Li-Jia Chen, Yong-Yu He, Yu-Qing Wang, Lin Liu, Jun Ying, Jin-Bao Peng
A base-promoted [4+3] annulation of pyrrole-2-carbaldehydes with indene-2-carbaldehydes for synthesizing indene-fused pyrrolo[1,2-a]azepines has been developed. The reaction proceeds under mild conditions and demonstrates a remarkably broad substrate scope, accommodating a wide range of functional groups with excellent tolerance. In addition, the photophysical properties of the synthesized compounds (3aa-3na, 3ab-3ap) were preliminarily investigated.
{"title":"DBU-Promoted [4+3] Annulation of Pyrrole-2-carbaldehyde Derivatives with Indene-2carbaldehydes: Synthesis of Indene-Fused Pyrrolo[1,2-a]azepines","authors":"Li-Jia Chen, Yong-Yu He, Yu-Qing Wang, Lin Liu, Jun Ying, Jin-Bao Peng","doi":"10.1039/d5qo01433f","DOIUrl":"https://doi.org/10.1039/d5qo01433f","url":null,"abstract":"A base-promoted [4+3] annulation of pyrrole-2-carbaldehydes with indene-2-carbaldehydes for synthesizing indene-fused pyrrolo[1,2-a]azepines has been developed. The reaction proceeds under mild conditions and demonstrates a remarkably broad substrate scope, accommodating a wide range of functional groups with excellent tolerance. In addition, the photophysical properties of the synthesized compounds (3aa-3na, 3ab-3ap) were preliminarily investigated.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"32 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145600102","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}
A substrate-controlled, metal-free strategy for the divergent synthesis of α-sulfonyl amides and nitriles from N-sulfonyl ynamides is disclosed. Under photocatalytic or thermal conditions, sulfonyl radicals initiate a radical chain process, where the reaction pathway is solely dictated by the substrate structure: non-allylic ynamides afford α-sulfonyl amides via hydration, while allylic ynamides exclusively yield α-sulfonyl nitriles through an aza-Claisen rearrangement. This method features broad functional group tolerance, excellent scalability, and 100% atom economy for nitrile formation. This work represents the first general metal-free approach to achieve radical divergence in ynamide chemistry, offering a versatile platform for accessing valuable sulfonyl-containing building blocks.
{"title":"Metal-free divergent radical reactions of N-sulfonyl ynamides: substrate-controlled synthesis of α-sulfonyl amides and α-sulfonyl nitriles","authors":"Xinsong Liu, Ruotong Chen, Yu Yan, Yu Li, Junbiao Chang, Xiao-Na Wang","doi":"10.1039/d5qo01373a","DOIUrl":"https://doi.org/10.1039/d5qo01373a","url":null,"abstract":"A substrate-controlled, metal-free strategy for the divergent synthesis of <em>α</em>-sulfonyl amides and nitriles from <em>N</em>-sulfonyl ynamides is disclosed. Under photocatalytic or thermal conditions, sulfonyl radicals initiate a radical chain process, where the reaction pathway is solely dictated by the substrate structure: non-allylic ynamides afford <em>α</em>-sulfonyl amides via hydration, while allylic ynamides exclusively yield <em>α</em>-sulfonyl nitriles through an <em>aza</em>-Claisen rearrangement. This method features broad functional group tolerance, excellent scalability, and 100% atom economy for nitrile formation. This work represents the first general metal-free approach to achieve radical divergence in ynamide chemistry, offering a versatile platform for accessing valuable sulfonyl-containing building blocks.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"5 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145600230","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}
Fluorinated molecules hold prominent significance in pharmaceutical chemistry. However, the construction of complex fluorinated compounds bearing multiple chiral centers has long remained a challenge in organic synthesis. Herein, we report an efficient organocatalytic asymmetric strategy for accessing a series of O,O-acetal fused tetracyclic scaffolds featuring fluorinated tetrasubstituted centers, which exhibit excellent diastereoselectivity (>20:1 dr) and enantioselectivity (up to 99% ee). The reaction proceeds via an asymmetric multistep cascade sequence, ultimately affording O,O-acetal fused tetracyclic scaffolds bearing both fluorinated tetrasubstituted centers and five consecutive stereocenters. Notably, the hydrogen-bonding interaction of the fluorine atom plays a crucial role in this transformation.
