Alageswaran Jayaram, , , Yu- Ming Liu, , , Nian-Qi Chen, , , Genin Gary Huang, , , Gopal Chandru Senadi, , and , Wei-Yu Lin*,
{"title":"Activation of gem-Dichloroacetamides and Epoxides Using Elemental Sulfur and Amines: A Route to Monothiooxalamides and α-Ketothioamides","authors":"Alageswaran Jayaram, , , Yu- Ming Liu, , , Nian-Qi Chen, , , Genin Gary Huang, , , Gopal Chandru Senadi, , and , Wei-Yu Lin*, ","doi":"10.1021/acs.joc.5c01684","DOIUrl":"10.1021/acs.joc.5c01684","url":null,"abstract":"<p >The selective activation of C–X bonds to generate value-added products via transition metal-free methodologies remains a formidable challenge in modern synthetic chemistry. Herein, we report a metal-free didechlorinative strategy for the construction of unsymmetrical monothiooxalamides through C–S and C–N bond formation. This transformation proceeds via a one-pot functionalization of <i>gem</i>-dichloroacetamides with various amines and elemental sulfur (S<sub>8</sub>) under ambient conditions in an open-air atmosphere, offering a sustainable and operationally simple approach. Additionally, a regioselective epoxide ring-opening approach was implemented using I<sub>2</sub>/DMSO, enabling the efficient synthesis of <span>α</span>-ketothioamides through the incorporation of S<sub>8</sub> and diverse amine nucleophiles. Furthermore, ligand studies revealed that monothiooxalamides exhibit high efficacy as ligands in Cu-catalyzed C–N cross-coupling reactions. The method’s synthetic utility was further demonstrated through gram-scale synthesis and the preparation of natural product derivatives and drug analogues, highlighting its potential for industrial applications.</p>","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"90 41","pages":"14673–14682"},"PeriodicalIF":3.6,"publicationDate":"2025-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.joc.5c01684","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145203809","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":"HFIP/BF3·Et2O Synergistic Catalysis Enables Intramolecular Alkyne Cyclization to Coumarins","authors":"Yu Zhao, , , Yu Cheng, , , Quanye Liu, , , Mengyi Li, , , Wei Li*, , and , Di Wu*, ","doi":"10.1021/acs.joc.5c01199","DOIUrl":"10.1021/acs.joc.5c01199","url":null,"abstract":"<p >We have successfully developed a novel synergistic catalytic system employing hexafluoroisopropanol (HFIP)/BF<sub>3</sub>·Et<sub>2</sub>O for intramolecular alkyne cyclization, which enables efficient construction of coumarin frameworks. This metal-free protocol features mild reaction conditions and exceptional substrate generality. The methodology has been directly applied to the synthesis of pharmacologically important natural products and drug molecules. Systematic mechanistic investigations have uncovered the cooperative catalytic mechanism of HFIP in this transformation, providing new fundamental principles for reaction design.</p>","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"90 40","pages":"14304–14311"},"PeriodicalIF":3.6,"publicationDate":"2025-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145203797","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":"Semiheterogeneous Intrinsic FeTiO3-Photoredox/Ph3N Dual-Catalyzed Fluoroalkylation of N-Heteroarenes with Alkenes and RfSO2Cl","authors":"Qiong-Hui Peng, , , Ying-Li Cai, , , Hui Dai, , , Chun-Lin Zhuang, , , Sheng-Hua Wang*, , , Zi Yang*, , , Zu-Li Wang, , , Jun Jiang*, , and , Wei-Min He*, ","doi":"10.1021/acs.joc.5c02000","DOIUrl":"10.1021/acs.joc.5c02000","url":null,"abstract":"<p >Herein, we report the sustainable semiheterogeneous synthesis of various fluoroalkylated <i>N</i>-heteroarenes using natural intrinsic iron(II) titanium oxide (FeTiO<sub>3</sub>) as a semiconductor photocatalyst and Ph<sub>3</sub>N as a redox mediator. This synergistic system combines photogenerated electron-mediated fluoroalkyl sulfonyl chloride (R<sub>f</sub>SO<sub>2</sub>Cl) reduction with photogenerated hole-induced oxidative dehydrogenation aromatization, enabling high-yielding transformations with excellent functional-group tolerance while avoiding stoichiometric redox reagents or sacrificial electron donors/acceptors.</p>","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"90 41","pages":"14786–14795"},"PeriodicalIF":3.6,"publicationDate":"2025-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145203796","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":"Direct Synthesis of Various Thioesters from Acyl Fluorides and Thiosilanes through the Assistance of a Si–F Bond Formation","authors":"Ryuki Takeuchi, , , Kento Ishida, , and , Norio Sakai*, ","doi":"10.1021/acs.joc.5c01677","DOIUrl":"10.1021/acs.joc.5c01677","url":null,"abstract":"<p >Herein it is described that the coupling reactions of aromatic and aliphatic acyl fluorides with phenyl trimethylsilyl sulfide proceeded smoothly under neat conditions to produce thioester derivatives. The addition of a catalytic amount of typical bases, such as triethylamine (Et<sub>3</sub>N) and potassium butoxide (KO<sup><i>t</i></sup>Bu), effectively activates thiosilanes, which could facilitate the coupling reactions of aroyl fluorides with a variety of aryl/alkyl thiosilanes containing an alkyl group, a halogen, an ester, or a heterocyclic ring to produce a variety of thioesters in practical yields.