A visible-light-driven, photocatalyst-free C-C bond formation strategy is reported, enabling the decarboxylative arylation of 3-indoleacetic acid with (hetero)aromatic nitriles via electron donor-acceptor (EDA) complex activation. In addition, this strategy is also applicable to the coupling reaction between 3-indoleacetic acids and 2-sulfonylated benzothiazoles. Diverse indole-containing diarylmethanes were afforded in moderate to excellent yields. Moreover, biological evaluation revealed that several products exhibited antiproliferative activity against B16, HCT116, and HepG2 cancer cell lines. This protocol features mild conditions and a broad substrate scope and avoids external photocatalysts, offering a practical approach for constructing indole-based bioactive scaffolds.
{"title":"Photo-Promoted Decarboxylative Arylation of 3-Indoleacetic Acids for the Synthesis of Indole-Containing Diarylmethanes.","authors":"Jiaxin Wang,Xiaofeng Wu,Weiya Kong,Jiacheng Li,Xingang Yao,Xiaodong Tang","doi":"10.1021/acs.joc.5c03166","DOIUrl":"https://doi.org/10.1021/acs.joc.5c03166","url":null,"abstract":"A visible-light-driven, photocatalyst-free C-C bond formation strategy is reported, enabling the decarboxylative arylation of 3-indoleacetic acid with (hetero)aromatic nitriles via electron donor-acceptor (EDA) complex activation. In addition, this strategy is also applicable to the coupling reaction between 3-indoleacetic acids and 2-sulfonylated benzothiazoles. Diverse indole-containing diarylmethanes were afforded in moderate to excellent yields. Moreover, biological evaluation revealed that several products exhibited antiproliferative activity against B16, HCT116, and HepG2 cancer cell lines. This protocol features mild conditions and a broad substrate scope and avoids external photocatalysts, offering a practical approach for constructing indole-based bioactive scaffolds.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"7 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2026-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147383574","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
As antisense oligonucleotides, phosphorodiamidate morpholino oligonucleotides (PMOs) exhibit excellent properties. However, they possess two stereoisomers for each phosphorus atom, and these stereoisomers exhibit different physicochemical and biological properties. In this study, we developed a stereocontrolled synthesis method of dimethylamino phosphorochloridate monomers, which was used for a practical synthesis method of PMOs, from oxazaphospholidine derivatives. However, the condensation of a 5'-oxazaphospholidine derivative with an amine under acidic conditions is challenging because the resulting phosphoramidite intermediate can be activated under such conditions. To address this challenge, in the proposed synthesis method, a morpholino nucleoside 5'-oxazaphospholidine derivative was condensed with a phenol derivative with a low pKa value under acidic conditions. Subsequently, the resulting aryl phosphite was reacted with dimethylamine to yield a phosphoramidite, thereby liberating the phenol derivative as a leaving group. Chlorination of the phosphoramidite yielded a phosphorochloridate monomer in a highly stereoselective manner (dr = 93:7-97:3). Subsequently, the resulting chloridate monomer was stereospecifically condensed with the amino group of the morpholino nucleoside. The stereochemistry of the phosphorodiamidate morpholino dimers was unambiguously determined by nuclear magnetic resonance analysis. The results of this study facilitate the synthesis of stereocontrolled PMOs and the elucidation of their properties.
