Carbene radical coupling reactions are rarely developed due to their high reactivity. Here, we present a distinct electrochemical one-pot difunctionalization of diazo compounds with triazoles and nucleophiles. This method represents an effective strategy to access to fully-substituted triazole derivatives which can’t be accessible using the known methods. This transformation exhibits synthetically useful yields and high regioselectivity, without the need for external chemical oxidants or metal catalysts. Furthermore, a variety of nucleophiles can be employed in this reaction to construct quaternary Csp3-N and Csp3-X (X = O/F) bonds. The reaction mechanism investigations show that this unprecedent pathway was promoted via a carbene radical coupling process followed by further oxidation and nucleophilic addition.
{"title":"Electrochemical Oxidative One-Pot Difunctionalization of Diazo Compounds with Triazoles and Nucleophiles","authors":"Yaqi Deng, Jian Xue, Bajiba Bian, Shunying Liu","doi":"10.1039/d5qo00333d","DOIUrl":"https://doi.org/10.1039/d5qo00333d","url":null,"abstract":"Carbene radical coupling reactions are rarely developed due to their high reactivity. Here, we present a distinct electrochemical one-pot difunctionalization of diazo compounds with triazoles and nucleophiles. This method represents an effective strategy to access to fully-substituted triazole derivatives which can’t be accessible using the known methods. This transformation exhibits synthetically useful yields and high regioselectivity, without the need for external chemical oxidants or metal catalysts. Furthermore, a variety of nucleophiles can be employed in this reaction to construct quaternary Csp3-N and Csp3-X (X = O/F) bonds. The reaction mechanism investigations show that this unprecedent pathway was promoted via a carbene radical coupling process followed by further oxidation and nucleophilic addition.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"34 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143661084","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}
Transposition reactions have emerged as a powerful and sustainable strategy in organic synthesis, offering efficient pathways for the construction of complex molecules with minimal environmental impact. These reactions enable the selective rearrangement of molecular fragments, facilitating strategic bond disconnections that simplify synthetic routes and enhance atom economy. By reducing reliance on high-energy intermediates or specialized reagents, transposition methodologies align with key principles of green metrics, promoting waste reduction, energy efficiency, and sustainability. Furthermore, transposition reactions often proceed under mild conditions, making them attractive alternatives to traditional synthetic approaches. Due to the limited availability of well-structured reviews in this domain, we first presented a distinct classes of transposition reactions, with an emphasis on the influence of catalytic systems, reaction conditions, and substrate characteristics on both efficiency and selectivity predominantly relevant to individual significance of carbonyl, alkene, chirality, allylic alcohol, and functional group transpositions. The versatility of these reactions in creating diverse molecular scaffolds from readily available substrates opens up new avenues for the synthesis of bioactive compounds, pharmaceuticals, and natural products. By simplifying synthetic pathways and reducing waste generation, transposition reactions represent a compelling tool for advancing greener, more efficient approaches to organic synthesis.