{"title":"Enantioselective Synthesis of O,O-Acetal-Fused Tetracyclic Scaffolds with Fluorinated Tetrasubstituted Centers via Fluorine-Assisted Asymmetric Induction","authors":"Yuzhen Chen, Jialiang Qin, Guohui Zeng, Huicai Huang, Yongbo Xue","doi":"10.1039/d5qo01486g","DOIUrl":"https://doi.org/10.1039/d5qo01486g","url":null,"abstract":"Fluorinated molecules hold prominent significance in pharmaceutical chemistry. However, the construction of complex fluorinated compounds bearing multiple chiral centers has long remained a challenge in organic synthesis. Herein, we report an efficient organocatalytic asymmetric strategy for accessing a series of O,O-acetal fused tetracyclic scaffolds featuring fluorinated tetrasubstituted centers, which exhibit excellent diastereoselectivity (>20:1 dr) and enantioselectivity (up to 99% ee). The reaction proceeds via an asymmetric multistep cascade sequence, ultimately affording O,O-acetal fused tetracyclic scaffolds bearing both fluorinated tetrasubstituted centers and five consecutive stereocenters. Notably, the hydrogen-bonding interaction of the fluorine atom plays a crucial role in this transformation.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"120 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145594254","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}
Ivan Alekseev, Ioann Shugaev, Alexander Gorbunov, Dmitry Cheshkov, Elena Tarasenko, Elena Kudryashova, Stanislav Bezzubov, Vladimir Kovalev, Ivan Vatsouro
An efficient strategy is presented for the synthesis of rare-type inherently chiral calix[4]arenes having asymmetric arrangement of functional groups at the wide rim of the cone macrocycle and possessing virtually unlimited functionalization capabilities. Selective protection of two proximal amino groups in the Cs-symmetrical wide-rim calixarene triamine by tert-butoxycarbonyl groups is suggested as the key synthesis step allowing desymmetrization of the core, the efficiency of which can be improved due to the facile recovery of the starting material from the mixture of reaction byproducts. The insertion of an auxiliary chiral unit to the remaining free amide group enables early-step separation of stereoisomers, which allows for further derivatization of the enantiopure calixarene cores without the need for any stereocontrol conditions. This derivatization may include, for instance, the amine deprotection followed by acylation/sulfonylation, and/or conversion of amines into diazonium salts and azides, which can be further involved into a copper(I)-catalyzed azide-alkyne cycloaddition. As a proof of concept, three pairs of optically active enantiomers of inherently chiral calix[4]arenes bearing two proximal triazole groups accompanied with amine, sulfonamide or urea functionalities were prepared, and their high optical purity (>99% ee) was confirmed. Using 2D NMR data supported by quantum-chemical calculations, and X-ray diffraction data, the absolute stereoconfiguration of the inherently chiral calixarene core in these compounds was established. To evaluate enantiodiscriminative capabilities of the asymmetrically arranged triazole groups and the asymmetric cavity (the permanent parts of the enantiomer structures), qualitative NMR study was performed using excess of selected chiral guest molecules. The study showed distinct complexation-induced spectral changes that were clearly different between (P)- and (M)-enantiomers of calixarenes confirming that these structural elements may contribute to complexation provided by the ‘main’ receptor units. The latter can be easily varied in asymmetric calixarene cores using azide-alkyne cycloaddition and/or amine acylation/sulfonylation, enabling the design of multifunctional chiral host structures tailored to the functionality of the target chiral guest molecules.
