ACS Organic & Inorganic Au最新文献

{"title":"Multicomponent Photochemical Assembly of C(sp2)–S Substituted Imidazoles via Exciplex Formation","authors":"Illán Tagarro,&nbsp;Helena F. Piedra,&nbsp;Daniel González-Pinardo,&nbsp;Israel Fernández,&nbsp;Irene Bosque,&nbsp;Manuel Plaza","doi":"10.1021/acsorginorgau.6c00004","DOIUrl":"10.1021/acsorginorgau.6c00004","url":null,"abstract":"<p>We report a visible-light-driven multicomponent strategyfor thesynthesis of <em>S</em>-functionalized imidazoles from readilyavailable organic halides, isothiocyanates, and isocyanides. The methodoperates under mild, photocatalyst-free conditions and exhibits broadsubstrate scope with excellent functional-group tolerance. Detailedmechanistic investigations support a reaction pathway involving directphotoexcitation of in situ generated thiophenolate intermediates andsubsequent radical-based C–S bond formation. This process islikely governed by exciplex-type interactions rather than preassembledelectron donor–acceptor complexes. Overall, this work introducesa distinct photochemical activation mode for C–S bond constructionand expands the synthetic toolbox for accessing sulfur-containingheterocycles.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"6 3","pages":"337–345"},"PeriodicalIF":5.2,"publicationDate":"2026-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148200097","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Electrochemical N-Propargylation of N-Heterocycles via Decarboxylation of Allenoic Acids","authors":"Sarah Abdoun,&nbsp;Christophe Bour,&nbsp;Robert J. Mayer,&nbsp;Marie Vayer","doi":"10.1021/acsorginorgau.5c00117","DOIUrl":"10.1021/acsorginorgau.5c00117","url":null,"abstract":"<p>Broadly applicableand selective C–N bond formation remainsa cornerstone challenge in organic synthesis. Although electrochemicalmethods have recently emerged as an efficient way for achieving decarboxylativeC–N coupling, transforming allenoic acids into N-functionalizedproducts remains elusive. Herein, we report the development of anelectrochemical strategy for the decarboxylative <em>N</em>-propargylation of <em>N</em>-heterocycles using readilyavailable 2,3-allenoic acids. By correlating the oxidation potentialsof allenoic acids and nucleophilic coupling partners, we derived predictivecriteria for anticipating reaction efficiency across a broad substratescope. Mechanistic studies (cyclic voltammetry, in situ infrared (IR)kinetics, and density functional theory (DFT) calculations) supporta two-step sequence involving oxidative decarboxylation to an allenylradical rapidly oxidized to a highly electrophilic allenyl/propargylcation and regioselective heterocycle attack yielding N-propargylatedproducts. This work showcases a straightforward method for accessingreactive allenyl cation intermediates and expands the toolkit forsustainable electrosynthetic C–N bond formation.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"6 3","pages":"314–324"},"PeriodicalIF":5.2,"publicationDate":"2026-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148200111","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Computational and Chemical Analysis of the Oxygen Atom Transfer Process of a Dioxo–Molybdenum Complex Incorporated into a Modified UiO-67 (Zr/Ti)","authors":"Laura Milena Valdivieso Zárate,&nbsp;Ernesto David González Cruz,&nbsp;Kerry Jeffry Wrighton-Araneda,&nbsp;Katherine Paredes-Gil,&nbsp;David Contreras,&nbsp;Fernando Martínez Ortega","doi":"10.1021/acsorginorgau.5c00097","DOIUrl":"10.1021/acsorginorgau.5c00097","url":null,"abstract":"<p>In the present work, a combined theoretical–experimentalapproach was employed to elucidate the structure of a modified UiO-67(Zr/Ti) MOF functionalized with MoO₂Cl₂ througha three-step process and to propose a detailed mechanism for the oxygenatom transfer reaction. Experimental characterization techniques (X-raydiffraction, X-ray photoelectron spectroscopy, and electron paramagneticresonance (EPR)) were integrated with periodic and cluster-based densityfunctional theory calculations to validate the synthesis and to modelthe catalytic behavior. EPR data confirmed the formation of Mo^(V) species during the catalytic cycle, supporting the intermediatesproposed by theoretical studies. This synergistic strategy enableda deep understanding of both the synthesis process and the catalyst’sfunction, demonstrating how theory-guided design and experimentalvalidation can drive the development of next-generation MOFs withtunable reactivity and scalable application potential.