Organic chemistry frontiers : an international journal of organic chemistry最新文献

{"title":"Bis-Fischer indole[3,2-b]carbazole modification of [10]cycloparaphenylenes: tuning optical properties through rigid substitution†","authors":"Wanchun Duan ,&nbsp;Dongming Chen ,&nbsp;Dang Zheng ,&nbsp;Shidong He ,&nbsp;Wanqun Hu ,&nbsp;Lvyuan Hao ,&nbsp;Xin Xu","doi":"10.1039/d5qo00539f","DOIUrl":"10.1039/d5qo00539f","url":null,"abstract":"<div><div>The rigid bis-Fischer indolo[3,2-<em>b</em>]carbazole and [<em>n</em>]cycloparaphenylenes ([<em>n</em>]CPP) have garnered interest due to their unique electronic behavior and optoelectronic properties. We have combined 2,8-di-<em>tert</em>-butyl-5,11-dihydroindolo [3,2-<em>b</em>]carbazole () with [10]CPP to form , where the introduced fragment reduces the symmetry of the original [10]CPP parent structure, and amplifies the previously weak absorption band at 450 nm. Compared with unmodified [10]CPP, the fluorescence wavelength shows a significant redshift, and the solvatochromic effect becomes more pronounced with increasing solvent polarity, reaching 553 nm in dimethyl sulfoxide. Its photoluminescence quantum yield (PLQY) initially increases and then decreases, peaking at 0.92 in dichloromethane, which is significantly higher than that of both [10]CPP and . Calculations highlight the origin of intramolecular charge transfer within and the elimination of Laporte-forbidden transitions. The interaction between the fragment and the solvent enhances the solvatochromic effect, underscoring the critical role of the introduced fragment in tuning fluorescence behavior. This research makes it a promising and worthwhile area for exploration.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 17","pages":"Pages 4800-4807"},"PeriodicalIF":0.0,"publicationDate":"2025-04-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143872748","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Acidic pH-modulated photoswitching of sulfur-bridged seven-membered cyclic azopyridines†","authors":"Fengying Lan ,&nbsp;Cefei Zhang ,&nbsp;Zhihao Liu ,&nbsp;Sitong Li ,&nbsp;Jinmeng Yan ,&nbsp;Xiaohu Zhao ,&nbsp;Changwei Hu ,&nbsp;Zhishan Su ,&nbsp;Pengchi Deng ,&nbsp;Zhipeng Yu","doi":"10.1039/d5qo00315f","DOIUrl":"10.1039/d5qo00315f","url":null,"abstract":"<div><div>Azoarene molecular photoswitches with bistability are a family of widely employed structure-tuning units for photopharmacology and smart material construction. Notably, medium-ring azobenzenes, especially seven-membered dibenzo[<em>b</em>,<em>f</em>][1,4,5]thiadiazepines (DBTD), are characterized as fast-responsive T-type molecular photoswitches with particular features for light-energy conversion to ring-strain energy. The proliferation of azoheteroarenes with enhanced bistability and solubility has considerably broadened the horizon of their utilization. Herein, we present a novel class of seven-membered cyclic azoheteroarenes, benzo[<em>b</em>]pyrido[<em>f</em>][1,4,5]thiadiazepines (BPTD) and dipyrido[2,3-<em>b</em>:3′,2′-<em>f</em>][1,4,5]thiadiazepine (DPTD). The integration of pyrido-heteroarenes in BPTD and DPTD enables pH-modulated T-type photoswitching performance spanning from pH = −0.33 to 7.0, distinguishing them from DBTD. Importantly, benzo[<em>b</em>]pyrido[3,4-<em>f</em>][1,4,5]thiadiazepine (3-BPTD) exhibits slightly enhanced photoswitching amplitude (photostationary distribution of <em>E</em> isomers) as well as decent photo- and thermal stability in highly acidic environments. These features make them promising T-type photoswitches for potential acid-resistant light-energy converters and acid-endurable fast-responsive smart materials.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 17","pages":"Pages 4842-4851"},"PeriodicalIF":0.0,"publicationDate":"2025-04-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143866483","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Countercation- and solvent-controlled selective borohydride hydrogenation of alkenes in diaryl enones†","authors":"Miguel Espinosa ,&nbsp;Miquel Molina-García ,&nbsp;Daniel Ciscares-Velázquez ,&nbsp;Antonio Leyva-Pérez","doi":"10.1039/d5qo00883b","DOIUrl":"10.1039/d5qo00883b","url":null,"abstract":"<div><div>Borohydrides are considered benchmark reagents for the selective hydrogenation of ketones in the presence of alkenes, a reaction described in organic textbooks. However, the opposite, <em>i.e.