{"title":"Stereocontrolled Synthesis of Dimethylamino Phosphorochloridate Monomers toward Stereopure Phosphorodiamidate Morpholino Oligonucleotides.","authors":"Ryuichi Inutake,Hironao Hasegawa,Taiki Tsurusaki,Taiichi Sakamoto,Kazuki Sato,Takeshi Wada","doi":"10.1021/acs.joc.5c02914","DOIUrl":"https://doi.org/10.1021/acs.joc.5c02914","url":null,"abstract":"As antisense oligonucleotides, phosphorodiamidate morpholino oligonucleotides (PMOs) exhibit excellent properties. However, they possess two stereoisomers for each phosphorus atom, and these stereoisomers exhibit different physicochemical and biological properties. In this study, we developed a stereocontrolled synthesis method of dimethylamino phosphorochloridate monomers, which was used for a practical synthesis method of PMOs, from oxazaphospholidine derivatives. However, the condensation of a 5'-oxazaphospholidine derivative with an amine under acidic conditions is challenging because the resulting phosphoramidite intermediate can be activated under such conditions. To address this challenge, in the proposed synthesis method, a morpholino nucleoside 5'-oxazaphospholidine derivative was condensed with a phenol derivative with a low pKa value under acidic conditions. Subsequently, the resulting aryl phosphite was reacted with dimethylamine to yield a phosphoramidite, thereby liberating the phenol derivative as a leaving group. Chlorination of the phosphoramidite yielded a phosphorochloridate monomer in a highly stereoselective manner (dr = 93:7-97:3). Subsequently, the resulting chloridate monomer was stereospecifically condensed with the amino group of the morpholino nucleoside. The stereochemistry of the phosphorodiamidate morpholino dimers was unambiguously determined by nuclear magnetic resonance analysis. The results of this study facilitate the synthesis of stereocontrolled PMOs and the elucidation of their properties.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"1 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2026-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147393956","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The synthesis and characterization of a series of donor-acceptor diazabenz[cd]fluoranthenium derivatives (PC1-PC8) are reported. Spectroscopic and computational studies reveal that compound PC4, which features a carbazole-donor (D) and fluoranthenium-acceptor (A) cationic scaffold with CB9H10- as the counteranion, exhibits a 3-fold enhancement in the molar extinction coefficient at 400 nm relative to its parent compound PC8, along with a broad absorption across the visible and ultraviolet regions. Furthermore, the pronounced intramolecular charge transfer (ICT) effect induced by this architecture gives rise to a substantial Stokes shift of 7143 cm-1 for the compound. Transient absorption spectroscopy resolves the dynamics of picosecond electron transfer between the *PC4 (*Cz-diNFluo+) and DIPEA, evidenced by the rapid decay of the S1 state and the concomitant formation of the reduced radical species (Cz-diNFluȯ). The application of PC4 in the reductive dehalogenation of organic halides is also disclosed. The reaction proceeds via a consecutive photoinduced electron transfer (ConPET) mechanism, establishing a potent reducing platform far exceeding the thermodynamic limits of a single excitation event. This reducing ability is directly demonstrated by the efficient dehalogenative conversion of diverse substrates, including aryl bromides, alkyl bromides, and even recalcitrant aryl chlorides.
{"title":"Design and Characterization of Diazabenz[cd]fluoranthenium-Based Donor-Acceptor Organophotoredox Catalysts.","authors":"Qing Jiang,Jiayi Yang,Xinyi Li,Yunjun Shen,Yuzhen Zhang","doi":"10.1021/acs.joc.5c03254","DOIUrl":"https://doi.org/10.1021/acs.joc.5c03254","url":null,"abstract":"The synthesis and characterization of a series of donor-acceptor diazabenz[cd]fluoranthenium derivatives (PC1-PC8) are reported. Spectroscopic and computational studies reveal that compound PC4, which features a carbazole-donor (D) and fluoranthenium-acceptor (A) cationic scaffold with CB9H10- as the counteranion, exhibits a 3-fold enhancement in the molar extinction coefficient at 400 nm relative to its parent compound PC8, along with a broad absorption across the visible and ultraviolet regions. Furthermore, the pronounced intramolecular charge transfer (ICT) effect induced by this architecture gives rise to a substantial Stokes shift of 7143 cm-1 for the compound. Transient absorption spectroscopy resolves the dynamics of picosecond electron transfer between the *PC4 (*Cz-diNFluo+) and DIPEA, evidenced by the rapid decay of the S1 state and the concomitant formation of the reduced radical species (Cz-diNFluȯ). The application of PC4 in the reductive dehalogenation of organic halides is also disclosed. The reaction proceeds via a consecutive photoinduced electron transfer (ConPET) mechanism, establishing a potent reducing platform far exceeding the thermodynamic limits of a single excitation event. This reducing ability is directly demonstrated by the efficient dehalogenative conversion of diverse substrates, including aryl bromides, alkyl bromides, and even recalcitrant aryl chlorides.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"88 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2026-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147393959","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Fernanda Liu,Alessandro Vicidomini,Stacey E Brenner-Moyer
A mild direct remote hydroxylation of α,β-unsaturated aldehydes is reported. Air is the oxidant, and tertiary alcohol products are generated in up to 80% yield. This method selectively hydroxylates enals with acidic γ-carbons and therefore may be suitable for late-stage installation of remote hydroxyl groups on medicinal aldehydes. Mechanistic studies that enabled the development of this transformation are described, as is the first example of catalytic enantioselective γ-hydroxylation of an enal.
