Organic Chemistry Frontiers最新文献

{"title":"Photoinduced β-fragmentation for efficient pyridine alkylation via N-alkoxypyridinium salts","authors":"Heng Liu, Fangrui Wu, Zhidong Wan, Changhai Yue, Changsheng Wang, Chengkou Liu, Yuguang Li, Zheng Fang, Hong Qin, Zhao Yang","doi":"10.1039/d5qo00400d","DOIUrl":"https://doi.org/10.1039/d5qo00400d","url":null,"abstract":"Pyridine is a key structural motif in pharmaceuticals, and its functionalization is of great research value. We present an efficient alkylation method using <em>N</em>-alkoxypyridinium salts as bifunctional reagents. This protocol operates under mild conditions and offers a broad substrate scope, enabling rapid molecular construction <em>via</em> β-fragmentation with low catalyst loading.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"38 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-05-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144122600","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Chelation-Controlled Stereospecific Ring-Opening Arylation of α-Aminoaryl-Tethered Alkylidenecyclopropanes: Stereoselective Synthesis of Polysubstituted Conjugated Dienes","authors":"Miao-Miao Ji, Ying Tang, Wen-Mei Luo, Yong-Yu He, Ai-Jun Ma, Jin-Bao Peng","doi":"10.1039/d5qo00496a","DOIUrl":"https://doi.org/10.1039/d5qo00496a","url":null,"abstract":"Conjugated dienes are vital due to their presence in natural products, bioactive molecules and functional materials as well as their wide synthetic applications. Herein, we report a palladium catalyzed stereospecific ring-opening arylation of α-aminoaryl-tethered alkylidenecyclopropanes for the stereoselective synthesis of 1,1,2-trisubstituted conjugated dienes. This method features excellent functional group tolerance (tolerated functional groups include ether, thioether, halogen, aldehyde, cyano, ester, ketone, trifluoromethoxy and alkenyl), a good substrate scope (35 examples), and high regio- and stereoselectivity.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"20 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-05-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144122602","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Recent Progress in Selective Functionalization of Diols via Organocatalysis","authors":"Liaba Niaz, Sojeong Bang, Jeonghyo Lee","doi":"10.1039/d5qo00645g","DOIUrl":"https://doi.org/10.1039/d5qo00645g","url":null,"abstract":"Polyols bearing multiple hydroxyl groups present persistent challenges for site-selective functionalization due to their inherent reactivity similarity. As minimal polyol systems, diols offer a practical and conceptually rich platform for developing regioselective catalytic strategies. This review highlights recent progress in organocatalyzed diol functionalization, with a survey of organocatalysts incorporating boron, nitrogen, and phosphorus-based motifs, as well as emerging photoredox methodologies. These systems enable selective transformation under mild conditions, avoiding stoichiometric activation and minimizing reaction complexity. Steric and electronic effects, along with noncovalent interactions, are examined in detail to rationalize the observed selectivity and guide the rational design of catalysts. Collectively, this review offers a conceptual foundation for advancing sustainable, selective methods in diol derivatization.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"157 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-05-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144122601","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"BF3-Enabled Unusual (3 + 2) Cycloaddition of Bicyclobutanes with Aldimine Ester: Access to 2-Azabicyclo[2.1.1]hexanes","authors":"Qin Jiang, Jianyang Dong, Dejiang Yu, Fang Lei, Ting Li, Tengfei Kang, Huaming Sun, Juan Fan, Dong Xue","doi":"10.1039/d5qo00579e","DOIUrl":"https://doi.org/10.1039/d5qo00579e","url":null,"abstract":"Cycloaddition reactions involving bicyclobutanes (BCBs) have garnered significant interest in the synthesis of bicyclic frameworks, particularly due to their utility as saturated bioisosteres for benzenoid rings in contemporary drug discovery. Despite these advancements, the cycloaddition of BCBs with N-alkyl (hetero)aryl imines to construct 2-azabicyclo[2.1.1]hexanes (2-aza-BCHs) has remained an unresolved challenge. In this work, we disclose a BF3-enabled, unusual (3 + 2) cycloaddition between BCBs and aldimine esters, providing access to previously elusive 2-aza-BCH derivatives. This transformation not only introduces a novel strategy for cycloadditions involving BCBs and N-alkyl (hetero)aryl imines but also underscores the distinctive reactivity of aldimine esters as C=N two-atom synthons in cycloaddition chemistry. To further demonstrate the synthetic potential of this methodology, we conducted a scaled-up reaction and performed diverse synthetic modifications of the products, yielding a range of valuable nitrogen-containing bridged bicyclic scaffolds.