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}
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}
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}
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}
A palladium-complex-catalyzed cross-coupling reaction was achieved between benzyl diazo esters and aryl iodides bearing ortho-substituents, which had previously not been tolerated for such reactions. In the quest for an optimal catalyst for reactions with ortho-iodobenzaldehyde, the yields of the desired coupling compound were unsatisfactory in many catalyst systems, and the aldol reaction frequently occurred competitively. However, the catalyst prepared from Pd(dba)2 and P(2-furyl)3 promoted the cross-coupling reaction, generating α-diazophenyl acetate in excellent yield. The cross-coupling was also acceptable for aryl iodides with various ortho-substituents, delivering a variety of coupling products in moderate to good yields.
{"title":"A Cross-Coupling Reaction between Ortho-Substituted Aryl Iodide and Diazoester Using Tri-(2-furyl)phosphine as a Ligand of Palladium Catalyst.","authors":"Kazuki Naoi,Shinji Nagumo","doi":"10.1021/acs.joc.5c02786","DOIUrl":"https://doi.org/10.1021/acs.joc.5c02786","url":null,"abstract":"A palladium-complex-catalyzed cross-coupling reaction was achieved between benzyl diazo esters and aryl iodides bearing ortho-substituents, which had previously not been tolerated for such reactions. In the quest for an optimal catalyst for reactions with ortho-iodobenzaldehyde, the yields of the desired coupling compound were unsatisfactory in many catalyst systems, and the aldol reaction frequently occurred competitively. However, the catalyst prepared from Pd(dba)2 and P(2-furyl)3 promoted the cross-coupling reaction, generating α-diazophenyl acetate in excellent yield. The cross-coupling was also acceptable for aryl iodides with various ortho-substituents, delivering a variety of coupling products in moderate to good yields.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"14 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2026-03-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147383579","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}
Zeyuan Zhao,Xiang Wang,Youcan Zhang,Tiefeng Xu,Ya Li
An efficient and practical method for the synthesis of S-alkyl-substituted 2-cyanoacrylate derivatives is described. This transformation relies on a base-promoted ring-opening thioalkylation of cyclic sulfonium salts in which C-S bond cleavage and recombination occur smoothly with commercially available isothiocyanates and alkyl nitriles under an air atmosphere, affording the desired products in good to excellent yields. This process operates under mild, transition-metal- and additive-free reaction conditions, showcasing high selectivity and good tolerance to various functional groups.
{"title":"Base-Promoted Ring-Opening Reaction of Sulfonium Salts with Isothiocyanates and Alkyl Nitriles for Accessing 2-Cyanoacrylate Derivatives.","authors":"Zeyuan Zhao,Xiang Wang,Youcan Zhang,Tiefeng Xu,Ya Li","doi":"10.1021/acs.joc.6c00013","DOIUrl":"https://doi.org/10.1021/acs.joc.6c00013","url":null,"abstract":"An efficient and practical method for the synthesis of S-alkyl-substituted 2-cyanoacrylate derivatives is described. This transformation relies on a base-promoted ring-opening thioalkylation of cyclic sulfonium salts in which C-S bond cleavage and recombination occur smoothly with commercially available isothiocyanates and alkyl nitriles under an air atmosphere, affording the desired products in good to excellent yields. This process operates under mild, transition-metal- and additive-free reaction conditions, showcasing high selectivity and good tolerance to various functional groups.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"6 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2026-03-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147383578","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}
Bipolarizens A-O (1-15), 15 previously undescribed ophiobolin derivatives, and one known analog, 3-anhydroophiobolin A (16), were discovered from the fungus Bipolaris maydis. All of the compounds were elucidated by extensive spectroscopic data, DP4+ analyses, electronic circular dichroism (ECD) calculations, and X-ray crystallography studies. Compound 1 had a 15-oxatetracyclo[9.3.2.02,12.04,8]hexadecane-bridged system. Compound 2 featured a 5/8/5/7-tetracyclic sesterterpenoid framework, constituting only the second reported example of this structural class. Bioactivity research revealed that compound 16 exhibited moderate antimicrobial activity against Bacillus cereus, with a MIC of 50 μg/mL. Further crystal-violet assay, fluorescent staining, and scanning electron microscopy significantly demonstrated that compound 16 could inhibit biofilm formation and cellular morphological integrity of B. cereus. These findings not only enrich the structural diversity of ophiobolins but also offer a promising molecular scaffold to control foodborne contamination associated with B. cereus and its biofilm.
{"title":"Antimicrobial Activities of Ophiobolins from Bipolaris maydis against Foodborne Pathogenic Bacteria via Biofilm Formation Inhibition.","authors":"Yong Shen,Xiaotian Zhang,Xian Xia,Mingbo Li,Chunmei Chen,Qin Li,Yonghui Zhang,Hucheng Zhu","doi":"10.1021/acs.joc.6c00055","DOIUrl":"https://doi.org/10.1021/acs.joc.6c00055","url":null,"abstract":"Bipolarizens A-O (1-15), 15 previously undescribed ophiobolin derivatives, and one known analog, 3-anhydroophiobolin A (16), were discovered from the fungus Bipolaris maydis. All of the compounds were elucidated by extensive spectroscopic data, DP4+ analyses, electronic circular dichroism (ECD) calculations, and X-ray crystallography studies. Compound 1 had a 15-oxatetracyclo[9.3.2.02,12.04,8]hexadecane-bridged system. Compound 2 featured a 5/8/5/7-tetracyclic sesterterpenoid framework, constituting only the second reported example of this structural class. Bioactivity research revealed that compound 16 exhibited moderate antimicrobial activity against Bacillus cereus, with a MIC of 50 μg/mL. Further crystal-violet assay, fluorescent staining, and scanning electron microscopy significantly demonstrated that compound 16 could inhibit biofilm formation and cellular morphological integrity of B. cereus. These findings not only enrich the structural diversity of ophiobolins but also offer a promising molecular scaffold to control foodborne contamination associated with B. cereus and its biofilm.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"73 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2026-03-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147374037","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}
Here, we report that commercial aryl sulfonyl azides efficiently convert primary aliphatic amines into azides under mild conditions. We further show that this diazotransfer reaction exhibits a pronounced preference for aliphatic over aromatic amino groups. This chemoselectivity enables the one-step synthesis of bifunctional molecules bearing both azido and aniline moieties, offering a practical and scalable route to orthogonally "clickable" building blocks for chemical biology and materials modification.
{"title":"Chemoselective Diazotransfer of Primary Aliphatic Amines into Azides Using Commercial Aryl Sulfonyl Azides.","authors":"Linlin Xu,Ningning Song,Yu Wang,Xiu Wang,Shengtao Ding","doi":"10.1021/acs.joc.5c03200","DOIUrl":"https://doi.org/10.1021/acs.joc.5c03200","url":null,"abstract":"Here, we report that commercial aryl sulfonyl azides efficiently convert primary aliphatic amines into azides under mild conditions. We further show that this diazotransfer reaction exhibits a pronounced preference for aliphatic over aromatic amino groups. This chemoselectivity enables the one-step synthesis of bifunctional molecules bearing both azido and aniline moieties, offering a practical and scalable route to orthogonally \"clickable\" building blocks for chemical biology and materials modification.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"45 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2026-03-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147381220","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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