Journal of Organic Chemistry最新文献

{"title":"Exploring the Azabenzannulation of Benzothioxanthene Imide","authors":"Arthur H. G. David*,&nbsp;, ,&nbsp;Darío Puchán Sánchez,&nbsp;, ,&nbsp;Ahmad Kassem,&nbsp;, ,&nbsp;Maxime Roger,&nbsp;, ,&nbsp;Magali Allain,&nbsp;, ,&nbsp;Tangui Le Bahers,&nbsp;, ,&nbsp;Cyrille Monnereau,&nbsp;, ,&nbsp;Antoine Goujon*,&nbsp;, and ,&nbsp;Clément Cabanetos*,&nbsp;","doi":"10.1021/acs.joc.5c01303","DOIUrl":"10.1021/acs.joc.5c01303","url":null,"abstract":"<p >We report herein the synthesis and characterization of azabenzannulated benzothioxanthene imides (BTIs) functionalized with various appended aromatic units. This new class of polycyclic aromatic hydrocarbons is prepared <i>via</i> a straightforward and efficient synthetic strategy that involves a visible-light-mediated photocyclization of imines. The latter are formed <i>in situ</i> from the condensation of an amine moiety at the <i>bay</i> position of the BTI core with aldehydes, followed by oxidative rearomatization. These green-yellow fluorescent emitters (φ_f ∼ 0.14–0.20) combine dual redox properties with significant triplet state generation─resulting from a combination of strong spin–orbit coupling and the energetic proximity between their S₁ and triplet states─with notable singlet oxygen sensitization efficiencies (φ_Δ ∼ 0.39–0.49). Hence, this design principle enables accessible, tailored structural modifications through the incorporation of diverse functional groups into the BTI core with minimal synthetic effort, paving the way to original and versatile functional materials with broad potential in optoelectronics, biophotonics, and photodynamic therapy.</p>","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"90 41","pages":"14479–14486"},"PeriodicalIF":3.6,"publicationDate":"2025-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145236047","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}

{"title":"Synthesis of Fluorine-Terminated Phenanthrimidazole under Precise Regulation and Structure–Activity Relationship","authors":"Kexuan Li*,&nbsp;, ,&nbsp;Xiao Song,&nbsp;, ,&nbsp;Qianqian Zhao,&nbsp;, ,&nbsp;Yongliang Liu,&nbsp;, ,&nbsp;Wenbo Wang,&nbsp;, and ,&nbsp;Shengbo Zhu*,&nbsp;","doi":"10.1021/acs.joc.5c01160","DOIUrl":"10.1021/acs.joc.5c01160","url":null,"abstract":"<p >Designing hybrid local and charge transfer (HLCT) molecules with an appropriate charge transfer (CT) or local excited (LE) ratio often requires careful consideration. To explore the suitable mixing ratio of CT and LE in the phenanthroimidazole system, in this study, different numbers of fluorine atoms were precisely regulated and introduced onto the terminal benzene ring. A series of D–A type molecules were successfully designed and synthesized using phenanthrimidazole as the donor and varying amounts of fluorobenzene as the acceptor (namely, <b>0F-mP</b>, <b>1F-mP</b>, <b>2F-mP</b>, and <b>3F-mP</b>). The research results show that the four types of molecules designed demonstrate HLCT characteristics, as confirmed by theoretical calculations and varying the practical experiments. The introduction of fluorine at the C4 position significantly affects the relevant photophysical properties: increasing the photoluminescence quantum yield (PLQY), narrowing the full width at half-maximum (fwhm), and effectively reducing the Stokes shift. The PLQYs of <b>1F-mP</b> in THF solution and solid states are 50.8 and 50.4%, respectively. However, <b>1F-mP</b> exhibits a higher PLQY and either unchanged or narrower fwhm in most solvents, which indicated that the appropriate CT/LE ratio regulation could significantly affect the photophysical properties.</p>","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"90 41","pages":"14439–14451"},"PeriodicalIF":3.6,"publicationDate":"2025-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145215957","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}