</p>","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"90 41","pages":"14664–14672"},"PeriodicalIF":3.6,"publicationDate":"2025-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.joc.5c01677","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145209049","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}
Federico Dini, , , Giorgia Puntoni, , , Lilia Tinagli, , , Lorenzo Di Bari, , , Gennaro Pescitelli*, , and , Gianluigi Albano*,
{"title":"Synthesis and Chiroptical Properties of Bithiophene-Functionalized Open and Methylene-Bridged Binaphthyl Derivatives","authors":"Federico Dini, , , Giorgia Puntoni, , , Lilia Tinagli, , , Lorenzo Di Bari, , , Gennaro Pescitelli*, , and , Gianluigi Albano*, ","doi":"10.1021/acs.joc.5c01954","DOIUrl":"10.1021/acs.joc.5c01954","url":null,"abstract":"<p >Thiophene-based π-conjugated compounds are one of the most important classes of organic materials for optoelectronic applications. In this context, herein we report the synthesis of two enantiopure binaphthyl systems: an open and a methylene-bridged 1,1′-bi-2-naphthol (BINOL) derivative, functionalized at the C6/C6′ positions with lateral 2,2′-bithiophen-5-yl moieties (compounds (a<i>R</i>)-<b>3</b> and (a<i>R</i>)-<b>6</b>, respectively). Both final products were subjected, together with their synthetic precursors (i.e., the corresponding unsubstituted and 6,6′-dibrominated BINOL derivatives), to UV–vis absorption and electronic circular dichroism (ECD) investigation in solution and thin films. A computational analysis based on density functional theory (DFT) and time-dependent DFT (TD-DFT) allowed us to gain physical insight into the observed (chiro)optical properties, emphasizing the crucial role of thiophene rings as C6/C6′ substituents. Moreover, the occurrence of induced ECD and circularly polarized luminescence (CPL) signals was observed in preliminary tests of chiroptical induction, performed for thin films of achiral benzothiadiazole (BTD) dye <b>7</b> in the presence of small percentages (0.5–5.0 mol %) of the methylene-bridged target molecule (a<i>R</i>)-<b>6</b> as chiral inducer.</p>","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"90 41","pages":"14754–14768"},"PeriodicalIF":3.6,"publicationDate":"2025-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.joc.5c01954","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145203798","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":"Aminoquinoline-Directed Electrochemical Cobalt-Catalyzed C(sp²)–H Alkoxylation","authors":"Li-Bo Li, , , Zhi-Xiong Ou, , , Bu-Hong Zhang, , , Min-Xuan Yang, , , Jun-Qi Zhang*, , and , Xing-Wang Wang*, ","doi":"10.1021/acs.joc.5c01585","DOIUrl":"10.1021/acs.joc.5c01585","url":null,"abstract":"<p >Electrochemically, earth-abundant cobalt(II)-catalyzed C(sp<sup>2</sup>)–H alkoxylation of ferrocenyl and arenyl amides with 8-aminoquinoline directing groups was developed under mild, oxidant-free conditions. This protocol afforded a broad range of alkoxylated products in moderate to high yields, employing readily available alcohols as both alkoxy sources and green solvents. Notably, this method enabled efficient C–O bond formation via sustainable electrolysis and offered a practical route to alkylated organic compounds.</p>","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"90 40","pages":"14118–14131"},"PeriodicalIF":3.6,"publicationDate":"2025-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145205172","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":"Analysis of Cyclohexa-1,4-dienes with an Asymmetrically Substituted, 3° Carbon Atom as Chiral Dihydrogen Surrogates in Reagent-Controlled Transfer Hydrogenation of Alkenes","authors":"Paul E. Rucker, and , Martin Oestreich*, ","doi":"10.1021/acs.joc.5c02009","DOIUrl":"10.1021/acs.joc.5c02009","url":null,"abstract":"<p >Building on a reagent-controlled, trityl-cation-initiated enantioselective transfer hydrogenation of alkenes recently developed by us, a broad set of chiral cyclohexa-1,4-diene-based dihydrogen surrogates was synthesized and applied to the reduction of 1,1-disubstituted alkenes. The expanded structural diversity allowed for a more refined investigation of the structure-selectivity relationship. The experimental results are in agreement with earlier computational predictions and highlight the role of steric factors proximal (gray circle) and distal (black circle) to the stereocenter in governing the efficiency of transfer hydrogenation.</p>","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"90 41","pages":"14856–14859"},"PeriodicalIF":3.6,"publicationDate":"2025-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.joc.5c02009","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145209050","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}