{"title":"Mild Direct Remote Hydroxylation of Enals in Air.","authors":"Fernanda Liu,Alessandro Vicidomini,Stacey E Brenner-Moyer","doi":"10.1021/acs.joc.6c00095","DOIUrl":"https://doi.org/10.1021/acs.joc.6c00095","url":null,"abstract":"A mild direct remote hydroxylation of α,β-unsaturated aldehydes is reported. Air is the oxidant, and tertiary alcohol products are generated in up to 80% yield. This method selectively hydroxylates enals with acidic γ-carbons and therefore may be suitable for late-stage installation of remote hydroxyl groups on medicinal aldehydes. Mechanistic studies that enabled the development of this transformation are described, as is the first example of catalytic enantioselective γ-hydroxylation of an enal.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"104 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2026-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147383575","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Man Jiang,Wan-Zhen Li,Yu Luo,Bing Zhao,Xue-Lian Lan,Ying Li,Hai-Lei Cui
A sulfoxide-based modification of tryptophan derivatives has been established through sulfenylation and selenylation, affording various highly functionalized tryptophan derivatives of great interest in acceptable-to-good yields. Sequential sulfenylation and bromination occur at the C2 and C6 positions of tryptophan derivatives, respectively, under an AcBr/TMSO/thiol reaction system. In contrast, only selenylation can be realized at the C2 position of tryptophan derivatives by the use of AcCl/DMSO and RSeSeR.
{"title":"Sulfoxide-Based Functionalization of Tryptophan Derivatives through Sulfenylation and Selenylation.","authors":"Man Jiang,Wan-Zhen Li,Yu Luo,Bing Zhao,Xue-Lian Lan,Ying Li,Hai-Lei Cui","doi":"10.1021/acs.joc.6c00009","DOIUrl":"https://doi.org/10.1021/acs.joc.6c00009","url":null,"abstract":"A sulfoxide-based modification of tryptophan derivatives has been established through sulfenylation and selenylation, affording various highly functionalized tryptophan derivatives of great interest in acceptable-to-good yields. Sequential sulfenylation and bromination occur at the C2 and C6 positions of tryptophan derivatives, respectively, under an AcBr/TMSO/thiol reaction system. In contrast, only selenylation can be realized at the C2 position of tryptophan derivatives by the use of AcCl/DMSO and RSeSeR.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"231 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2026-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147383580","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
1,2-N-Migration into metal carbenes has proven to be a powerful method for the efficient construction of various valuable N-heterocycles. However, most of them are so far limited to diazo substrates and noble-metal catalysts. Herein, we report a highly selective 1,2-N migration into copper carbenes generated by the copper-catalyzed cyclization of vinylallenes, enabling the practical and atom-economical construction of diverse tetrahydropyridazines. Moreover, employing nBu-substituted vinylallenes as starting materials, 4-butylidene-tetrahydropyridazines can be exclusively formed in an orderly manner by 1,2-N migration and 1,5-H migration.