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"6 3","pages":"288–302"},"PeriodicalIF":5.2,"publicationDate":"2026-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148200134","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Site-Selective C–H Functionalization on Coumarins Directed by Manganese: Mechanistic Insights from Time-Resolved Spectroscopy and Catalytic Development","authors":"Thomas J. Burden,&nbsp;Jonathan B. Eastwood,&nbsp;Emily A. Thompson,&nbsp;Matteo Albino,&nbsp;Ian P. Clark,&nbsp;Adrian C. Whitwood,&nbsp;Jean-Philippe Krieger,&nbsp;Matthew J. Harper,&nbsp;Huw T. Jenkins,&nbsp;Ian J. S. Fairlamb,&nbsp;Jason M. Lynam","doi":"10.1021/acsorginorgau.6c00003","DOIUrl":"10.1021/acsorginorgau.6c00003","url":null,"abstract":"<p>Mn-catalyzed C–H bond functionalization offersgreat potentialin the synthesis of highly functionalized aromatic and heteroaromaticcompounds, involving the intermediacy of manganacycles and their interceptionthrough reactions with appropriate acceptor compounds. The coumarinmotif is widely embedded in an eclectic array of compounds possessinginteresting biological and photophysical properties. In this study,we examined the effect of changing the position of a manganese 2-pyridyl-directinggroup from C3 to C4 on a coumarin moiety, directing C4–H functionalizationor C3–H functionalization, respectively. The reactions of cyclomanganatedintermediates with phenylacetylene have been studied using time-resolvedinfrared spectroscopic methods on a pico- to microsecond time scale,unraveling the bond-forming processes that underpin the differingsite C–H bond functionalizations. The findings facilitatedthe development of a catalytic methodology for the C3-alkenylationof a 4-(2-pyridyl)coumarin using phenylacetylene.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"6 3","pages":"325–336"},"PeriodicalIF":5.2,"publicationDate":"2026-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148200228","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Revisiting the Crystal Structure of Metal–Organic Framework UTSA-16 for Chemical Consistency","authors":"Giulio Bresciani,&nbsp;Marco Taddei","doi":"10.1021/acsorginorgau.6c00018","DOIUrl":"10.1021/acsorginorgau.6c00018","url":null,"abstract":"<p>The metal–organic framework UTSA-16, based onK⁺, Co²⁺, and citrate as the organic linkerand first reportedin 2005, is one of the most attractive candidates as a solid adsorbentfor postcombustion CO₂ capture. Here, we revisit the crystalstructure of UTSA-16 on the basis of clear evidence that the amountof potassium has been systematically underestimated in previous literaturereports dealing with crystallographic characterization. By combiningCHN elemental analysis, inductively coupled plasma optical emissionspectroscopy, and thermogravimetric analysis, we find that the actualchemical formula for UTSA-16 is K₂Co₃(cit)₂·8H₂O, with a K/Co ratio twice as large asthe one assumed in previous literature. Single crystal X-ray diffractionanalysis leads to identifying two extraframework positions occupiedby previously overlooked K⁺ ions, which are likely to playa key role in the adsorption behavior of UTSA-16.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"6 3","pages":"277–281"},"PeriodicalIF":5.2,"publicationDate":"2026-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148200276","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"pH-Driven Hydrothermal Synthesis of Leiteite ZnAs2O4: Structure, Characterization, and Multifunctional Applications including Photocatalytic Dye Degradation, Catalytic Organic Transformation, and Antibacterial and Antioxidant Properties","authors":"Bibaswan Sen,&nbsp;Sayantani Paul,&nbsp;Ankita Banik,&nbsp;Nilendu Basak,&nbsp;Nityananda Dutta,&nbsp;Nayim Sepay,&nbsp;Uttam Das,&nbsp;Ekramul Islam,&nbsp;Sk Imran