{"title":"Recent Developments on Constructing Carbon Framework in Organic Synthesis Using Transposition Strategies","authors":"Savita Gat, Piyusa Priyadarsan Pattanaik, Rambabu Dandela","doi":"10.1039/d5qo00163c","DOIUrl":"https://doi.org/10.1039/d5qo00163c","url":null,"abstract":"Transposition reactions have emerged as a powerful and sustainable strategy in organic synthesis, offering efficient pathways for the construction of complex molecules with minimal environmental impact. These reactions enable the selective rearrangement of molecular fragments, facilitating strategic bond disconnections that simplify synthetic routes and enhance atom economy. By reducing reliance on high-energy intermediates or specialized reagents, transposition methodologies align with key principles of green metrics, promoting waste reduction, energy efficiency, and sustainability. Furthermore, transposition reactions often proceed under mild conditions, making them attractive alternatives to traditional synthetic approaches. Due to the limited availability of well-structured reviews in this domain, we first presented a distinct classes of transposition reactions, with an emphasis on the influence of catalytic systems, reaction conditions, and substrate characteristics on both efficiency and selectivity predominantly relevant to individual significance of carbonyl, alkene, chirality, allylic alcohol, and functional group transpositions. The versatility of these reactions in creating diverse molecular scaffolds from readily available substrates opens up new avenues for the synthesis of bioactive compounds, pharmaceuticals, and natural products. By simplifying synthetic pathways and reducing waste generation, transposition reactions represent a compelling tool for advancing greener, more efficient approaches to organic synthesis.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"6 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143661088","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}
Ya-ling Tian, Tao Liu, Yao Chai, Zhi-bin Wang, Zhengyin Du, Xi-Cun Wang, Xiaofeng Wu, Zheng-Jun Quan
In this study, we developed a pre-activation reduction strategy to enable the efficient activation, reduction, and conversion of inert phosphate. Our method allows for the direct activation of [TBA][H2PO4] using oxalyl chloride at room temperature, followed by reduction with HSiCl₃, enabling rapid synthesis of the low-valent bis(trichlorosilyl)phosphorylated anion [P(SiCl₃)₂]⁻ in 24 h. Follow-up experiments demonstrated that the resulting anion could be successfully coupled with aryl halides by Pd-catalyst leading to the synthesis of a series of triaryl phosphine compounds with good tolerance to a wide range of functionalized aryl halides. This represents a novel strategy for synthesizing organophosphorus compounds (OPCs) from phosphoric acid
{"title":"Phosphoric acid activation, reduction and transformation processes: efficient preparation of triarylphosphines","authors":"Ya-ling Tian, Tao Liu, Yao Chai, Zhi-bin Wang, Zhengyin Du, Xi-Cun Wang, Xiaofeng Wu, Zheng-Jun Quan","doi":"10.1039/d5qo00278h","DOIUrl":"https://doi.org/10.1039/d5qo00278h","url":null,"abstract":"In this study, we developed a pre-activation reduction strategy to enable the efficient activation, reduction, and conversion of inert phosphate. Our method allows for the direct activation of [TBA][H2PO4] using oxalyl chloride at room temperature, followed by reduction with HSiCl₃, enabling rapid synthesis of the low-valent bis(trichlorosilyl)phosphorylated anion [P(SiCl₃)₂]⁻ in 24 h. Follow-up experiments demonstrated that the resulting anion could be successfully coupled with aryl halides by Pd-catalyst leading to the synthesis of a series of triaryl phosphine compounds with good tolerance to a wide range of functionalized aryl halides. This represents a novel strategy for synthesizing organophosphorus compounds (OPCs) from phosphoric acid","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"7 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143654068","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}
Metal-free carbenes are high-energy reactive intermediates that have been harnessed for numerous useful transformations. However, access to these versatile intermediates is often limited by the requirement for highly energetic diazoalkane precursors, which release thermodynamically stable N₂ as an enthalpic driving force. Herein, we report the formal homolysis of a common phosphonium ylide to generate a useful carbene intermediate. This strategy enables the direct transformation of glucosylphosphonium ylides into glycals, involving the formation of a glycosylidene carbene intermediate and a subsequent 1,2-H migration. Furthermore, theoretical calculations rationalize the chemical driving force behind the homolytic fission of phosphonium ylide bonds and propose an acid-base pairs model of phosphonium ylides, namely phosphine-protected carbenes. This study presents a novel method for preparing metal-free carbenes and expands the applications of phosphonium ylides.
