Hai Kuan Yang,Qin Yang,Yang Fu,Qiuping Ding,Yiyuan Peng
Herein, we report an efficient strategy for the direct construction of polysubstituted benzo[h][1,6]naphthyridines through skeletal editing of quinazoline N-oxides with enynones. Under TsOH catalysis, an initial [3+2] cyclization triggers a cascade rearrangement involving quinazoline ring opening and recyclization, enabling direct access to a broad range of structurally diverse benzo[h][1,6]naphthyridines. The resulting benzo[h][1,6]naphthyridine scaffolds are readily amenable to further functionalization, providing a versatile platform for the development of π-conjugated organic functional materials with tuneable structures and potential optoelectronic applications.
{"title":"Skeletal Editing of Quinazoline N-Oxides with Enynones: Synthesis of Polysubstituted Benzo[h][1,6]naphthyridines and Their Photophysical Properties","authors":"Hai Kuan Yang,Qin Yang,Yang Fu,Qiuping Ding,Yiyuan Peng","doi":"10.1039/d6qo01297c","DOIUrl":"https://doi.org/10.1039/d6qo01297c","url":null,"abstract":"Herein, we report an efficient strategy for the direct construction of polysubstituted benzo[h][1,6]naphthyridines through skeletal editing of quinazoline N-oxides with enynones. Under TsOH catalysis, an initial [3+2] cyclization triggers a cascade rearrangement involving quinazoline ring opening and recyclization, enabling direct access to a broad range of structurally diverse benzo[h][1,6]naphthyridines. The resulting benzo[h][1,6]naphthyridine scaffolds are readily amenable to further functionalization, providing a versatile platform for the development of π-conjugated organic functional materials with tuneable structures and potential optoelectronic applications.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"13 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149230175","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}
We report an efficient cross-electrophile coupling between easily available aryl thianthrenium salts and aryl nonaflates. The reactions proceeded effectively by means of C-S and C-O bonds breakage under the assistance of Pd(PPh3)2Cl2, SPhos, B2(OH)4, and Na2CO3 in MeOH, enabling the facile assembly of a wide spectrum of biaryls in moderate-to-excellent yields. The reaction features good substrate generality, wide functional group tolerance, capability for scale-up preparation, and feasibility for the late-stage elaboration of bioactive complex molecules. Remarkably, one-pot, two-step reactions with the direct use of broadly available and simple arenes and phenols as substrates could also be successfully achieved.
{"title":"Palladium-catalyzed cross-electrophile couplings of aryl thianthrenium salts with aryl nonaflates","authors":"Yuan-De Li,Yun Zhou,Han-Han Zhang,Xue-Qiang Chu,Hao Xu,Haiqing Luo,Yu-Cai Tang,Zi Yang,Zhi-Liang Shen","doi":"10.1039/d6qo01307d","DOIUrl":"https://doi.org/10.1039/d6qo01307d","url":null,"abstract":"We report an efficient cross-electrophile coupling between easily available aryl thianthrenium salts and aryl nonaflates. The reactions proceeded effectively by means of C-S and C-O bonds breakage under the assistance of Pd(PPh3)2Cl2, SPhos, B2(OH)4, and Na2CO3 in MeOH, enabling the facile assembly of a wide spectrum of biaryls in moderate-to-excellent yields. The reaction features good substrate generality, wide functional group tolerance, capability for scale-up preparation, and feasibility for the late-stage elaboration of bioactive complex molecules. Remarkably, one-pot, two-step reactions with the direct use of broadly available and simple arenes and phenols as substrates could also be successfully achieved.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"33 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149241517","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}
Si-Jing Jiang,Xiao-Han Qiu,Li-Na Yang,Bang-Yi Zhang,Yu-Ning Gao,Ming Bian,Cun-Feng Song,Hui-Yu Chen,Zhen-Jiang Liu
An additive-free protocol is developed for the synthesis of 3-(trifluoromethylthio)benzofurans, benzothiophenes, and benzopyrans from alkoxyalkynylbenzenes, alkylthioalkynylbenzenes, and alkoxypropargylbenzenes, respectively, using trifluoromethanesulfinyl chloride as the electrophilic trifluoromethylthiolating reagent. Over 40 examples are demonstrated with 63-94% yields, and gram-scale reactions proceed with maintained efficiency. The possible mechanism involves initial electrophilic addition of in situ generated CF₃SCl to the alkyne to form a three-membered sulfonium intermediate, followed by 5-endo or 6-endo cyclization and subsequent O-demethylation to afford the desired products.