{"title":"Syntheses of Pyrene-4,5-dione and Pyrene-4,5,9,10-tetraone","authors":"Omolola Balogun,&nbsp;, ,&nbsp;Besan Khader,&nbsp;, ,&nbsp;Tetyana Ignatova,&nbsp;, and ,&nbsp;Aleksandrs Prokofjevs*,&nbsp;","doi":"10.1021/acs.joc.5c01542","DOIUrl":"10.1021/acs.joc.5c01542","url":null,"abstract":"<p >Improved gram scale synthesis procedures for the preparation of pyrene-4,5-dione and pyrene-4,5,9,10-tetraone are reported. Pyrene-4,5-dione has been synthesized using potassium persulfate as the oxidant and RuO₂·<i>n</i>H₂O as the catalyst in the biphasic CH₂Cl₂/H₂O solvent mixture containing K₂CO₃ as the base. We also developed several procedures for multigram scale oxidation of pyrene-4,5-dione to pyrene-4,5,9,10-tetraone, eliminating the need for chromatographic purification of the poorly soluble tetraone product.</p>","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"90 41","pages":"14835–14838"},"PeriodicalIF":3.6,"publicationDate":"2025-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.joc.5c01542","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145216278","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Rapid Mechanochemical Ring-Opening and 1,3-Bisfunctionalization of Donor–Acceptor Cyclopropanes: Regioselective C(sp2)–H Alkylation of Coumaran and Chromane","authors":"Sumeyye Atis,&nbsp;, ,&nbsp;Ferruh Lafzi,&nbsp;, and ,&nbsp;Haydar Kilic*,&nbsp;","doi":"10.1021/acs.joc.5c01198","DOIUrl":"10.1021/acs.joc.5c01198","url":null,"abstract":"<p >Regioselective alkylation of 2,3-dihydrobenzofuran (coumaran) and chromane was accomplished through the ring-opening of donor–acceptor cyclopropanes (DACs) under mechanochemical conditions. The developed mechanochemical protocol efficiently promotes the ring-opening of DACs. Importantly, it enabled the first mechanochemical 1,3-bisfunctionalization of DACs using a range of electrophiles, furnishing the target products in high yields and significantly reducing reaction times.</p>","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"90 41","pages":"14408–14414"},"PeriodicalIF":3.6,"publicationDate":"2025-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145215961","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}

{"title":"DABCO-Catalyzed β-C(sp2)-H Indolylation of 4-Arylidene Pyrazolones and 5-Arylidene Thiazolones with N-Tosyliminoindoles","authors":"Shikha Singh Rathor,&nbsp;, ,&nbsp;Poonam Rani,&nbsp;, and ,&nbsp;Sampak Samanta*,&nbsp;","doi":"10.1021/acs.joc.5c01931","DOIUrl":"10.1021/acs.joc.5c01931","url":null,"abstract":"<p >A simple, efficient tactic for the direct β-C(sp²-H) functionalization reaction of various 4- or 5-arylidene pyrazolones/thiazolones using <i>N</i>-tosyliminoindoles catalyzed by 20 mol % DABCO in an open atmosphere is reported for the first time. This metal-free reaction represents a rare example of C3-alkenylation of 2-<i>N</i>-tosylaminoindoles, creating an efficient C(sp²)–C(sp²) bond selectively through a Michael-aerial oxidation process under aerobic conditions. Consequently, this method allows for the <i>de novo</i> access to value-added β-(2-<i>N</i>-tosylaminoindol-3-yl)-β-arylmethylene pyrazolones and unexpectedly, oxazolin-4(5<i>H</i>)-ones in satisfactory chemical yields and excellent selectivities (up to <i>Z/E</i> ≤ 99:1 or <i>E/Z</i> ≤ 99:1) with 100% carbon-atom efficiency. Moreover, incorporating a fluorine atom and alkyl peroxy group at the C4 and C3 positions on pyrazolone and indole rings, respectively, of β-(2-<i>N</i>-tosylaminoindol-3-yl) methylene pyrazolones was successfully achieved with remarkable selectivity through a dearomatization process, demonstrating the synthetic usefulness of the synthesized unsaturated pyrazolones.</p>","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"90 41","pages":"14732–14753"},"PeriodicalIF":3.6,"publicationDate":"2025-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145215959","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}