Hanieh Mahmoodi, , , Nuno Basílio*, , , Paula S. Branco, , , João Carlos Lima, , and , Fernando Pina*,
{"title":"Calculation of the Absorption Spectra of Various Anthocyanin Species in an Acidic Medium Using Stopped-Flow Spectroscopy","authors":"Hanieh Mahmoodi, , , Nuno Basílio*, , , Paula S. Branco, , , João Carlos Lima, , and , Fernando Pina*, ","doi":"10.1021/acs.joc.5c02019","DOIUrl":"10.1021/acs.joc.5c02019","url":null,"abstract":"<p >Equilibrated solutions of anthocyanins in a moderately acidic medium contain quinoidal base, hemiketal, and the <i>cis-</i> and <i>trans</i>-chalcone forms in a reversible, pH-dependent equilibrium. Reverse pH jumps to pH ≤1, monitored by stopped-flow spectroscopy, reveal the stepwise formation of the flavylium cation: initially from the quinoidal base within the mixing time, followed by slower conversion from the hemiketal, and then from the <i>cis</i>-chalcone. Final equilibration through <i>cis</i>–<i>trans</i> isomerization to <i>trans</i>-chalcone was monitored by using a standard spectrophotometer. Exploiting these kinetic differences, we reconstructed the individual absorption spectra of all anthocyanin species. This study demonstrates the utility of reverse pH jumps combined with complementary spectroscopic analysis for resolving transient species in complex chemical networks.</p>","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"90 40","pages":"14285–14290"},"PeriodicalIF":3.6,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145194969","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}
Christoph Suster, , , Nicolas Kratena, , , Kyryl Bocharov, , and , Christian Stanetty*,
{"title":"Organocatalytic Stetter Cyclization of Pentoses for the Synthesis of Polyhydroxylated Cyclopentanone Scaffolds","authors":"Christoph Suster, , , Nicolas Kratena, , , Kyryl Bocharov, , and , Christian Stanetty*, ","doi":"10.1021/acs.joc.5c01792","DOIUrl":"10.1021/acs.joc.5c01792","url":null,"abstract":"<p >An organocatalytic approach for the carbocyclization of aldopentoses is disclosed. After initial activation, with the introduction of the intramolecular Michael acceptor in the substrate, the NHC-catalyzed Stetter reaction can be performed, giving rise to cyclopentanone scaffolds bearing multiple chiral centers and protected hydroxy groups. An optional controlled one-pot elimination provides the corresponding cyclopentenones as well. Due to the commercial availability of <span>d</span>- and <span>l</span>-pentoses all possible stereochemical permutations of the products can be prepared conveniently and affordably.</p>","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"90 40","pages":"14328–14332"},"PeriodicalIF":3.6,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.joc.5c01792","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145195124","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}
Mariana Vardé, , , Sebastian Suarez, , , Evangelina Repetto*, , and , Oscar Varela*,
{"title":"Asymmetric Induction of Sugar-Derived Dipole and Dipolarophile in 1,3-Dipolar Cycloadditions Leading to Pyrrolidines","authors":"Mariana Vardé, , , Sebastian Suarez, , , Evangelina Repetto*, , and , Oscar Varela*, ","doi":"10.1021/acs.joc.5c01627","DOIUrl":"10.1021/acs.joc.5c01627","url":null,"abstract":"<p >The 1,3-dipolar cycloaddition reaction of achiral dipolarophiles (maleates) with chiral, open-chain sugar-derived azomethine ylides yielded enantiomerically pure or diastereomeric mixtures of pyrrolidine cycloadducts. The outcome of the reaction, whether diastereoselective or not, depended on the substitution pattern and length of the sugar chain in the dipole. Diastereoselectivity was successfully achieved for 3-deoxy sugar imino esters (precursors of ylides) having a seven-membered sugar chain substituted with two isopropylidene rings. The use of pyranones, which are derived from common pentoses, as chiral dipolarophiles with chiral or achiral azomethine ylides led to pyrrolidines in a highly diastereoselective manner. The asymmetry was induced by the stereocenter of the dipolarophile, which prevailed over the stereocenters of the sugar chain of the dipole (dipolarophile-based stereocontrol). In many instances, the resulting pyrrolidines were entirely carbohydrate-based, as both the dipolarophile and dipole were derived from sugars.</p>","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"90 40","pages":"14157–14171"},"PeriodicalIF":3.6,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145203804","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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