{"title":"Fragmentation of Glucosylphosphonium-ylides for Synthesis of Glycals","authors":"Chao Chen, Zhichao Mei, Mengyao You, Ziwei Zhang, Haiyang Huang, Qiang Xiao","doi":"10.1039/d5qo00283d","DOIUrl":"https://doi.org/10.1039/d5qo00283d","url":null,"abstract":"Metal-free carbenes are high-energy reactive intermediates that have been harnessed for numerous useful transformations. However, access to these versatile intermediates is often limited by the requirement for highly energetic diazoalkane precursors, which release thermodynamically stable N₂ as an enthalpic driving force. Herein, we report the formal homolysis of a common phosphonium ylide to generate a useful carbene intermediate. This strategy enables the direct transformation of glucosylphosphonium ylides into glycals, involving the formation of a glycosylidene carbene intermediate and a subsequent 1,2-H migration. Furthermore, theoretical calculations rationalize the chemical driving force behind the homolytic fission of phosphonium ylide bonds and propose an acid-base pairs model of phosphonium ylides, namely phosphine-protected carbenes. This study presents a novel method for preparing metal-free carbenes and expands the applications of phosphonium ylides.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"18 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143654067","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}
Yijie Long, Pinpin Feng, Hongyan Long, Yi Huang, Xingxing Wu
Alkyl sulfonyl chlorides widely serve as sulfene precursors to facilitate diverse transformations but suffer from poor hydrolytic stability under basic conditions, posing notable operational challenges. Consequently, the development of stable, easy-to-handle alternatives has garnered considerable interest for broad synthetic applications. Herein, we describe the efficient synthesis of spirocyclopropyloxindoles through a NaH-mediated formal [2+1] annulation using stable while reactive 4-nitrophenyl sulfonates as C1 synthons. Unexpectedly, the reaction proceeds through an unconventional [(2+2)-1] pathway under basic conditions when using sulfonates and alkylidene oxindole substrates, deviating from conventional reaction modes. This approach affords spirocyclopropyloxindoles with high yields and good diastereoselectivity. Futhermore, these scaffolds demonstrate promising antibacterial activity against plant pathogens, highlighting their potential as novel agrochemical agents.
{"title":"Stable Sulfonate Esters as C1-Synthons for Cyclopropanation Reaction to Access Antimicrobial Active 3,3’-Spirocyclopropyl-oxindoles","authors":"Yijie Long, Pinpin Feng, Hongyan Long, Yi Huang, Xingxing Wu","doi":"10.1039/d5qo00153f","DOIUrl":"https://doi.org/10.1039/d5qo00153f","url":null,"abstract":"Alkyl sulfonyl chlorides widely serve as sulfene precursors to facilitate diverse transformations but suffer from poor hydrolytic stability under basic conditions, posing notable operational challenges. Consequently, the development of stable, easy-to-handle alternatives has garnered considerable interest for broad synthetic applications. Herein, we describe the efficient synthesis of spirocyclopropyloxindoles through a NaH-mediated formal [2+1] annulation using stable while reactive 4-nitrophenyl sulfonates as C1 synthons. Unexpectedly, the reaction proceeds through an unconventional [(2+2)-1] pathway under basic conditions when using sulfonates and alkylidene oxindole substrates, deviating from conventional reaction modes. This approach affords spirocyclopropyloxindoles with high yields and good diastereoselectivity. Futhermore, these scaffolds demonstrate promising antibacterial activity against plant pathogens, highlighting their potential as novel agrochemical agents.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"91 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143654069","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}
Yuzhu Wang, Xiaoyan Wei, Yinuo Chen, Yueyue Liu, Lu Liu
An unprecedented chemo- and site-selective para-C(sp2)-H bond functionalization of aniline and phenol derivatives with aryl/aryl diazo compounds was successfully developed. The cooperative catalysis of bismuth(III) triflate and Brønsted acid promoted this transformation instead of the well-known N-H/O-H insertion, furnishing the corresponding triarylmethane compounds in mild conditions. The protocol features broad substrate scope, excellent chemo- and site-selective C-H bond functionalization, as well as non-noble metal catalysts.