{"title":"Chemodivergent Synthesis of 1,3-Benzoxazines, Indolin-3-ols, and Indoles from the Designer Amides: Applications to the Synthesis of Phenanthridine Natural Products","authors":"Waseem I. Lone,&nbsp;, ,&nbsp;Gowhar Ahmad Rather,&nbsp;, ,&nbsp;Bilal A. Bhat*,&nbsp;, and ,&nbsp;Showkat Rashid*,&nbsp;","doi":"10.1021/acs.joc.5c01463","DOIUrl":"10.1021/acs.joc.5c01463","url":null,"abstract":"<p >A chemodivergent synthesis of 1,3-benzoxazines, indolin-3-ols, and indoles has been conceptualized from readily accessible 2-bromoacetylphenyl benzamides. The strategy emanates from the NaBH₄-mediated reduction of the designer amides, triggering an intramolecular cyclization cascade and furnishing three distinct classes of heterocycles with high precision. A unified synthesis of phenanthridine natural products was also accomplished to work out the utility of this strategy. Broad substrate scope, operational flexibility, and successful implementation at the gram-scale level are notable highlights of this strategy.</p>","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"90 41","pages":"14520–14540"},"PeriodicalIF":3.6,"publicationDate":"2025-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145215963","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}

{"title":"Odorless and Air-Stable Thionating Reagent for Broad Scope Thioamide Synthesis without H2S Emission","authors":"Tomoya Sugai,&nbsp;, ,&nbsp;Mizuki Oyanagi,&nbsp;, ,&nbsp;Takashi Nakamura,&nbsp;, ,&nbsp;Atsuya Momotake,&nbsp;, and ,&nbsp;Noriki Kutsumura*,&nbsp;","doi":"10.1021/acs.joc.5c00982","DOIUrl":"10.1021/acs.joc.5c00982","url":null,"abstract":"<p >A novel thionating reagent, 7-phenyl-2,4,6,8,9-pentathia-1,3,5-triphosphaadamantane 1,3,5-trisulfide (<b>1</b>), bearing an S–P adamantane framework, has been developed as a practical and environmentally benign alternative to conventional thionating reagents. Unlike Lawesson's reagent and P₄S₁₀, compound <b>1</b> is air- and thermally stable, odorless, and does not release detectable H₂S under ambient storage conditions. It enables efficient thionation of a broad range of amides─including primary, secondary, tertiary, aliphatic, and aromatic─into the corresponding thioamides in moderate to excellent yields. The reagent exhibits excellent chemoselectivity and functional group tolerance, allowing late-stage thionation of complex molecules, such as pharmaceuticals and natural product derivatives. It is also recyclable and retains reactivity after storage or heating. Moreover, a postreaction H₂S-trapping protocol ensures odorless and safe operation. These features establish compound <b>1</b> as a next-generation thionating reagent that addresses the critical drawbacks of existing reagents, offering a green and scalable platform for thioamide synthesis.</p>","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"90 41","pages":"14383–14394"},"PeriodicalIF":3.6,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145216279","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}

{"title":"Extensive Evaluation of Dinitropyrazole and Tetrazole-Based Energetic Compounds: Role of Isomerism and Oxygen Balance on the Overall Performance","authors":"Priyanka Das,&nbsp;, ,&nbsp;Prachi Bhatia,&nbsp;, ,&nbsp;Shivanshu Verma,&nbsp;, ,&nbsp;Aditya Yadav,&nbsp;, ,&nbsp;Satyabrata Sahoo,&nbsp;, and ,&nbsp;Dheeraj Kumar*,&nbsp;","doi":"10.1021/acs.joc.5c01729","DOIUrl":"10.1021/acs.joc.5c01729","url":null,"abstract":"<p >Nitrogen-rich heterocycles have been instrumental in the pursuit of design, synthesis, and modification of advanced energetic materials developed to fulfill evolving requirements. Thus, the role of material chemists is to bridge the research gap by understanding how different rings and functional groups influence overall performance. In this work, 3,4-dinitritropyrazole (3,4-DNP) and 3,5-dinitropyrazole (3,5-DNP) were taken as precursors for the synthesis of energetic materials having harmonized energy and safety. Utilizing <i>N</i>-methylene-C bridging, they were paired with tetrazole and <i>N</i>-hydroxytetrazole explosophores, followed by salt formation for performance modification. The isomeric dinitropyrazoles were found to be more favorable for pairing with the <i>N</i>-hydroxytetrazole than commonly utilized 4-substituted 3,5-dinitropyrazoles. Consequently, this marks the first report of an asymmetric combination involving the <i>N</i>-hydroxytetrazole moiety, achieved through the bridging approach. After the performance evaluation, a comparative assessment of isomeric analogues was implemented. The presence of an additional oxygen supplement results in higher energetic properties with respect to tetrazole-based compounds. All compounds demonstrated energetic performance superior to TNT and good physical stability. This study revealed that among the isomeric 3,4-DNP and 3,5-DNP derivatives, the energetic performance of neutral 3,4-DNP derivatives (<b>7</b> and <b>15</b>) was higher, and the thermal stability of the 3,5-DNP derivatives (<b>8</b> and <b>16</b>) was superior.</p>","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"90 41","pages":"14683–14694"},"PeriodicalIF":3.6,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145209808","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}