{"title":"Accessing inherently chiral multifunctional structures by desymmetrization of wide-rim calix[4]arene triamine","authors":"Ivan Alekseev, Ioann Shugaev, Alexander Gorbunov, Dmitry Cheshkov, Elena Tarasenko, Elena Kudryashova, Stanislav Bezzubov, Vladimir Kovalev, Ivan Vatsouro","doi":"10.1039/d5qo01509j","DOIUrl":"https://doi.org/10.1039/d5qo01509j","url":null,"abstract":"An efficient strategy is presented for the synthesis of rare-type inherently chiral calix[4]arenes having asymmetric arrangement of functional groups at the wide rim of the cone macrocycle and possessing virtually unlimited functionalization capabilities. Selective protection of two proximal amino groups in the Cs-symmetrical wide-rim calixarene triamine by tert-butoxycarbonyl groups is suggested as the key synthesis step allowing desymmetrization of the core, the efficiency of which can be improved due to the facile recovery of the starting material from the mixture of reaction byproducts. The insertion of an auxiliary chiral unit to the remaining free amide group enables early-step separation of stereoisomers, which allows for further derivatization of the enantiopure calixarene cores without the need for any stereocontrol conditions. This derivatization may include, for instance, the amine deprotection followed by acylation/sulfonylation, and/or conversion of amines into diazonium salts and azides, which can be further involved into a copper(I)-catalyzed azide-alkyne cycloaddition. As a proof of concept, three pairs of optically active enantiomers of inherently chiral calix[4]arenes bearing two proximal triazole groups accompanied with amine, sulfonamide or urea functionalities were prepared, and their high optical purity (>99% ee) was confirmed. Using 2D NMR data supported by quantum-chemical calculations, and X-ray diffraction data, the absolute stereoconfiguration of the inherently chiral calixarene core in these compounds was established. To evaluate enantiodiscriminative capabilities of the asymmetrically arranged triazole groups and the asymmetric cavity (the permanent parts of the enantiomer structures), qualitative NMR study was performed using excess of selected chiral guest molecules. The study showed distinct complexation-induced spectral changes that were clearly different between (P)- and (M)-enantiomers of calixarenes confirming that these structural elements may contribute to complexation provided by the ‘main’ receptor units. The latter can be easily varied in asymmetric calixarene cores using azide-alkyne cycloaddition and/or amine acylation/sulfonylation, enabling the design of multifunctional chiral host structures tailored to the functionality of the target chiral guest molecules.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"139 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-11-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145594255","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}
Chengli Mou, Siyi Chen, Jun Huang, Xin Liu, Liejin Zhou, Shoulei Wang
Herein, we report a bifunctional hydrogen-bonding organocatalysis that enables the synthesis of chiral ε-sultams through two distinct annulation pathways: a [3+2] cycloaddition between seven-membered cyclic N-sulfonylimines and γ-hydroxy-α,β-unsaturated ketones (C-O bond formation), and a [4+2] cycloaddition employing 2-aminophenyl enones (C-N bond formation). This method proceeds under mild conditions with broad substrate compatibility, affording the corresponding products in good yields with excellent stereoselectivities.
{"title":"Asymmetric [3+2]/[4+2] Annulations for the Synthesis of ε-Sultams Promoted by Bifunctional Base Catalysts","authors":"Chengli Mou, Siyi Chen, Jun Huang, Xin Liu, Liejin Zhou, Shoulei Wang","doi":"10.1039/d5qo01474c","DOIUrl":"https://doi.org/10.1039/d5qo01474c","url":null,"abstract":"Herein, we report a bifunctional hydrogen-bonding organocatalysis that enables the synthesis of chiral ε-sultams through two distinct annulation pathways: a [3+2] cycloaddition between seven-membered cyclic N-sulfonylimines and γ-hydroxy-α,β-unsaturated ketones (C-O bond formation), and a [4+2] cycloaddition employing 2-aminophenyl enones (C-N bond formation). This method proceeds under mild conditions with broad substrate compatibility, affording the corresponding products in good yields with excellent stereoselectivities.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"68 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145553891","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}
Qiyuan Cai, Fengyi Zhao, Dong Jiang, Hiroyasu Sato, Yusuke Yamauchi, Gang Zhang, Weifan Wang
While π-conjugation extension represents an effective strategy to expand phenothiazine derivatives, the fusion of pentagonal and hexagonal rings into the phenothiazine core remains underexplored. Herein, we present a new class of πextended phenothiazines synthesized via a ring-fusion strategy. Their structural and photophysical properties were comprehensively characterized through single-crystal X-ray analysis, UV-vis absorption and emission spectroscopy, electrochemical measurements, and computational studies, revealing how π-extension influences their behavior. Additionally, we evaluated the potential of the derivatives as antiproliferative agents, demonstrating their promise for biomedical applications.