</em> the borohydride-promoted hydrogenation of an alkene in the presence of a ketone, is barely described. Here we show that the alkene functionality in diaryl enones is preferentially hydrogenated to the ketone under standard uncatalyzed reaction conditions, after using a stoichiometric amount of a metal borohydride (<em>i.e.</em> NaBH₄). For <em>gem</em>-diaryl enones, mechanistic studies indicate that the combination of a suitably cation-substituted borohydride (from Li⁺ to K⁺) and the particular disposition of the highly-conjugated terminal alkene favors a highly selective 1,4-hydride addition, giving access to α-benzyl-substituted propiophenones in high yields, at room temperature and after just 30 min reaction time, without the assistance of any catalyst or additive. For <em>trans</em>-diaryl enones (chalcones), the simple change of the protic co-solvent from MeOH to electron-deficient and sterically-hindered alcohols triggers the selective hydrogenation of the alkene group. These results defy the established reactivity of borohydrides for enones and open a way to employ common borohydride reagents for selective alkene hydrogenation reactions, with potential application in synthetic chemistry.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 17","pages":"Pages 4708-4721"},"PeriodicalIF":0.0,"publicationDate":"2025-04-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144594870","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Green and modular synthesis of azepino[4,3,2-cd]indoles and diazepino[6,5,4-cd]indoles via hydride transfer-involved cascade cyclization in ethanol†","authors":"Qian-Hao Zhuang ,&nbsp;Xiao-Lin Wang ,&nbsp;Wei Gao ,&nbsp;Bin Qiu ,&nbsp;Xiao-De An ,&nbsp;Houchen Wang ,&nbsp;Yao-Bin Shen ,&nbsp;Jian Xiao","doi":"10.1039/d5qo00058k","DOIUrl":"10.1039/d5qo00058k","url":null,"abstract":"<div><div>The modular synthesis of high-value azepino[4,3,2-<em>cd</em>]indole and its analogs from versatile synthons and readily available feedstocks has been a challenging area of research. Herein, we report a 1,6-hydride transfer-involved cascade [6 + 1] cyclization of 4-dialkylamino-indole-3-carbaldehydes with diverse 1<em>C</em>,1<em>C</em>- and 1<em>N</em>,1<em>N</em>-bisnucleophiles in ethanol, enabling the green and modular synthesis of azepino[4,3,2-<em>cd</em>]indoles and diazepino[6,5,4-<em>cd</em>]indoles. The key features of this method are: catalyst-free, redox-neutral conditions, excellent substrate compatibility, operational simplicity, gram-scale applicability, and versatile product derivatization.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 17","pages":"Pages 4808-4817"},"PeriodicalIF":0.0,"publicationDate":"2025-04-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143862654","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Tetraphenylethylene or naphthalimide-functionalized dendritic carbazole AIEgens: self-assembly visualization, three disparate force-triggered fluorescence responses, and advanced anticounterfeiting applications†","authors":"Yijie Zou ,&nbsp;Zhao Chen ,&nbsp;Fei Zhao ,&nbsp;Ya Yin ,&nbsp;Kaixin He ,&nbsp;Xingru Liang ,&nbsp;Hai-feng He ,&nbsp;Zhijian Li ,&nbsp;Sheng Hua Liu","doi":"10.1039/d5qo00393h","DOIUrl":"10.1039/d5qo00393h","url":null,"abstract":"<div><div>Three 1,8-naphthalimide-modified donor–π–acceptor-type and three tetraphenylethylene-functionalized fluorogenic dendritic carbazole derivatives are designed and synthesized. These six dendrimer-like carbazole-containing compounds are typical aggregation-induced emission (AIE) luminogens. Specially, the AIE-active possessing trimeric carbazole and two 1,8-naphthalimide groups features aggregation-triggered self-assembly, and the visualization of its intriguing self-assembly process is successfully realized through scanning electron microscopy technology. Notably, three types of contrasting anisotropic mechanical force-induced fluorescence responses from the six prepared dendritic carbazole AIEgens are