•<sup>+</sup>) as the key electrophilic intermediate. The efficiency of both EC and PEC pathways is rationalized by the stability of these radical cations, which is tunable by substituent effects.</p>\u0000 </div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"15 3","pages":""},"PeriodicalIF":2.7,"publicationDate":"2026-02-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147570159","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Huimei Zhong, Zijing Xing, Zi Yang, Huaixin Wei, Mingming Yu, Jinhui Cai
{"title":"Facile Synthesis of 1,2-Dicarbonyls From Alkynes Enabling by Oxone/PhSeSePh Under Mild Conditions","authors":"Huimei Zhong, Zijing Xing, Zi Yang, Huaixin Wei, Mingming Yu, Jinhui Cai","doi":"10.1002/ajoc.70345","DOIUrl":"10.1002/ajoc.70345","url":null,"abstract":"<div>\u0000 \u0000 <p>A robust, mild, and straightforward strategy for the efficient synthesis of structurally valuable 1,2-dicarbonyls from alkynes under the cooperative work of Oxone/diselenide was reported. This method proceeded with high efficiency under mild conditions, accommodating various symmetric and unsymmetric alkynes, which yielded the corresponding 1,2-diketones in 40%–96% yields. The control experiments indicated that both Oxone and diphenyl diselenide were crucial to this transformation. Furthermore, the preliminary mechanistic investigations revealed that a radical pathway was possibly involved in this reaction.</p>\u0000 </div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"15 3","pages":""},"PeriodicalIF":2.7,"publicationDate":"2026-02-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147569897","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Recognition of Two Ammonium Ions by Borate-Containing Crown Ether: Selectivity of the Internal and External Recognition of Distinct Ammonium Ions","authors":"Takumi Takizawa, Shinobu Miyagawa, Yuji Tokunaga","doi":"10.1002/ajoc.70337","DOIUrl":"10.1002/ajoc.70337","url":null,"abstract":"<div>\u0000 \u0000 <p>This study investigates the recognition properties of (pseudo)rotaxanes comprising bis-catechol-borate-containing crown ether and ammonium-containing axles. Nuclear magnetic resonance spectroscopy revealed that the borate-based (pseudo)rotaxanes could bind additional secondary ammonium ions outside the crown ether cavity. The association constant between an acidic ammonium ion and (pseudo)rotaxane was higher than that for the less acidic analogue. When an equimolar mixture of two ammonium ions with different acidities was introduced, the borate-based crown ether predominantly bound the more acidic ion within its cavity. Furthermore, the recognition of an additional ammonium ion decreased the selectivity toward internal binding of the more acidic ammonium ion.</p>\u0000 </div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"15 2","pages":""},"PeriodicalIF":2.7,"publicationDate":"2026-02-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147385677","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Kamal Kant, Reetu Reetu, Arup K. Kabi, Nayyef Aljaar, Susanta Ghanta, Chandi C. Malakar, Reda A. Haggam
{"title":"Iodine-Mediated [2+2+1+1] Annulation Using N,N-Dimethylformamide as a One-Carbon Synthon: Access to Pyridine and Triazine Scaffolds","authors":"Kamal Kant, Reetu Reetu, Arup K. Kabi, Nayyef Aljaar, Susanta Ghanta, Chandi C. Malakar, Reda A. Haggam","doi":"10.1002/ajoc.70334","DOIUrl":"10.1002/ajoc.70334","url":null,"abstract":"<div>\u0000 \u0000 <p>A metal-free approach to the synthesis of pyridine and 1,3,5-triazine derivatives is attempted under the influence of molecular iodine, utilizing a [2+2+1+1] annulation strategy. This annulation strategy operates effectively with <i>N</i>,<i>N-</i>dimethylformamide (DMF) as a C1 Source under mild reaction conditions, yielding the corresponding products in high yields ranging from 68% to 87%. A detailed mechanistic proposal is presented and supported by density functional theory calculations, which corroborate key intermediates and the iodine-mediated C1-incorporation pathway.</p>\u0000 </div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"15 2","pages":""},"PeriodicalIF":2.7,"publicationDate":"2026-02-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147385770","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Synthesis of (R)-Rasagiline and its Analogues via Chemo- and Enantioselective Hydrosilylation of N-Propargyl-indan-1-imines","authors":"Xinlei Long, Jianfeng Cheng, Juan Wang, Quntao Gu, Yingkun Yan, Xiaomei Zhang","doi":"10.1002/ajoc.70329","DOIUrl":"10.1002/ajoc.70329","url":null,"abstract":"<div>\u0000 \u0000 <p>By using a rigid chiral picolinamide Lewis base catalyst prepared from commercially available and cost-effective chloramphenicol base, chemo- and enantioselective hydrosilylation of <i>N</i>-propargyl-indan-1-imines has been realized. This transformation allowed the synthesis of various enantioenriched <i>N</i>-propargyl-1-indanamines including (<i>R</i>)-rasagiline with moderate to good yields (up to 99%) in low to good enantioselectivities, typically ranging 18%–75% ee and in one case up to 99% ee.</p>\u0000 </div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"15 2","pages":""},"PeriodicalIF":2.7,"publicationDate":"2026-02-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147385771","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Zixuan Liu, Jiaqi Tong, Bin Liu, Zelong Song, Xingxian Zhang