{"title":"π-extended phenothiazines with fused pentagons and hexagons","authors":"Qiyuan Cai, Fengyi Zhao, Dong Jiang, Hiroyasu Sato, Yusuke Yamauchi, Gang Zhang, Weifan Wang","doi":"10.1039/d5qo01459j","DOIUrl":"https://doi.org/10.1039/d5qo01459j","url":null,"abstract":"While π-conjugation extension represents an effective strategy to expand phenothiazine derivatives, the fusion of pentagonal and hexagonal rings into the phenothiazine core remains underexplored. Herein, we present a new class of πextended phenothiazines synthesized via a ring-fusion strategy. Their structural and photophysical properties were comprehensively characterized through single-crystal X-ray analysis, UV-vis absorption and emission spectroscopy, electrochemical measurements, and computational studies, revealing how π-extension influences their behavior. Additionally, we evaluated the potential of the derivatives as antiproliferative agents, demonstrating their promise for biomedical applications.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"369 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145553860","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}
Site-selective introduction of a glycosylthiol group into aromatic compounds is a crucial process in organic chemistry.However, the position that a glycosylthiol moiety can be introduced to is largely restricted to a pre-functionalized site; otherwise, electronically biased substrates or auxiliary groups are needed. Moreover, common ways to prepare stereoselective aryl thioglycosides often rely on cross-coupling reactions between aryl halides and glycosylthiols. These methods form carbon-sulfur (C-S) bonds at the ipso position of aryl halides; thus, the position of the installed sulfur moiety is restricted by the position of the halide. Switching ipso to ortho thioglycosylation is a formidable challenge andhas not yet been reported. In this study, we introduce for the first time a modular approach involving glycosyl thiosulfonate-enabled ortho-C-H thioglycosylation and ipso-functionalization of aryl iodides/aryl boronic acids via palladium/norbornene cooperative catalysis. Density functional theory (DFT) calculations and experimental studies support the tuning of ancillary ligand in the aryl-NBE palladacycle Pd(IV) intermediate enforces the selective reductive elimination to form a C(Ar)-S-Sug bond. The broad substrate scope with good regio-and stereoselectivity makes this dualtasked method attractive for the synthesis of poly-substituted arylthioglycosides through a three-component cascade reaction in a single synthetic step. Notable highlights include ipso-alkenylation, hydrogenation, cyanation, and methylation as flexible termination steps and derivatization of poly-substituted arylthioglycosides to obtain various synthetically useful motifs.
在芳香化合物中选择性地引入糖基硫醇是有机化学中的一个重要过程。然而，糖基硫醇片段可以引入的位置主要限于预功能化位点；否则，就需要电子偏置衬底或辅助基团。此外，制备立体选择性芳基硫甙的常用方法往往依赖于芳基卤化物和糖基硫醇之间的交叉偶联反应。这些方法在芳基卤化物的同位形成碳-硫（C-S）键；因此，所安装的硫部分的位置受到卤化物的位置的限制。将ipso转换为邻位巯基化是一个巨大的挑战，尚未有报道。在这项研究中，我们首次引入了一种模块化的方法，通过钯/降冰片烯协同催化，使糖基硫代磺酸使芳基碘化物/芳基硼酸的邻c - h巯基化和ipso功能化。密度泛函理论（DFT）计算和实验研究支持芳基- nbe钯环Pd（IV）中间体中辅助配体的调谐，强制选择性还原消除，形成C(Ar)- s - sugar键。底物范围广，具有良好的区域选择性和立体选择性，使得这种双要求方法在一次合成步骤中通过三组分级联反应合成多取代芳基硫甙具有吸引力。值得注意的亮点包括：益丙烯基化、氢化、氰化和甲基化作为灵活的终止步骤和衍生化的多取代芳基硫苷，以获得各种合成上有用的基序。