{"title":"Highly Chemo- and Site-selective C(sp2)-H Bond Functionalization of Aniline and Phenol Derivatives with Aryl/Aryl Diazo Compounds","authors":"Yuzhu Wang, Xiaoyan Wei, Yinuo Chen, Yueyue Liu, Lu Liu","doi":"10.1039/d5qo00051c","DOIUrl":"https://doi.org/10.1039/d5qo00051c","url":null,"abstract":"An unprecedented chemo- and site-selective para-C(sp2)-H bond functionalization of aniline and phenol derivatives with aryl/aryl diazo compounds was successfully developed. The cooperative catalysis of bismuth(III) triflate and Brønsted acid promoted this transformation instead of the well-known N-H/O-H insertion, furnishing the corresponding triarylmethane compounds in mild conditions. The protocol features broad substrate scope, excellent chemo- and site-selective C-H bond functionalization, as well as non-noble metal catalysts.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"49 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143660770","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 nickel-catalyzed C(sp3)–C(sp3) ring-opening cross-coupling reaction of cyclopropanols with α-boryl and α-silyl electrophiles is presented, offering an efficient route to access γ-carbonyl alkylboronates and alkylsilicons under mild conditions. The practical applicability of this method is illustrated by the gram-scale synthesis and various transformations of alkylboronates.
{"title":"Ni-Catalyzed C(sp3)–C(sp3) Cross-Coupling to Access γ-Carbonyl Alkylboronates and Alkylsilicons Enabled by Cyclopropanol-Derived Homoenolates","authors":"Linfei Zhu, Yang Sun, Hui Wang","doi":"10.1039/d5qo00320b","DOIUrl":"https://doi.org/10.1039/d5qo00320b","url":null,"abstract":"A nickel-catalyzed C(sp3)–C(sp3) ring-opening cross-coupling reaction of cyclopropanols with α-boryl and α-silyl electrophiles is presented, offering an efficient route to access γ-carbonyl alkylboronates and alkylsilicons under mild conditions. The practical applicability of this method is illustrated by the gram-scale synthesis and various transformations of alkylboronates.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"33 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143640310","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 novel acyl migration protocol based on reductive radical-polar crossover process enabled by redox-neutral photocatalysis. Employing tertiary amines or α-silylamines as the radical sources, modular access to various functionalized α-(hetero)aryl-α-keto-1,3-diamines could be efficiently realized via reactions of enamides with α-aminoalkyl radicals under mild reaction conditions. Additionally, the radical addition/acyl migration cascade process could be extended to the intramolecular version. Synthetic application of acyl migrated product was also demonstrated. Taking advantage of easy generation of α-aminoalkyl radical and α-imido carbanion via single-electron-transfer process, this new procedure features broad substrate scope and exogenous reductant-free conditions.
{"title":"Expedient access to α-(hetero)aryl-α-keto-1,3-diamines via redox-neutral photocatalyzed reactions of N-vinylimides with α-aminoalkyl radicals","authors":"Yu Zhao, Yutao Jing, Yan Li, Li Qiu, Yewen Fang","doi":"10.1039/d5qo00239g","DOIUrl":"https://doi.org/10.1039/d5qo00239g","url":null,"abstract":"Herein we report a novel acyl migration protocol based on reductive radical-polar crossover process enabled by redox-neutral photocatalysis. Employing tertiary amines or α-silylamines as the radical sources, modular access to various functionalized α-(hetero)aryl-α-keto-1,3-diamines could be efficiently realized via reactions of enamides with α-aminoalkyl radicals under mild reaction conditions. Additionally, the radical addition/acyl migration cascade process could be extended to the intramolecular version. Synthetic application of acyl migrated product was also demonstrated. Taking advantage of easy generation of α-aminoalkyl radical and α-imido carbanion via single-electron-transfer process, this new procedure features broad substrate scope and exogenous reductant-free conditions.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"183 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143640309","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}
Despite significant recent advances in the development of organic photosensitizers (PSs), designing a PS with both long-wavelength absorption and high reducing ability remains challenging. In this study, we introduce carbazol-3-olates as a novel class of PSs that exhibit these desirable properties. Compared to their neutral carbazole counterparts, anionic carbazol-3-olates exhibited a 70-nm red-shift in absorption and a 0.54-V negative shift in the excited-state reduction potential. The use of carbazol-3-olates as PSs enabled photocatalysis of hydrodefluorination and Birch-type reduction reactions under long-wavelength visible-light irradiation. Furthermore, the Birch reduction reactions exhibited tolerance toward aqueous environments when conducted using our PS, thus expanding their industrial applicability. Mechanistic studies revealed electron transfer from the excited carbazol-3-olates to inert substrates, such as fluoroarenes, highlighting the high catalytic efficiency of carbazol-3-olates as PSs for reduction reactions. Therefore, with their transition-metal-free nature and facile synthesis process, we expect carbazol-3-olates to be industrially advantageous PSs for catalyzing challenging photochemical reduction reactions.