{"title":"Electrochemical Regioselective C(sp2)–H Selenylation of Pyrrolo[2,3-d]pyrimidine Derivatives With Diselenides","authors":"Zixuan Liu, Jiaqi Tong, Bin Liu, Zelong Song, Xingxian Zhang","doi":"10.1002/ajoc.70343","DOIUrl":"10.1002/ajoc.70343","url":null,"abstract":"<div>\u0000 \u0000 <p>An efficient electrochemical strategy has been established for the direct selenylation of pyrrolo[2,3-<i>d</i>] pyrimidine derivatives employing diselenides as the selenium source. This transformation proceeds under catalyst- and oxidant-free conditions, enabling efficient formation of C(<i>sp</i><sup>2</sup>)─Se bonds. Moreover, this strategy offers notable advantages including broad substrate scope, good functional group compatibility, high site-selectivity, and exceptional atom economy. Furthermore, preliminary mechanistic studies suggest that the reaction likely involves radical cation intermediates, which play a key role in promoting the selenylation process.</p>\u0000 </div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"15 2","pages":""},"PeriodicalIF":2.7,"publicationDate":"2026-02-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147385676","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Cs2CO3-Mediated One-Pot Orthogonal Reactions of 5-Bromo-1,2,3-Triazine for the Modular Synthesis of Functionalized Pyrimidine Ligands for Metal Complexes in Cellular Imaging","authors":"Yu-Chen Wang, Ya-Chu Yu, Wan-Hsuan Liu, Niaz Wali, Jiun-Jie Shie","doi":"10.1002/ajoc.70335","DOIUrl":"10.1002/ajoc.70335","url":null,"abstract":"<div>\u0000 \u0000 <p>Pyrimidines are aromatic nitrogen-containing heterocycles with significant applications in medicinal chemistry and materials science. Conventional two-step strategies for synthesizing 2,5-disubstituted pyrimidines from 2,5-dihalopyrimidines often require toxic reagents, transition metal (TM) catalysts, harsh conditions, specialized substrates, or non-commercially available reagents. Therefore, this study aims to develop a TM-free synthetic route for producing 2,5-disubstituted pyrimidines via heterocyclic skeletal editing. This one-pot tandem reaction sequence integrates nucleophilic aromatic C─O, C─N, and C─S substitutions with an amidine-based inverse-electron demand Diels–Alder reaction, providing efficient synthesis of pyrimidine derivatives in moderate to excellent yields. The modular skeletal editing strategy employs 5-bromo-1,2,3-triazine <b>1</b> as a molecular platform, facilitating orthogonal coupling with various phenols, thiophenols, and sodium azide, followed by amidines to achieve skeletal editing under mild conditions using only Cs<sub>2</sub>CO<sub>3</sub>. This method offers several advantages, including ready substrate availability, operational simplicity, and high atom economy. To further demonstrate the functional utility of the pyrimidine derivatives, pyrimidine-based Ru(II) complexes were synthesized for fluorescence imaging in live cells. An alkynylated Ru(II) complex <b>13</b> served as a key precursor for the modular incorporation of organelle-targeting moieties via copper-catalyzed azide–alkyne cycloaddition. These functionalized metal complexes facilitate selective labeling of the nucleus and mitochondria in live cells.</p>\u0000 </div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"15 2","pages":""},"PeriodicalIF":2.7,"publicationDate":"2026-02-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147385671","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Biomimetic Cavity-Induced Catalysis Inside Synthetic Containers","authors":"Soumen K. Samanta","doi":"10.1002/ajoc.202500622","DOIUrl":"10.1002/ajoc.202500622","url":null,"abstract":"<div>\u0000 \u0000 <p>Catalysis plays an important role in synthetic chemistry to carry out chemical transformations. Metal-mediated catalysis and organo-catalysis provide ample opportunities to control selectivity and stereochemistry of products. Enzyme catalysis provides unique opportunities to carry out chemical transformations mostly by encapsulating the substrates within their binding pockets. The ability of natural enzymes to host substrates using noncovalent interactions has been tremendously effective in the field of catalysis (cavity-induced catalysis). Deep cavities in water are excellent hosts for studying molecular recognition by displacing frustrated water molecules to bulk solution (hydrophobic effect). They often lead to highly efficient catalytic reactions with much faster reaction rate, show unusual reactivity, greater control in regio- and stereo-selectivity in products when compared with chemical reactions without enzymes. Enzyme-based catalysis has inspired scientists to mimic catalytic reactions using manmade receptors (Host). In this review article, we discuss the ability of organic and metal–organic hosts to carry out chemical transformations in a biomimetic fashion. We focus on several covalent organic cages those discussed in the literature for performing catalysis in water. Metal–organic cages often provide a larger space inside and thus are able to encapsulate larger substrates as well as active metal catalysts inside. Both metal-free and metal-catalyst-driven chemical transformations inside metal–organic cages are discussed. Catalyst stabilization and unusual chemical transformations were achieved when metal–organic cages were used as hosts.</p>\u0000 </div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"15 2","pages":""},"PeriodicalIF":2.7,"publicationDate":"2026-02-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147385678","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}