{"title":"Additive-Free Tandem Trifluoromethylthiolation/Cyclization for the Synthesis of 3-(Trifluoromethylthio)benzofurans and Benzopyrans Using CF₃SOCl","authors":"Si-Jing Jiang,Xiao-Han Qiu,Li-Na Yang,Bang-Yi Zhang,Yu-Ning Gao,Ming Bian,Cun-Feng Song,Hui-Yu Chen,Zhen-Jiang Liu","doi":"10.1039/d6qo01057a","DOIUrl":"https://doi.org/10.1039/d6qo01057a","url":null,"abstract":"An additive-free protocol is developed for the synthesis of 3-(trifluoromethylthio)benzofurans, benzothiophenes, and benzopyrans from alkoxyalkynylbenzenes, alkylthioalkynylbenzenes, and alkoxypropargylbenzenes, respectively, using trifluoromethanesulfinyl chloride as the electrophilic trifluoromethylthiolating reagent. Over 40 examples are demonstrated with 63-94% yields, and gram-scale reactions proceed with maintained efficiency. The possible mechanism involves initial electrophilic addition of in situ generated CF₃SCl to the alkyne to form a three-membered sulfonium intermediate, followed by 5-endo or 6-endo cyclization and subsequent O-demethylation to afford the desired products.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"12 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149241464","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}
Isoxazolines and isoxazoles are important classes of N,O-containing heterocycles. Classic methods rely on the cycloaddition of nitrile oxides with alkenes/alkynes, but the generation of nitrile oxides often requires external oxidants or harsh conditions. In this paper, we unexpectedly discovered a class of isolable hydroxamic acid-derived p-toluenesulfonylated precursors that undergo [3 + 2] cycloaddition with alkenes or alkynes at room temperature in acetone in the presence of potassium carbonate, efficiently affording structurally diverse isoxazolines and isoxazoles. This method requires no external oxidants, features mild conditions, and exhibits a broad substrate scope, providing a new avenue for the mild carbonate-triggered activation of nitrogen–oxygen heterocycles.
{"title":"Isolable hydroxamic acid-derived precursors enable carbonate-triggered nitrile oxide cycloadditions","authors":"Xin Zhang,Guangxing Gu,Yuejia Zhang,Yanchuan Zhao","doi":"10.1039/d6qo01284a","DOIUrl":"https://doi.org/10.1039/d6qo01284a","url":null,"abstract":"Isoxazolines and isoxazoles are important classes of N,O-containing heterocycles. Classic methods rely on the cycloaddition of nitrile oxides with alkenes/alkynes, but the generation of nitrile oxides often requires external oxidants or harsh conditions. In this paper, we unexpectedly discovered a class of isolable hydroxamic acid-derived p-toluenesulfonylated precursors that undergo [3 + 2] cycloaddition with alkenes or alkynes at room temperature in acetone in the presence of potassium carbonate, efficiently affording structurally diverse isoxazolines and isoxazoles. This method requires no external oxidants, features mild conditions, and exhibits a broad substrate scope, providing a new avenue for the mild carbonate-triggered activation of nitrogen–oxygen heterocycles.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"14 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149241467","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}
Triarylmethanes are ubiquitous scaffolds in medicinal chemistry and materials chemistry. However, current synthetic methods often encounter significant challenges, including preinstallation of coupling partners and poor regioselectivity. Herein, we report a metal‑free arylation of pyridone-derived aldehydes with boronic acids via tetracoordinate boron species to synthesize triarylmethanes. This approach features readily available starting materials, good to excellent yields, without preinstalled directing groups. Importantly, the reaction proves to be an efficient strategy for construct drug derived compounds. Mechanistic investigations reveal that this unprecedented transformation involves two sequential 1,3 metallate shifts, and amide is the essential group for in situ-generated tetracoordinate boron intermediate. This method not only unlocks a straightforward synthetic route to triarylmethanes, but also offers a new perspective on the activation mode of organoboron compounds.