observed. More specifically, and do not exhibit fluorescence changes after grinding; and display irreversible mechanofluorochromic phenomena; and show reversible mechanofluorochromic characteristics. To deeply elucidate the three distinct types of force-responsive emissive features of the six dendritic AIEgens, powder and single-crystal X-ray diffraction, differential scanning calorimetry experiments, and theoretical simulation calculations of molecular packing structures before and after grinding are carried out. Based on the observed three disparate force-dependent fluorescence phenomena, two advanced information security systems involving multilevel painting anticounterfeiting and multimode information encryption are elaborately constructed.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 17","pages":"Pages 4862-4870"},"PeriodicalIF":0.0,"publicationDate":"2025-04-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143885181","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Chiral phosphoric acid catalyzed asymmetric synthesis of C–N axially chiral uracils with antitumor activity through kinetic resolution strategy†","authors":"Jiawei Xu ,&nbsp;Haisong Xu ,&nbsp;Yunyi Xu ,&nbsp;Zhongqi Peng ,&nbsp;Wei Zhang ,&nbsp;Xin Li","doi":"10.1039/d5qo00144g","DOIUrl":"10.1039/d5qo00144g","url":null,"abstract":"<div><div>An efficient method for the asymmetric synthesis of C–N axially chiral uracils has been developed by kinetic resolution of 6-NH₂-substituted uracils with achiral azlactones, using chiral phosphoric acid-catalyzed asymmetric acylation. A broad range of 6-NH₂ uracils were resolved with high efficiency and enantioselectivity, achieving a selectivity factor of up to 276. DFT calculations revealed the origins of the enantioselectivity. Large-scale reaction and straightforward transformations of the chiral products highlighted the practical value of this methodology. Furthermore, potential antitumor agents were identified through cellular assays, illustrating the synthetic utility of this approach.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 17","pages":"Pages 4764-4772"},"PeriodicalIF":0.0,"publicationDate":"2025-04-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143866793","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Mechanistic insights into Ni–Al co-catalyzed alkyne carbophosphination enabled by C–P bond activation†","authors":"Congcong Huang ,&nbsp;Yishi Li ,&nbsp;Juan Li","doi":"10.1039/d5qo00453e","DOIUrl":"10.1039/d5qo00453e","url":null,"abstract":"<div><div>Nickel–aluminum (Ni–Al) bimetallic catalysis has demonstrated remarkable efficiency in C–P bond activation, yet its underlying mechanism remains elusive. Key questions regarding the synergistic roles of Ni and Al, the advantages of the dual-catalyst system, and the effect of the substrate and ligand are critical for advancing this strategy. Here, we employ density functional theory (DFT) calculations to systematically investigate the Ni–Al cooperative catalysis mechanism, focusing on the interplay between Ni and Al, the impact of AlMe₂Cl, the role of PPh₃, and the effect of substituents on reaction efficiency. We explored two cooperative models for Ni–Al interactions and found that the uncommon Ni–LA interaction (Model A) is more favorable than the Ni–LA–L bridged system (Model B). This preference arises because the use of PPh₃ makes phenyl migration or phenyl dehydrogenation highly unfavorable, thereby directing the reaction toward Model A as the optimal pathway. Our results demonstrate that AlMe₂Cl plays a crucial role in stabilizing key transition states through non-covalent interactions, charge redistribution, electrostatic stabilization, and electron density distribution, as well as modulating HOMO and LUMO energies, effectively lowering activation barriers. Additionally, PPh₃ enhances reaction efficiency by facilitating stabilizing non-covalent interactions, strengthening Ni coordination through a Ni–P bond, and optimizing charge transfer. Furthermore, an analysis of substrate effects reveals that both steric congestion and electronic stabilization influence reaction efficiency, with smaller and more electronically favorable substituents facilitating charge transfer, lowering oxidative addition barriers, and leading to higher experimental yields. These findings provide a detailed mechanistic understanding of Ni–Al bimetallic catalysis in C–P bond activation and offer guiding principles for the rational design of more efficient catalytic systems. The study not only clarifies the synergistic roles of Ni and Al but also highlights the critical influence of ligands and substrate effects in optimizing reaction outcomes.