Ali","doi":"10.1021/acsorginorgau.6c00025","DOIUrl":"10.1021/acsorginorgau.6c00025","url":null,"abstract":"<p>The leiteite ZnAs₂O₄ mineral hasbeen successfullysynthesized in the laboratory by a pH-assisted hydrothermal technique,as discovered previously from the Tsumeb mine, Oshikoto, Namibia.The as-synthesized material has been developed as an efficient heterogeneousphotocatalyst toward methylene blue dye degradation and catalyst towardsolvent-free Knoevenagel condensation reaction and also is potenttoward important antimicrobial and antioxidant activities. SCXRD studiesreveal that no phase transition was observed upon lowering the temperatureup to 100 K, as the lattice parameters were found to be <em>a</em> = 4.5318(3) Å, <em>b</em> = 5.0085(3) Å, <em>c</em> = 17.5707(11) Å, β = 90.914(4)°, <em>V</em> = 398.76(4) ų, and SG: <em>P</em>2₁/<em>c</em>, with a slight contraction to thelattice parameters at room temperature. Solid-state DFT was employedto ascertain the nature of the semiconducting material. The chemicalcharacteristics of the material toward MB degradation, radical scavenging,and antibacterial activity are explained by its band characteristicsand partial density of states. Photocatalytic methylene blue dye degradationwas demonstrated, and the rate was enhanced by 2-fold with the additionof 0.1 mL of 6% H₂O₂. The reusability of thecatalyst has also been studied up to the 10^th cycle. Thecatalytic activity was confirmed for the solvent-free Knoevenagelcondensation reaction at moderate temperature, and the activitieswere also compared by varying the numbers of electron-donating andelectron-withdrawing groups. The antibacterial activity on severalGram-negative and Gram-positive pathogens, i.e., <em>Escherichia coli</em>, <em>Enterobacter</em> sp., <em>Bacillus</em> sp., <em>Klebsiella</em> sp., and <em>Pseudomonas</em> sp., was studied. Furthermore, the antioxidant activity was alsoconfirmed experimentally through the DPPH assays.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"6 3","pages":"346–360"},"PeriodicalIF":5.2,"publicationDate":"2026-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148200086","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Continuous-Flow Asymmetric Photocatalysis for the Synthesis of Natural and Unnatural α-Amino Acid Derivatives","authors":"Marcelo Straesser Franco,&nbsp;Rodrigo Costa e Silva,&nbsp;Rafael Alan Carvalho Souza,&nbsp;Eric Yoshitaka Lee,&nbsp;João Marcos Batista Junior,&nbsp;Julio Cezar Pastre","doi":"10.1021/acsorginorgau.6c00024","DOIUrl":"10.1021/acsorginorgau.6c00024","url":null,"abstract":"<p>Enantiomerically enriched α-amino acids and theirderivativesare important building blocks, widely used in the pharmaceutical industry,drug research, and materials science. Therefore, the development ofstraightforward and versatile synthetic methods remains highly desirable.Herein, we disclose a photochemical enantioselective addition of alkylradicals to α-imino esters, mediated by a chiral-at-metal rhodiumcatalyst under continuous flow conditions. This strategy providesrapid and direct access to enantioenriched derivatives of both naturaland unnatural α-amino acids, achieving yields of up to 75% andenantiomeric ratios of up to 1:99.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"6 3","pages":"282–287"},"PeriodicalIF":5.2,"publicationDate":"2026-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148200155","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Pyrene-4,5-dione as a Visible-Light Organic Photocatalyst for Photooxidation, Photoredox, Energy Transfer, and Hydrogen Atom Transfer Reactions","authors":"Rodolfo I. Teixeira,&nbsp;Joseph P. Anslow,&nbsp;Nanci C. de Lucas","doi":"10.1021/acsorginorgau.5c00111","DOIUrl":"10.1021/acsorginorgau.5c00111","url":null,"abstract":"<p>Pyrene-4,5-dione (PQ) is demonstrated to be a metal-free,visible-lightorganic photocatalyst capable of mediating four major photochemicalactivation modes: photooxidation, energy transfer, photoredox, andhydrogen atom transfer (HAT). Under mild conditions using blue LEDs,PQ enables diverse synthetic transformations, including singlet oxygenoxidations, [2 + 2] cycloadditions, C–H fluorination, reductiveC–C bond formation, oxidative hydroxylation