{"title":"Mechanistic Insights into Photocatalytic Reduction and Triplet Sensitization of 4-Azido-1-phenylbutan-1-ones to Selectively Form 2-Phenyl-1-pyrrolines","authors":"DeVonna M. Gatlin,&nbsp;, ,&nbsp;Nayera M. Abdelaziz,&nbsp;, ,&nbsp;Fiona J. Wasson,&nbsp;, ,&nbsp;Anindya Borah,&nbsp;, ,&nbsp;Brian D. Etz,&nbsp;, ,&nbsp;Sulaiman Umar Abbas,&nbsp;, ,&nbsp;Anntonette N. Perry,&nbsp;, ,&nbsp;Mikayla A. Hudak,&nbsp;, ,&nbsp;Khadyjah Diaw,&nbsp;, ,&nbsp;Shubham Vyas,&nbsp;, and ,&nbsp;Anna D. Gudmundsdottir*,&nbsp;","doi":"10.1021/acs.joc.5c01550","DOIUrl":"10.1021/acs.joc.5c01550","url":null,"abstract":"<p >Organic azides are valuable precursors in synthetic chemistry, particularly for nitrogen-based functionalization through photochemical activation. In this study, the photoreactivities of 4-azido-1-phenylbutan-1-one (<b>1a</b>) and 4-azido-(4-methoxy)phenylbutan-1-one (<b>1b</b>) were investigated using visible-light photocatalysts [Ir(dF(CF₃)ppy)₂(dtbpy)]PF₆ and [Ru(bpy)₃]Cl₂ to elucidate the mechanistic differences between triplet energy transfer and photoreductive electron transfer pathways. Direct irradiation of <b>1a</b> in methanol favors the formation of a biradical species via intramolecular H atom abstraction to generate its lowest triplet ketone (T_1K) with an (n,π*) configuration, which selectively yields 2-phenyl-1-pyrroline derivative <b>2a</b>. However, <b>1b</b> reacts through its less reactive T_1K, which has a (π,π*) configuration, to form 2-phenyl-1<i>H</i>-pyrrole as the major product. When sensitized by [Ir(dF(CF₃)ppy)₂(dtbpy)]PF₆, selective excitation of the triplet azido moiety (T_A) of both <b>1a</b> and <b>1b</b> yields the corresponding pyrroline (<b>2a</b> and <b>2b</b>) via triplet alkylnitrene (³<b>1aN</b> and³<b>1bN</b>) formation. In contrast, photoactivation of [Ru(bpy)₃]Cl₂ in the presence of diisopropylethylamine (DIPEA) results in photoreductive electron transfer, forming azido radical anion intermediates, which cyclize to also yield <b>2a</b> and <b>2b</b>. Product studies, cyclic voltammetry, laser flash photolysis, and DFT calculations supported these mechanistic assignments. This work demonstrates complementary approaches to control alkyl azide photoreactivity and unlock new strategies for visible-light-induced nitrogen incorporation.</p>","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"90 41","pages":"14597–14606"},"PeriodicalIF":3.6,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145216081","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}

{"title":"Construction of a BCDE Core of Furanosteroids Enabled by Nickel-Promoted Reductive Cyclization","authors":"Li-Jun Xu,&nbsp; and ,&nbsp;Yu Peng*,&nbsp;","doi":"10.1021/acs.joc.5c01840","DOIUrl":"10.1021/acs.joc.5c01840","url":null,"abstract":"<p >We developed a new synthetic strategy for furanosteroids and constructed the BE ring system in one step by a Ni-catalyzed reductive cyclization cascade. The subsequent oxidative elaboration led to the efficient formation of a BCDE tetracyclic core embedded in these furanosteroids. Furthermore, a synthesis of the carbon skeleton of nodulisporiviridin C was achieved, as well, through this method.</p>","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"90 41","pages":"14851–14855"},"PeriodicalIF":3.6,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145209809","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}