{"title":"Metal-free arylation of pyridone-derived aldehydes with boronic acids enables triarylmethane synthesis via two sequential 1,3-metallate shifts","authors":"Jia Xu,Shun-Xu Luan,Xue Li,Ya- Qian Lu,De-Jia Yang,Jie Lei,Zhong-Zhu Chen","doi":"10.1039/d6qo00791k","DOIUrl":"https://doi.org/10.1039/d6qo00791k","url":null,"abstract":"Triarylmethanes are ubiquitous scaffolds in medicinal chemistry and materials chemistry. However, current synthetic methods often encounter significant challenges, including preinstallation of coupling partners and poor regioselectivity. Herein, we report a metal‑free arylation of pyridone-derived aldehydes with boronic acids via tetracoordinate boron species to synthesize triarylmethanes. This approach features readily available starting materials, good to excellent yields, without preinstalled directing groups. Importantly, the reaction proves to be an efficient strategy for construct drug derived compounds. Mechanistic investigations reveal that this unprecedented transformation involves two sequential 1,3 metallate shifts, and amide is the essential group for in situ-generated tetracoordinate boron intermediate. This method not only unlocks a straightforward synthetic route to triarylmethanes, but also offers a new perspective on the activation mode of organoboron compounds.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"842 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149241463","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}
Tandem photocatalysis leveraging multi-photon/multi-electron processes of a single photocatalyst can further boost reducing power to overcome thermodynamic hurdles, yet such reactivity has so far been achieved only with precious iridium complexes. Flavin-dependent enzymes have been shown to undergo two-photon/two-electron processes that generate the excited flavin hydroquinone ([FLhq]*), enabling photocatalytic dehalogenation of monohalides typically with the assistance of the nicotinamide coenzyme (NADPH) and glucose dehydrogenase (GDH). However, this transformation is difficult to reproduce in unbound flavins such as riboflavin tetraacetate (RFT) outside the protein microenvironment, and one-electron reduction of molecular flavin by tertiary amines (e.g., triethylamine, TEA) has traditionally been regarded as the dominant pathway. Here, combined spectroscopic characterization (UV–Vis, NMR, MS), kinetic isotope effect (KIE) analysis, control experiments, and DFT calculations collectively indicated that the first-excited RFT could be two-electron-reduced by TEA to form RFTH−, which subsequently experienced a second photoexcitation to generate [RFTH−]* as the key reducing species, despite TEA being conventionally considered a one-electron donor. This cocatalyst-free RFT/TEA system enabled photocatalytic reduction of diverse vicinal dibromides (vic-Br2), delivering the corresponding internal, terminal, nonfunctionalized, and bioactive-motif-embedded alkenes in good yields. Meanwhile, this photocatalytic system could be scaled up using riboflavin (vitamin B2) and solar energy. Stereoisomeric selectivity and systematic control experiments further elucidated the catalytic debromination mechanism and the interaction between [RFTH−]* and vic-Br2 substrate. Beyond the long-standing one-photon/one-electron viewpoint on molecular flavins, this work uncovered a more reducing intermediate generated through a photon/electron/proton cascade, bridging the mechanistic gap between enzymatic and free flavin photocatalysis.