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 17","pages":"Pages 4722-4742"},"PeriodicalIF":0.0,"publicationDate":"2025-04-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143872747","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"meta-Selective thiofluoroalkylation of substituted pyridines via Zincke imines†","authors":"Will C. Hartley ,&nbsp;Arnau Huerta ,&nbsp;Júlia C. Negredo ,&nbsp;Omar Boutureira","doi":"10.1039/d5qo00533g","DOIUrl":"10.1039/d5qo00533g","url":null,"abstract":"<div><div>Zincke imines enable the regioselective thiofluoroalkylation of substituted pyridines, providing access to thioalkylated pyridines bearing a range of fluorination patterns. Crucial to the success of this strategy was the use of saccharine-derived thiofluoroalkylating reagents, which, upon reaction with TMSCl, generate electrophilic sulfenyl chlorides.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 17","pages":"Pages 4794-4799"},"PeriodicalIF":0.0,"publicationDate":"2025-04-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143876086","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Fluorine-containing macrocyclic peptides and peptidomimetics","authors":"Neshat Rozatian ,&nbsp;Stefan Roesner","doi":"10.1039/d5qo00219b","DOIUrl":"10.1039/d5qo00219b","url":null,"abstract":"<div><div>Fluorination plays a vital role in medicinal chemistry due to the unique properties of the fluorine atom. Macrocyclic peptides offer advantageous properties compared to linear peptides in drug discovery. In recent years, the development of fluorinated macrocyclic peptides and peptidomimetics, such as voxilaprevir, MK-0616 and ulimorelin, has highlighted the growing interest in the combination of fluorination and cyclization for tuning the properties of peptidic drug leads. In this review, the effects of fluorination on biological properties of macrocyclic peptides will be discussed. The use of the fluorine atom as a ¹⁹F NMR spectroscopy probe for conformational studies of macrocyclic peptides will be reviewed. Finally, macrocyclic peptides containing the radionucleotide ¹⁸F as PET imaging agents will be highlighted.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 17","pages":"Pages 4871-4895"},"PeriodicalIF":0.0,"publicationDate":"2025-04-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143910185","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Synthesis of 8-membered trifluoromethyl benzoxazocines via a Pd-catalyzed ring-expansion reaction of trifluoromethyl benzoxazinones with 2-methylidenetrimethylene carbonate and mechanistic investigations†","authors":"Bo Yang ,&nbsp;Peng-Fei Sun ,&nbsp;Xue Ma ,&nbsp;Zhouyang Long ,&nbsp;Li-Ming Zhao","doi":"10.1039/d4qo02076f","DOIUrl":"10.1039/d4qo02076f","url":null,"abstract":"<div><div>We report a Pd-catalyzed ring-expansion reaction of trifluoromethyl benzoxazinones with 2-methylidenetrimethylene carbonate. This method exhibits high efficiency and broad functional group tolerance, which leads to the rapid assembly of a series of valuable 8-membered trifluoromethyl benzoxazocines with good yields in a simple manner. The synthetic utility of the approach is demonstrated by the facile transformation of product. The reaction mechanism was also investigated by density functional theory (DFT) calculations, suggesting that the carbonyl group has a greater influence on the site-selectivity than the trifluoromethyl group in the decarboxylative ring re-construction process of benzoxazinones.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 17","pages":"Pages 4825-4833"},"PeriodicalIF":0.0,"publicationDate":"2025-04-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143880874","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}