of boronic acids,and HAT-driven alkylation. Its performance is comparable to benchmarksystems, while offering the advantages of visible-light absorptionand a greener profile compared to typical metal-complex photocatalysts.PQ can be recovered chromatographically (typically 85–90% massrecovery) with no evidence of structural change or degradation. Further,as a proof-of-concept, the reductive C–C coupling was performedin continuous flow, delivering up to 85% yield at 0.17 mmol h^–1 in a 4 mL reactor and 83% yield at 0.41 mmol h^–1 upon numbering-up to a 10 mL reactor. This work highlightsthe potential of PQ as a practical and versatile photocatalyst forvisible-light-driven organic synthesis.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"6 3","pages":"303–313"},"PeriodicalIF":5.2,"publicationDate":"2026-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148200142","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Exploring the Competition between Halogen Bonding and CH Hydrogen Bonding in Bromoarenes Using an Aryldiyne Template","authors":"Maggie A. Schultz,&nbsp;Elijah T. Randazzo,&nbsp;Rachel A. Stindt,&nbsp;Shannon C. Riha,&nbsp;Joseph D. Scanlon,&nbsp;Eric Bosch,&nbsp;Nathan P. Bowling","doi":"10.1021/acsorginorgau.6c00009","DOIUrl":"10.1021/acsorginorgau.6c00009","url":null,"abstract":"<p>Hydrogens connectedto benzene rings functionalized withelectron-withdrawinggroups are found to provide attractions with electron donors thatare competitive with the halogen bond attraction to bromines on thesame rings. An aryldiyne bridge that adequately templates this CHhydrogen bonding, along with the competing halogen bonding, providesan experimental pathway for looking at these interactions in a systematicway. Calculations using the M06–2<em>x</em>/6–311+G­(2d,p)density functional and basis set, along with mapping of the molecularelectrostatic potentials using B3LYP/6–311++G**, support theexperimental conclusion that CH hydrogen bonding to bromoarenes canbe preferred to halogen bonding due to the greater positive potentialon the surface of the hydrogen compared to that of the bromine. Computationalevidence suggests a preference for the CH hydrogen bond conformerof the templated system regardless of the arrangement of electron-withdrawing(–F or −CF₃) substituents on the haloarenes.At ∼5 kJ/mol or less, the energy differences between CH hydrogenbonding conformers and bromine-based halogen bonding conformers areoften small, however, suggesting that selective crystal design usingeither interaction would be challenging.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"6 2","pages":"248–257"},"PeriodicalIF":5.2,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147623956","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Convergent Synthesis of Tetradentate Aminopyridine C–H Oxidation Catalysts","authors":"Yiheng Lu,&nbsp;Kanstantsin Anisovich,&nbsp;Konrad Tiefenbacher","doi":"10.1021/acsorginorgau.6c00006","DOIUrl":"10.1021/acsorginorgau.6c00006","url":null,"abstract":"<p>Controlling the oxidationof unactivated C­(sp³)–Hbonds through supramolecular catalyst–substrate interactionshas recently enabled site-selective transformations previously consideredinaccessible. However, progress has been hampered by lengthy linearsyntheses of supramolecular catalysts. Here we present a convergentstrategy that directly cross-couples preformed tetradentate aminopyridineligands with recognition motifs, streamlining access to functionalcatalysts. Using this approach, we prepared four catalysts, two featuringresorcin[4]­arene (RS) and two bearing calix[4]­arene (CX) units, forsubstrate recognition using the solvophobic effect in 2,2,2-trifluoroethanol.This convergent synthesis reduces the longest linear sequence from5 steps to 2 steps (starting from the recognition motif) by shiftingfrom a linear, catalyst-specific synthesis to a modular platform thatallows rapid assembly of catalyst libraries using premade, interchangeablebuilding blocks.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"6 2","pages":"202–208"},"PeriodicalIF":5.2,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147623921","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}