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"15 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-05-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144113528","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A formal vinylogous Schmidt reaction: nitrogen insertion of para-quinone methides","authors":"Bo Wang, Chen Zhu, Yanhao Dong, Chen Kong, Hanxiao Zhu, Tiandi Ding, Guoyue Wei, Yatong Yang, Xin Zhao, Magnus Rueping, Qingqiang Yao, Kun Zhao, Yan Li, Ying Zhi","doi":"10.1039/d5qo00476d","DOIUrl":"https://doi.org/10.1039/d5qo00476d","url":null,"abstract":"Compared with recent nitrogen addition reactions, which mainly focus on the styrene motif, feasible modification of a conjugated C(sp<small>²</small>)–C(sp<small>²</small>) single bond is rare due to its robustness. Herein, we report a facile nitrogen introduction to the conjugated C(sp<small>²</small>)–C(sp<small>²</small>) bond of <em>p</em>-QMs through a vinylogous Schmidt process, using N-OTs carbamate as a bench-stable ambiphilic nitrogen source. Depending on the electron-donating ability of the <em>ortho</em>-substituent on the benzene ring, the reaction underwent the formal vinylogous Schmidt process through an aziridine intermediate or a 1,6-addition/cyclization step delivering benzoxazolidine or dihydroindazole scaffolds, respectively. This study not only expands the application boundary of the Schmidt reaction but also provides a new strategy for nitrogen addition to a C(sp<small>²</small>)–C(sp<small>²</small>) bond.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"13 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-05-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144104247","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"α-Sulfonylated ketazine synthesis from vinyl azides and sodium sulfinates using CAN: Radical C-S/N-N coupling cascade as a key reaction pathway","authors":"Mikhail M. Doronin, Alexander S. Klikushin, Olga Mikhailovna Mulina, Michael Medvedev, Vera A. Vil', Liang-Nian He, Alexander Olegovich Terent'ev","doi":"10.1039/d5qo00508f","DOIUrl":"https://doi.org/10.1039/d5qo00508f","url":null,"abstract":"Synthesis of α-sulfonylated ketazines from vinyl azides and sodium sulfinates proceeding via radical C-S/N-N coupling cascade has been developed. The cascade starts from the generation of sulfonyl radicals through RSO2Na oxidation by cerium (IV) ammonium nitrate (CAN). Their addition to the double bond of vinyl azides, followed by N2 elimination, leads to the formation of iminyl radicals, whose N-N coupling provides α-sulfonylated ketazines in yields up to 96%. This process represents one of the rare facets of iminyl radical reactivity, namely, N-N radical coupling while bypassing their reduction, intramolecular cyclization, and 1,n-HAT that are typical for them. The EPR-spectra study and quantum chemical calculations revealed that the selective N-N coupling of iminyl radicals was facillitated by the inertness of Ce(III) towards coordination with iminyl radicals and the inaccessibility of charge transfer. In contrast, Mn(II) coordinates with iminyl radicals and converts them into enamines.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"41 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-05-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144088024","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Palladium-catalyzed intramolecular redox-relay Heck cyclization: access to heterocycles bearing all-carbon quaternary centers","authors":"Linjun Qi, Rongjing He, Xiaofeng Tong, Shuling Yu","doi":"10.1039/d5qo00431d","DOIUrl":"https://doi.org/10.1039/d5qo00431d","url":null,"abstract":"While the intramolecular Heck reaction of aryl/vinyl halides with various alkenes has been well studied, the exploration of acyclic alkenol systems <em>via</em> a redox-relay strategy remains unexploited. Herein, we disclose the first palladium-catalyzed intramolecular redox-relay Heck cyclization of vinyl/aryl iodides with alkenols for establishing heterocyclic all-carbon quaternary centers. Diverse 5–7-membered (benzo)heterocycles with a remote carbonyl functionality are obtained in good to excellent yields using a bipyridine ligand. Moreover, an asymmetric version of this transformation could be realized in good yield with promising enantioselectivity.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"151 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-05-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144088026","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"2-Pyridone-Enabled Manganese-Catalyzed ortho-Selective Deuteration of Aromatic Amides with D₂O","authors":"Tao Qian, Zhi-Jiang Jiang, Jinfeng Zheng, Jia Chen, Zhanghua Gao, Jian-Fei Bai","doi":"10.1039/d5qo00606f","DOIUrl":"https://doi.org/10.1039/d5qo00606f","url":null,"abstract":"We present a highly efficient and regioselective methodology for the synthesis of ortho-deuterated aromatic amides, utilizing Mn(CO)₅Br as the catalyst, 2-pyridone as the CMD base, and D₂O as the deuterium source. This approach exhibits a broad substrate scope and exceptional functional group tolerance, enabling the late-stage deuteration of complex molecules with high yields and substantial deuterium incorporation. Mechanistic investigations suggest that 2-pyridone plays a critical role in the success of the