{"title":"Tandem Two-photon-excitation/Two-electron-reduction of Molecular Flavin for Photocatalytic Reductive Debromination","authors":"Xuan Zhang,Xiaoyu Wang,Ge Jin,Guiwen Guo,Qin Zhang,Yun Han,Jiangtong Zhang,Peiwei Gong,Fanjun Zhang,Mianran Chao,Binju Wang,Duyi Shen","doi":"10.1039/d6qo01365a","DOIUrl":"https://doi.org/10.1039/d6qo01365a","url":null,"abstract":"Tandem photocatalysis leveraging multi-photon/multi-electron processes of a single photocatalyst can further boost reducing power to overcome thermodynamic hurdles, yet such reactivity has so far been achieved only with precious iridium complexes. Flavin-dependent enzymes have been shown to undergo two-photon/two-electron processes that generate the excited flavin hydroquinone ([FLhq]*), enabling photocatalytic dehalogenation of monohalides typically with the assistance of the nicotinamide coenzyme (NADPH) and glucose dehydrogenase (GDH). However, this transformation is difficult to reproduce in unbound flavins such as riboflavin tetraacetate (RFT) outside the protein microenvironment, and one-electron reduction of molecular flavin by tertiary amines (e.g., triethylamine, TEA) has traditionally been regarded as the dominant pathway. Here, combined spectroscopic characterization (UV–Vis, NMR, MS), kinetic isotope effect (KIE) analysis, control experiments, and DFT calculations collectively indicated that the first-excited RFT could be two-electron-reduced by TEA to form RFTH−, which subsequently experienced a second photoexcitation to generate [RFTH−]* as the key reducing species, despite TEA being conventionally considered a one-electron donor. This cocatalyst-free RFT/TEA system enabled photocatalytic reduction of diverse vicinal dibromides (vic-Br2), delivering the corresponding internal, terminal, nonfunctionalized, and bioactive-motif-embedded alkenes in good yields. Meanwhile, this photocatalytic system could be scaled up using riboflavin (vitamin B2) and solar energy. Stereoisomeric selectivity and systematic control experiments further elucidated the catalytic debromination mechanism and the interaction between [RFTH−]* and vic-Br2 substrate. Beyond the long-standing one-photon/one-electron viewpoint on molecular flavins, this work uncovered a more reducing intermediate generated through a photon/electron/proton cascade, bridging the mechanistic gap between enzymatic and free flavin photocatalysis.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"9 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149230176","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}
Senthilkumar V Swetha,Murali Ardra,P. K. M. Imran,Samuthira Nagarajan
Building upon the donor-acceptor design principle, a series of six new compounds was designed and synthesised by integrating a tetraphenylphenylenediamine (TPPA) electron donor moiety coupled with the structurally diverse quinoxalinebased electron acceptor moiety to probe the impact of structural modulation on resistive memory device performance. A comprehensive structure-property relationship was established through photophysical studies, thin-film morphology, density functional theory (DFT) calculations, and memory characteristics. The synthesised compounds exhibited pronounced intramolecular charge transfer with broad visible absorption and a narrow optical band gap of 2.6-2.9 eV, demonstrating the efficient nature of D-A segments. FESEM and AFM analyses revealed continuous, homogeneous thin films with interconnected molecular packing, providing favorable pathways for charge transport. The fabricated devices exhibited excellent non-volatile resistive switching characteristics, including low operating voltages (-1.19 to -1.49 V), an ON/OFF current ratio of 10 3 -10 4 , stable data retention exceeding 5 s, and reliable endurance over 10² switching cycles, with negligible device-to-device variation. Remarkably, the dimethoxydiphenyl-substituted quinoxaline derivative exhibited ternary writeonce-read-many (WORM) memory behaviour, whereas the remaining derivatives demonstrated binary WORM characteristics. The results were further substantiated by DFT calculations, which revealed efficient intramolecular charge transfer between the donor TPPA and acceptor quinoxaline moiety. By systematically tailoring the quinoxaline acceptor unit, this work demonstrates how subtle molecular modifications can precisely regulate structural and memory properties. The insights provided a fundamental framework for the rational design of D-A molecular systems for efficient, stable, and low operating-voltage organic non-volatile memory devices.