{"title":"Carbazol-3-olate photosensitizers enable photocatalytic hydrodefluorination and Birch-type reduction reactions","authors":"Huilong Kuang, Weibin Xie, Tatsushi Yabuta, Masaaki Fuki, Masahiro Higashi, Yasuhiro Kobori, Nozomi Sakai, Seiji Akimoto, Masahiko Hayashi, Ryosuke Matsubara","doi":"10.1039/d5qo00056d","DOIUrl":"https://doi.org/10.1039/d5qo00056d","url":null,"abstract":"Despite significant recent advances in the development of organic photosensitizers (PSs), designing a PS with both long-wavelength absorption and high reducing ability remains challenging. In this study, we introduce carbazol-3-olates as a novel class of PSs that exhibit these desirable properties. Compared to their neutral carbazole counterparts, anionic carbazol-3-olates exhibited a 70-nm red-shift in absorption and a 0.54-V negative shift in the excited-state reduction potential. The use of carbazol-3-olates as PSs enabled photocatalysis of hydrodefluorination and Birch-type reduction reactions under long-wavelength visible-light irradiation. Furthermore, the Birch reduction reactions exhibited tolerance toward aqueous environments when conducted using our PS, thus expanding their industrial applicability. Mechanistic studies revealed electron transfer from the excited carbazol-3-olates to inert substrates, such as fluoroarenes, highlighting the high catalytic efficiency of carbazol-3-olates as PSs for reduction reactions. Therefore, with their transition-metal-free nature and facile synthesis process, we expect carbazol-3-olates to be industrially advantageous PSs for catalyzing challenging photochemical reduction reactions.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"69 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143640312","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}
Rongxing Linghu, Jun Shi, Biaobiao Jiang, Junrong Song, Wei Wu, Hai Ren
The hydration of olefins is the most direct and effective method for producing alcohol molecules; however, it mainly procedes with Markovnikov selectivity, and anti-Markovnikov hydration of olefins for the direct construction of primary alcohols remains challenging. Herein, we report a metal-free electrochemical anti-Markovnikov hydration of aryl alkenes, providing direct access to a wide spectrum of primary, secondary, and tertiary alcohols in moderate to high yields without the need for expensive transition metals or stoichiometric concentrations of chemical oxidants. Mechanistic experiments indicated that the reaction involves a collaborative electrooxidation of chloride ions at the anode and single-electron-transfer-induced reduction of epoxide at the cathode.
{"title":"Metal-free Electrochemical Anti-Markovnikov Hydration of Aryl Alkenes","authors":"Rongxing Linghu, Jun Shi, Biaobiao Jiang, Junrong Song, Wei Wu, Hai Ren","doi":"10.1039/d5qo00289c","DOIUrl":"https://doi.org/10.1039/d5qo00289c","url":null,"abstract":"The hydration of olefins is the most direct and effective method for producing alcohol molecules; however, it mainly procedes with Markovnikov selectivity, and anti-Markovnikov hydration of olefins for the direct construction of primary alcohols remains challenging. Herein, we report a metal-free electrochemical anti-Markovnikov hydration of aryl alkenes, providing direct access to a wide spectrum of primary, secondary, and tertiary alcohols in moderate to high yields without the need for expensive transition metals or stoichiometric concentrations of chemical oxidants. Mechanistic experiments indicated that the reaction involves a collaborative electrooxidation of chloride ions at the anode and single-electron-transfer-induced reduction of epoxide at the cathode.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"92 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143654220","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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