reaction, acting as an endogenous base that facilitates reversible C−H activation and subsequent hydrogen-deuterium exchange. Deuterium-labeled compounds have become indispensable tools in a wide array of scientific domains[1], including mechanistic investigations of organic reactions[2], the development of deuterated drugs[3], and quantitative mass spectrometry analyses[4]. Consequently, the synthesis of deuterium-labeled organic compounds has attracted significant research attention. Aromatic carboxylic acids and their derivatives, as fundamental structural units, play a pivotal role in drug development and are commonly incorporated into the molecular frameworks of a wide variety of pharmacologically active compounds[5], such as Procainamide[6], Amisulpride[7], and Nemonapride[8]. Among these, benzamide derivatives have garnered substantial interest due to their broad spectrum of biological and pharmacological activities. Therefore, the design and development of selective synthetic methodologies for site-specific deuterated amide compounds is of considerable academic importance and holds significant potential for both theoretical advancements and practical applications in pharmaceutical chemistry. The direct hydrogen-deuterium (H/D) exchange of amide compounds is typically facilitated under catalytic conditions that involve acids, bases, or transition metals (such as Pd, Pt, Ru, Rh, and Ir)[9]. The use of directing groups to promote these exchanges has been extensively studied. For example, Yu et al. demonstrated efficient ortho-deuteration of aromatic amides using a palladium catalyst and 8-aminoquinoline as a directing group (Scheme 1a)[10]. More recently, our group developed an alternative methodology utilizing Ni(OTf)2 or CuO as catalysts to achieve efficient ortho-deuteration of benzamide derivatives[11]. However, these approaches often rely on costly deuterium sources and HFIP as the solvent, which reduces the theoretical deuterium incorporation and limits their broader applicability, as well as their potential for further functionalization.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"10 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-05-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144088025","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Selective separation of meta- and para-cresol using nonporous adaptive crystals of perpropoxylated pillar[5]arene","authors":"Hongyan Zhang, Ming Li, Li Shao, Haozhong Liang, Bin Hua, Niveen M. Khashab, Feihe Huang","doi":"10.1039/d5qo00620a","DOIUrl":"https://doi.org/10.1039/d5qo00620a","url":null,"abstract":"The selective separation of meta-cresol (MC) and para-cresol (PC) remains a significant challenge due to their nearly identical physicochemical properties. Here, we report nonporous adaptive crystals (NACs) based on perpropoxylated pillar[5]arene (PrP5) for the efficient and selective adsorption of MC over PC. Specifically, PrP5 crystals demonstrate exceptional selectivity, achieving 94.00% purity in the separation of MC from an equimolar MC/PC mixture while maintaining robust regenerability across multiple cycles. Furthermore, the incorporation of PrP5 into a molecular sieve facilitates the selective removal of trace MC impurities, enhancing PC purity from 98.40% to 99.06% in a single cycle. These findings underscore the potential of PrP5-based NACs as a promising material for the separation and high-purity purification of compounds in industrial processes.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"37 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-05-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143979492","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Pyrrolyl radical-involved di-/tri-functionalization of alkenes by sulfonyl pyrroles via radical/radical cross-coupling","authors":"Jia-Xuan Luo, Ze Zhuang, Yu-Zhang Huang, Xiaohui Kang, Yong Luo","doi":"10.1039/d5qo00557d","DOIUrl":"https://doi.org/10.1039/d5qo00557d","url":null,"abstract":"Installation of a pyrrolyl group on the adjacent position of an electron-withdrawing group presents significant challenges, as either the electrophilic or radical addition to pyrrole is suffered from some drawbacks. Herein, by using the sulfonyl pyrrole as the novel precursor of sulfonyl radical and pyrrolyl radical, a visible light-mediated radical/radical cross-coupling strategy has been developed to construct dipyrrolyl acetonitriles and benzhydryl pyrroles in good efficiency. This success highlighted the utilization of carbon-centered pyrrolyl radical derived from N–S bond activation in synthetic chemistry. This protocol broadened the transformations of sulfonamides and achieved multi-functionalization of alkenes to build quaternary carbon centers. DFT calculation demonstrated that the energy transfer between the excited photocatalyst and sulfonyl pyrrole contributed to N–S bond cleavage and resulted in pyrrolylation.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"81 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-05-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143979494","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}