{"title":"Acceptor-Driven Structural Modulation of Tetraphenylphenylenediamine-Based Donor-Acceptor Architectures for Non-Volatile Resistive Memory Devices","authors":"Senthilkumar V Swetha,Murali Ardra,P. K. M. Imran,Samuthira Nagarajan","doi":"10.1039/d6qo01154c","DOIUrl":"https://doi.org/10.1039/d6qo01154c","url":null,"abstract":"Building upon the donor-acceptor design principle, a series of six new compounds was designed and synthesised by integrating a tetraphenylphenylenediamine (TPPA) electron donor moiety coupled with the structurally diverse quinoxalinebased electron acceptor moiety to probe the impact of structural modulation on resistive memory device performance. A comprehensive structure-property relationship was established through photophysical studies, thin-film morphology, density functional theory (DFT) calculations, and memory characteristics. The synthesised compounds exhibited pronounced intramolecular charge transfer with broad visible absorption and a narrow optical band gap of 2.6-2.9 eV, demonstrating the efficient nature of D-A segments. FESEM and AFM analyses revealed continuous, homogeneous thin films with interconnected molecular packing, providing favorable pathways for charge transport. The fabricated devices exhibited excellent non-volatile resistive switching characteristics, including low operating voltages (-1.19 to -1.49 V), an ON/OFF current ratio of 10 3 -10 4 , stable data retention exceeding 5 s, and reliable endurance over 10² switching cycles, with negligible device-to-device variation. Remarkably, the dimethoxydiphenyl-substituted quinoxaline derivative exhibited ternary writeonce-read-many (WORM) memory behaviour, whereas the remaining derivatives demonstrated binary WORM characteristics. The results were further substantiated by DFT calculations, which revealed efficient intramolecular charge transfer between the donor TPPA and acceptor quinoxaline moiety. By systematically tailoring the quinoxaline acceptor unit, this work demonstrates how subtle molecular modifications can precisely regulate structural and memory properties. The insights provided a fundamental framework for the rational design of D-A molecular systems for efficient, stable, and low operating-voltage organic non-volatile memory devices.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"42 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149225873","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}
The two-component cross-heterocyclization of α-acidic isocyanides has proven to be an efficient method for constructing various mono- or bi-heterocyclic scaffolds. However, the multicomponent biheterocyclization of two different isocyanides remains challenging due to their propensity for side reactions. Herein, we report the first example of a highly chemoselective three-component biheterocyclization-chalcogenation of two distinct isocyanides and readily available chalcogen nucleophiles, providing straightforward access to diverse 4-chalcogenylated pyrrolo[2,3-c]quinolines. Furthermore, gram-scale synthesis and several transformations of the resulting product underscore the synthetic utility of the developed methodology.
{"title":"Chemoselective three-component biheterocyclization-chalcogenation of two distinct isocyanides with chalcogen nucleophiles for modular synthesis of 4-chalcogenylated pyrrolo[2,3-c]quinolines","authors":"Jinhuan Dong,Shangying Qiao,Lianshun Zhang,Wei Yang,Xianxiu Xu","doi":"10.1039/d6qo01195k","DOIUrl":"https://doi.org/10.1039/d6qo01195k","url":null,"abstract":"The two-component cross-heterocyclization of α-acidic isocyanides has proven to be an efficient method for constructing various mono- or bi-heterocyclic scaffolds. However, the multicomponent biheterocyclization of two different isocyanides remains challenging due to their propensity for side reactions. Herein, we report the first example of a highly chemoselective three-component biheterocyclization-chalcogenation of two distinct isocyanides and readily available chalcogen nucleophiles, providing straightforward access to diverse 4-chalcogenylated pyrrolo[2,3-c]quinolines. Furthermore, gram-scale synthesis and several transformations of the resulting product underscore the synthetic utility of the developed methodology.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"64 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149225918","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}
Herein, we report a visible-light-mediated hydroalkylation of [1.1.1]propellane with α-bromocarbonyl compounds using a metal-free photoredox catalytic system. This protocol operates under exceptionally mild conditions and accommodates a broad range of esters, amides, and ketones, delivering the corresponding BCP adducts in moderate to excellent yields. Experimental and computational mechanistic studies support a radical pathway initiated by single-electron transfer from the photocatalyst, followed by radical addition to [1.1.1]propellane and subsequent hydrogen atom transfer from the solvent. The synthetic utility of this approach is further underscored by its scalability and its compatibility with complex molecular scaffolds. This strategy provides a modular and efficient entry to structurally diverse BCP derivatives, offering promising opportunities for drug discovery and advanced synthesis.