{"title":"1,2-N-Migration of Metal Carbenes In Situ-Derived from Copper-Catalyzed Cyclization of Vinylallenes: Rapid Access to Pyridazine Derivatives","authors":"Kua-Fei Wei,Ning Wang,Xiaoming Ji,Dong-Can Lv,Guang-Ce Jiang,Qi Guo,Mingqin Zhao,Wen-Bo Shen","doi":"10.1021/acs.joc.6c00283","DOIUrl":"https://doi.org/10.1021/acs.joc.6c00283","url":null,"abstract":"1,2-N-Migration into metal carbenes has proven to be a powerful method for the efficient construction of various valuable N-heterocycles. However, most of them are so far limited to diazo substrates and noble-metal catalysts. Herein, we report a highly selective 1,2-N migration into copper carbenes generated by the copper-catalyzed cyclization of vinylallenes, enabling the practical and atom-economical construction of diverse tetrahydropyridazines. Moreover, employing nBu-substituted vinylallenes as starting materials, 4-butylidene-tetrahydropyridazines can be exclusively formed in an orderly manner by 1,2-N migration and 1,5-H migration.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"231 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2026-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147383767","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The development of energetic materials that simultaneously achieve high energy density and low sensitivity remains a challenging objective. This study presents the synthesis and characterization of a novel C-N methylene bridged compound, 2, strategically integrating the backbones of furazan with 1,2,4-triazole. This molecular design exploits the high nitrogen-oxygen content of furazan and the stability of triazole, while further nitration enhances the overall performance. Compound 2 exhibits an outstanding balance of energetic properties and molecular stability, featuring a high density (1.84 g·cm-3), superior thermal stability (Td = 267 °C), and remarkable insensitivity (IS > 40 J). Its calculated detonation performance (D = 8425 m·s-1, P = 29.51 GPa) surpasses that of the classic explosive TNT. This work demonstrates the C-N methylene bridging strategy as a highly effective approach for designing high-performance and low-sensitivity energetic materials.
{"title":"A High-Density, Thermally Stable Energetic Compound: Strategic Integration of Furazan and Triazole Rings via a C-N Methylene Bridge.","authors":"Yangyang Long,Man Xu,Qi Lai,Ping Yin,Siping Pang","doi":"10.1021/acs.joc.5c02905","DOIUrl":"https://doi.org/10.1021/acs.joc.5c02905","url":null,"abstract":"The development of energetic materials that simultaneously achieve high energy density and low sensitivity remains a challenging objective. This study presents the synthesis and characterization of a novel C-N methylene bridged compound, 2, strategically integrating the backbones of furazan with 1,2,4-triazole. This molecular design exploits the high nitrogen-oxygen content of furazan and the stability of triazole, while further nitration enhances the overall performance. Compound 2 exhibits an outstanding balance of energetic properties and molecular stability, featuring a high density (1.84 g·cm-3), superior thermal stability (Td = 267 °C), and remarkable insensitivity (IS > 40 J). Its calculated detonation performance (D = 8425 m·s-1, P = 29.51 GPa) surpasses that of the classic explosive TNT. This work demonstrates the C-N methylene bridging strategy as a highly effective approach for designing high-performance and low-sensitivity energetic materials.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"234 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2026-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147393957","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Qingqing Dong, Lizhe He, Adam Czader, Robert J Comito
{"title":"Correction to \"Cascade Photofragmentation/Photoalkylation for the Synthesis of α-Tertiary Alkyl Primary Amines\".","authors":"Qingqing Dong, Lizhe He, Adam Czader, Robert J Comito","doi":"10.1021/acs.joc.6c00438","DOIUrl":"10.1021/acs.joc.6c00438","url":null,"abstract":"","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":" ","pages":""},"PeriodicalIF":3.6,"publicationDate":"2026-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147429629","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Sebastian O Oloo,Petia Bobadova-Parvanova,Alexis A Lueders,Mina Kim,Frank R Fronczek,Kevin M Smith,Maria da Graça H Vicente
The regioselective mono- and tribromination of a BOPPY dye followed by its reactivity under Pd-catalyzed cross-coupling and nucleophilic substitution reactions are reported. The brominated BOPPYs undergo Pd(0)-catalyzed cross-couplings with a variety of boronic acids and organotin reagents to give the corresponding products in good-to-excellent yields. Nucleophilic aromatic substitutions occur both on the mono- and tribromo-BOPPYs. The reactivity order of the latter is C3-Br > C1-Br > C2-Br, while in the cross-coupling reactions using Pd(PPh3)4, it is C1-Br > C3-Br > C2-Br, likely due to steric interaction upon Pd(PPh3)2 insertion into the C3-Br bond and the slightly longer and weaker C1-Br bond. The functionalized BOPPY derivatives showed pronounced bathochromic shifts in their absorption and emission bands compared with the starting compound, and fluorescence quantum yields depend on the nature and position of the substituent.