{"title":"Glycosyl Thiosulfonate-Enabled Ortho-Thiolation via the Catellani Strategy: A Modular Synthesis of Polysubstituted Aryl Thioglycosides","authors":"Zanjila Azeem, Shalini ., Neetu Malya, Ruchir Kant, Sathish Kumar Mudedla, Pintu Kumar Mandal","doi":"10.1039/d5qo01342a","DOIUrl":"https://doi.org/10.1039/d5qo01342a","url":null,"abstract":"Site-selective introduction of a glycosylthiol group into aromatic compounds is a crucial process in organic chemistry.However, the position that a glycosylthiol moiety can be introduced to is largely restricted to a pre-functionalized site; otherwise, electronically biased substrates or auxiliary groups are needed. Moreover, common ways to prepare stereoselective aryl thioglycosides often rely on cross-coupling reactions between aryl halides and glycosylthiols. These methods form carbon-sulfur (C-S) bonds at the ipso position of aryl halides; thus, the position of the installed sulfur moiety is restricted by the position of the halide. Switching ipso to ortho thioglycosylation is a formidable challenge andhas not yet been reported. In this study, we introduce for the first time a modular approach involving glycosyl thiosulfonate-enabled ortho-C-H thioglycosylation and ipso-functionalization of aryl iodides/aryl boronic acids via palladium/norbornene cooperative catalysis. Density functional theory (DFT) calculations and experimental studies support the tuning of ancillary ligand in the aryl-NBE palladacycle Pd(IV) intermediate enforces the selective reductive elimination to form a C(Ar)-S-Sug bond. The broad substrate scope with good regio-and stereoselectivity makes this dualtasked method attractive for the synthesis of poly-substituted arylthioglycosides through a three-component cascade reaction in a single synthetic step. Notable highlights include ipso-alkenylation, hydrogenation, cyanation, and methylation as flexible termination steps and derivatization of poly-substituted arylthioglycosides to obtain various synthetically useful motifs.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"99 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145553867","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}
Viktor Saraiva Câmara, Marcio Hayashi, Alex S Moraes, Pedro Henrique de Oliveira Santiago, Javier Ellena, Marco Antonio Barbosa Ferreira, Antonio C. B. Burtoloso
Despite the well-documented use of sulfur ylides in organic synthesis, the reactivity of α-carbonyl sulfoxonium ylides with carbocations remains largely unexplored. We report the first reaction between sulfoxonium ylides and allylic carbocations, which establishes an unprecedented, highly stereoselective pathway to carbocyclic scaffolds. The transformation involves a key nucleophilic attack by the sulfoxonium ylide to the carbocation (generated in situ from an allylic alcohol and HFIP), followed by intramolecular cyclization. This process affords fully substituted cyclopropanes, simultaneously establishing four new contiguous stereocenters in a single and efficient step, with high diastereocontrol. Intriguingly, two divergent pathways are observed: the major cyclization pathway and a competitive simple deprotonation, which yields -alkylated sulfoxonium ylides. This protocol was successfully applied to a broad scope of allylic alcohols and sulfoxonium ylides, demonstrating its utility for the synthesis of complex, stereochemically rich structures. DFT calculations were performed to elucidate the origin of the observed high diastereoselectivity and provide a comprehensive rationale for stereochemical control.