{"title":"Synthesis of α‑BCP carbonyls through visible‑light‑driven hydroalkylation of [1.1.1]propellane","authors":"Yating Du,Xinchang Wang,Xiaoyang Yao,An Chen,Pengfei Zhang,Jun Xu","doi":"10.1039/d6qo01153e","DOIUrl":"https://doi.org/10.1039/d6qo01153e","url":null,"abstract":"Herein, we report a visible-light-mediated hydroalkylation of [1.1.1]propellane with α-bromocarbonyl compounds using a metal-free photoredox catalytic system. This protocol operates under exceptionally mild conditions and accommodates a broad range of esters, amides, and ketones, delivering the corresponding BCP adducts in moderate to excellent yields. Experimental and computational mechanistic studies support a radical pathway initiated by single-electron transfer from the photocatalyst, followed by radical addition to [1.1.1]propellane and subsequent hydrogen atom transfer from the solvent. The synthetic utility of this approach is further underscored by its scalability and its compatibility with complex molecular scaffolds. This strategy provides a modular and efficient entry to structurally diverse BCP derivatives, offering promising opportunities for drug discovery and advanced synthesis.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"2 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149225872","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}
Miao-Ying Wang,Fei-Hu Cui,Hai-Tao Tang,Ying-Ming Pan
Chalcogen-containing compounds serve as essential scaffolds in drugs and natural products. Electrocatalytic multicomponent reactions offer a sustainable strategy for constructing organosulfur, organoselenium, and organotellurium compounds. By leveraging electrons as clean reactants, this method eliminates the need for additional chemical oxidants, reducing waste generation and environmental footprint. Precise regulation of reaction potential and current density enables adjustable reaction pathways, which improves reaction selectivity, efficiency and product purity. This review focuses on electrocatalytic multicomponent reactions for the synthesis of organic chalcogenide compounds, with emphasis on reaction design, process optimization, substrate scope and the mechanism of selectivity. It also discusses catalyst development and stability for sulfur, selenium and tellurium-based reaction systems. Current challenges, including limited substrate compatibility, catalyst deactivation and large-scale synthesis difficulties, are also analyzed. Future research directions include developing more efficient electrocatalysts, expanding applications in pharmaceutical synthesis, and integrating the method with renewable energy sources. The insights presented in this review are intended to guide the green and efficient synthesis of valuable organochalcogen compounds, and contribute to the development of sustainable organic chemistry.
{"title":"Recent advances in electrocatalytic multicomponent reactions for synthesizing organic chalcogenide compounds","authors":"Miao-Ying Wang,Fei-Hu Cui,Hai-Tao Tang,Ying-Ming Pan","doi":"10.1039/d6qo01329e","DOIUrl":"https://doi.org/10.1039/d6qo01329e","url":null,"abstract":"Chalcogen-containing compounds serve as essential scaffolds in drugs and natural products. Electrocatalytic multicomponent reactions offer a sustainable strategy for constructing organosulfur, organoselenium, and organotellurium compounds. By leveraging electrons as clean reactants, this method eliminates the need for additional chemical oxidants, reducing waste generation and environmental footprint. Precise regulation of reaction potential and current density enables adjustable reaction pathways, which improves reaction selectivity, efficiency and product purity. This review focuses on electrocatalytic multicomponent reactions for the synthesis of organic chalcogenide compounds, with emphasis on reaction design, process optimization, substrate scope and the mechanism of selectivity. It also discusses catalyst development and stability for sulfur, selenium and tellurium-based reaction systems. Current challenges, including limited substrate compatibility, catalyst deactivation and large-scale synthesis difficulties, are also analyzed. Future research directions include developing more efficient electrocatalysts, expanding applications in pharmaceutical synthesis, and integrating the method with renewable energy sources. The insights presented in this review are intended to guide the green and efficient synthesis of valuable organochalcogen compounds, and contribute to the development of sustainable organic chemistry.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"12 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149218265","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}
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