{"title":"Regioselective Halogenation of BOPPY Fluorophores and Subsequent Diversification via Cross-Coupling and Aromatic Nucleophilic Substitution Strategies.","authors":"Sebastian O Oloo,Petia Bobadova-Parvanova,Alexis A Lueders,Mina Kim,Frank R Fronczek,Kevin M Smith,Maria da Graça H Vicente","doi":"10.1021/acs.joc.5c03121","DOIUrl":"https://doi.org/10.1021/acs.joc.5c03121","url":null,"abstract":"The regioselective mono- and tribromination of a BOPPY dye followed by its reactivity under Pd-catalyzed cross-coupling and nucleophilic substitution reactions are reported. The brominated BOPPYs undergo Pd(0)-catalyzed cross-couplings with a variety of boronic acids and organotin reagents to give the corresponding products in good-to-excellent yields. Nucleophilic aromatic substitutions occur both on the mono- and tribromo-BOPPYs. The reactivity order of the latter is C3-Br > C1-Br > C2-Br, while in the cross-coupling reactions using Pd(PPh3)4, it is C1-Br > C3-Br > C2-Br, likely due to steric interaction upon Pd(PPh3)2 insertion into the C3-Br bond and the slightly longer and weaker C1-Br bond. The functionalized BOPPY derivatives showed pronounced bathochromic shifts in their absorption and emission bands compared with the starting compound, and fluorescence quantum yields depend on the nature and position of the substituent.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"53 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2026-03-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147383582","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Electrochemically driven manganese-catalyzed alkene diazidation represents a powerful strategy for C-N bond formation in organic synthesis, in which electrons serve as the sole redox mediator. Despite recent advances, the role of applied potential in directing catalyst speciation and reactivity remains poorly defined. Here, density functional theory (DFT) calculations were employed to map precatalyst speciation and to compute the Gibbs energy profiles of the two C-N bond-forming events. These calculations reveal that alternating anion injection and anodic single-electron oxidation steps dramatically lower the onset potential, enabling access to high-valent Mn(III), Mn(IV), and a formal Mn(V) manifold under mild conditions. Mechanistic analysis reveals that both C-N couplings can proceed via Mn(IV) and Mn(V) pathways, in which the first C-N bond formation is turnover-determining. Different Mn oxidation states exhibit distinct preferences for distal versus proximal C-N coupling. These insights clarify how electrochemical tuning orchestrates high-valent manganese catalysis and furnish a mechanistic blueprint for the rational design of future electrochemical alkene difunctionalization protocols.
{"title":"Electrochemical Alkene Diazidation via Voltage-Controlled High-Valent Mn Catalysis: A DFT Mechanistic Study.","authors":"Xiao-Yi Yang,Man Li,Rong-Zhen Liao","doi":"10.1021/acs.joc.5c02812","DOIUrl":"https://doi.org/10.1021/acs.joc.5c02812","url":null,"abstract":"Electrochemically driven manganese-catalyzed alkene diazidation represents a powerful strategy for C-N bond formation in organic synthesis, in which electrons serve as the sole redox mediator. Despite recent advances, the role of applied potential in directing catalyst speciation and reactivity remains poorly defined. Here, density functional theory (DFT) calculations were employed to map precatalyst speciation and to compute the Gibbs energy profiles of the two C-N bond-forming events. These calculations reveal that alternating anion injection and anodic single-electron oxidation steps dramatically lower the onset potential, enabling access to high-valent Mn(III), Mn(IV), and a formal Mn(V) manifold under mild conditions. Mechanistic analysis reveals that both C-N couplings can proceed via Mn(IV) and Mn(V) pathways, in which the first C-N bond formation is turnover-determining. Different Mn oxidation states exhibit distinct preferences for distal versus proximal C-N coupling. These insights clarify how electrochemical tuning orchestrates high-valent manganese catalysis and furnish a mechanistic blueprint for the rational design of future electrochemical alkene difunctionalization protocols.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"54 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2026-03-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147383581","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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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