{"title":"Reactions of Ketosulfoxonium Ylides with Allylic Carbocations: Stereoselective and Direct Access to Highly-Substituted Cyclopropanes and α-Alkylated Ylides","authors":"Viktor Saraiva Câmara, Marcio Hayashi, Alex S Moraes, Pedro Henrique de Oliveira Santiago, Javier Ellena, Marco Antonio Barbosa Ferreira, Antonio C. B. Burtoloso","doi":"10.1039/d5qo01425e","DOIUrl":"https://doi.org/10.1039/d5qo01425e","url":null,"abstract":"Despite the well-documented use of sulfur ylides in organic synthesis, the reactivity of α-carbonyl sulfoxonium ylides with carbocations remains largely unexplored. We report the first reaction between sulfoxonium ylides and allylic carbocations, which establishes an unprecedented, highly stereoselective pathway to carbocyclic scaffolds. The transformation involves a key nucleophilic attack by the sulfoxonium ylide to the carbocation (generated in situ from an allylic alcohol and HFIP), followed by intramolecular cyclization. This process affords fully substituted cyclopropanes, simultaneously establishing four new contiguous stereocenters in a single and efficient step, with high diastereocontrol. Intriguingly, two divergent pathways are observed: the major cyclization pathway and a competitive simple deprotonation, which yields -alkylated sulfoxonium ylides. This protocol was successfully applied to a broad scope of allylic alcohols and sulfoxonium ylides, demonstrating its utility for the synthesis of complex, stereochemically rich structures. DFT calculations were performed to elucidate the origin of the observed high diastereoselectivity and provide a comprehensive rationale for stereochemical control.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"107 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145536312","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}
Douglas de C. Vieira, Luiz H. Dapper, Rafael C. Brinkerhoff, Angelita M. Barcellos, Alex F. C. Flores and Gabriel P. da Costa
Over the past decade, the synthesis of alkynyl sulfones and alkynyl chalcogen derivatives has witnessed significant advances. Modern methodologies have increasingly focused on sustainable protocols, catalytic efficiency, milder reaction conditions, and atom-economical processes. Traditional approaches relying on harsh reagents or stoichiometric activators have increasingly been replaced by transition-metal-catalyzed couplings, photoredox transformations, electrochemical processes, and metal-free oxidative strategies. These innovations have enabled access to structurally diverse alkynyl sulfones, sulfides, selenides, tellurides, and their trifluoromethylated counterparts. This review highlights the progress made during the last ten years, emphasizing mechanistic innovations, improvements in selectivity and functional group tolerance, and the expanding chemical space accessible through chalcogen-substituted alkynes.
{"title":"A decade of advances in alkynyl sulfone and alkynyl chalcogenide synthesis","authors":"Douglas de C. Vieira, Luiz H. Dapper, Rafael C. Brinkerhoff, Angelita M. Barcellos, Alex F. C. Flores and Gabriel P. da Costa","doi":"10.1039/D5QO01359C","DOIUrl":"10.1039/D5QO01359C","url":null,"abstract":"<p >Over the past decade, the synthesis of alkynyl sulfones and alkynyl chalcogen derivatives has witnessed significant advances. Modern methodologies have increasingly focused on sustainable protocols, catalytic efficiency, milder reaction conditions, and atom-economical processes. Traditional approaches relying on harsh reagents or stoichiometric activators have increasingly been replaced by transition-metal-catalyzed couplings, photoredox transformations, electrochemical processes, and metal-free oxidative strategies. These innovations have enabled access to structurally diverse alkynyl sulfones, sulfides, selenides, tellurides, and their trifluoromethylated counterparts. This review highlights the progress made during the last ten years, emphasizing mechanistic innovations, improvements in selectivity and functional group tolerance, and the expanding chemical space accessible through chalcogen-substituted alkynes.</p>","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":" 1","pages":" 258-313"},"PeriodicalIF":4.7,"publicationDate":"2025-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145536466","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}
Chemo-and regioselective functionalization of free phenols is a continuing challenge. Herein, cobalt-catalyzed cross-dehydrogenative coupling (CDC) of phenols with distal C(sp 3 )-H bonds is achieved. The reaction exhibits good to excellent chemo-and regioselectivity, delivering ortho-alkylated phenols and alkyl aryl ethers respectively. The reaction could involve a radical process and the presence of Na 2 CO 3 or DBU in combination with Co catalyst is essential for the chemo- and regioselectivity
{"title":"N-Directed, Co-Catalyzed Functionalization of Distal C(sp 3 )-H Bonds with Phenols: Arylation vs. Aryloxylation","authors":"Yu-Han Wang, Hai-Tao Qin, Feng Liu","doi":"10.1039/d5qo01421b","DOIUrl":"https://doi.org/10.1039/d5qo01421b","url":null,"abstract":"Chemo-and regioselective functionalization of free phenols is a continuing challenge. Herein, cobalt-catalyzed cross-dehydrogenative coupling (CDC) of phenols with distal C(sp 3 )-H bonds is achieved. The reaction exhibits good to excellent chemo-and regioselectivity, delivering ortho-alkylated phenols and alkyl aryl ethers respectively. The reaction could involve a radical process and the presence of Na 2 CO 3 or DBU in combination with Co catalyst is essential for the chemo- and regioselectivity","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"18 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145515903","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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