Pierre Milcendeau, Mohammed Ramdani, Elsa van Elslande, Xavier Guinchard
{"title":"Cationic Au(I) Complexes of Indoles.","authors":"Pierre Milcendeau, Mohammed Ramdani, Elsa van Elslande, Xavier Guinchard","doi":"10.1021/acsorginorgau.5c00075","DOIUrl":"10.1021/acsorginorgau.5c00075","url":null,"abstract":"<p><p>Cationic Au-(I) complexes of indoles embedding Buchwald phosphine ligands are described. A study combining NMR and X-ray crystallography is described in order to understand the nature of the coordination of the cationic Au atom to the C2-C3 double bond of indoles. Our studies reveal an intermediate coordination between η<sup>2</sup> and η<sup>1</sup>, demonstrated by a strong sp<sup>3</sup> character of the C3 atom and a significant slippage toward the C3 atom of the indole rings.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"5 6","pages":"485-491"},"PeriodicalIF":3.3,"publicationDate":"2025-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12679316/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145701633","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Carmine Volpe, Luca Nicchio, Federica Santoro, Teresa Silvestri, Anna Di Porzio, Camilla Russo, Fabiana Quaglia, Antonio Randazzo, Alfonso Carotenuto, Diego Brancaccio, Stefano Protti, Mariateresa Giustiniano
{"title":"Arylazo Sulfones as 1,3-Dipole Acceptors in the (Photo)-Micellar van Leusen Triazole Synthesis.","authors":"Carmine Volpe, Luca Nicchio, Federica Santoro, Teresa Silvestri, Anna Di Porzio, Camilla Russo, Fabiana Quaglia, Antonio Randazzo, Alfonso Carotenuto, Diego Brancaccio, Stefano Protti, Mariateresa Giustiniano","doi":"10.1021/acsorginorgau.5c00080","DOIUrl":"10.1021/acsorginorgau.5c00080","url":null,"abstract":"<p><p>Arylazo sulfones represent a valuable class of organic compounds, which can be exploited as safer and bench-stable analogues of diazonium salts. Notwithstanding their significant applications in light-triggered reactions as precursors of either diazenyl or aryl radicals, their reactivity as 1,3-dipole acceptors has been poorly investigated. The present manuscript addresses the study of a [3 + 2] cycloaddition reaction between arylazo sulfones and α-acidic isonitriles such as TosMIC and related analogues. Reaction conditions have been optimized in a micellar medium, namely CTAC 2% aq solution, in order to afford sustainable synthetic access to 1,2,4-triazole derivatives, a relevant scaffold in medicinal and material chemistry. The substrate scope has been showcased with 24 examples (24-90% yield) with good functional group tolerability. Worthy of note, solution NMR techniques have been applied to characterize the reaction at the molecular level, providing a groundwork to drive a rational choice of the micellar medium on the basis of the substrates' chemical nature. Moreover, the recyclability of the micellar medium was investigated via dynamic light scattering (DLS) analyses.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"5 6","pages":"539-547"},"PeriodicalIF":3.3,"publicationDate":"2025-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12679303/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145702123","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Dimitra Kyrko, Tingting Cao, Pascal Retailleau, Julia Kaffy, Benoît Crousse
{"title":"Access to <i>N</i>‑Fluorinated Azapeptides and Azapeptoids as Peptidomimetic Scaffolds.","authors":"Dimitra Kyrko, Tingting Cao, Pascal Retailleau, Julia Kaffy, Benoît Crousse","doi":"10.1021/acsorginorgau.5c00073","DOIUrl":"10.1021/acsorginorgau.5c00073","url":null,"abstract":"<p><p>In this study, a diverse range of short azapeptides and azapeptoids incorporating -CH<sub>2</sub>CF<sub>3</sub> or -CH<sub>2</sub>CF<sub>2</sub>H groups was synthesized. The key strategy involved coupling fluorinated hydrazines with amino acids using acyl chloride derivatives or triphosgene activation. Structural and conformational analyses were conducted by using NMR spectroscopy and X-ray diffraction, revealing the impact of these fluorinated moieties on the overall molecular architecture. Crystallographic studies highlighted a preferential type II β-turn conformation with influences from short hydrogen bonding and fluorine-hydrogen interactions.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"5 6","pages":"531-538"},"PeriodicalIF":3.3,"publicationDate":"2025-09-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12679312/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145702165","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Luc A Mauro, Isabelle A Herlinger, Shane J Hall, Russell P Hughes, Roger E Cramer, Lisa A Fredin, David A Vicic
{"title":"Identifying Reactivity Differences of Two-Carbon-Atom-Based Legacy Refrigerants at Group 9 Metal Pincer Complexes.","authors":"Luc A Mauro, Isabelle A Herlinger, Shane J Hall, Russell P Hughes, Roger E Cramer, Lisa A Fredin, David A Vicic","doi":"10.1021/acsorginorgau.5c00071","DOIUrl":"10.1021/acsorginorgau.5c00071","url":null,"abstract":"<p><p>We describe the first comparative data on metal-mediated C-H activation and functionalization reactions at two-carbon-atom legacy refrigerants and density functional theory (DFT) analyses on the resulting organometallic products. We reveal that, depending on the degree of fluorination in the refrigerant, C-H activation could lead either to stable M-(H)-R<sub>f</sub> products or to a M-(fluoroolefin) complex. The first example of a metal-mediated dehydrofluorination of R-143a is described, resulting from a β-fluoride elimination reaction of a putative [Ir-(H)-(CH<sub>2</sub>CF<sub>3</sub>)] intermediate and the loss of hydrogen fluoride. This work also reports the first examples of metal-mediated activation of R-125 (CF<sub>3</sub>-CF<sub>2</sub>H) and R-134a (CF<sub>3</sub>-CFH<sub>2</sub>) where the direct C-H activation products can be observed spectroscopically and, in the case of R-125, structurally characterized. The stability of the [Ir-(H)-(R<sub>f</sub>)] complexes is notable, given that the direct products of C-H activation of nonchelating alkanes at transition metals remains relatively rare. The clean formation of isolable [Ir-(H)-(R<sub>f</sub>)] complexes is expected to facilitate studies of migratory insertion reactions in these species, which bodes well for efforts to repurpose high-global-warming-potential legacy refrigerants. Finally, DFT calculations provide insight into how the degree of fluorination affects CC bond lengths and energies of propellor-like rotations in the coordinated fluoroolefins, the relative free energies of fluoroolefin binding, and the role of observed CH···F contacts in the calculated structures.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"5 6","pages":"518-530"},"PeriodicalIF":3.3,"publicationDate":"2025-08-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12679306/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145701851","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Michał Biedrzycki, Jaime Martín, Alexandre Genoux, Elia Boschi, Cristina Nevado
{"title":"Synthesis of (P^N^C)Gold(III) Complexes via Tandem Oxidative Addition/C-H Auration.","authors":"Michał Biedrzycki, Jaime Martín, Alexandre Genoux, Elia Boschi, Cristina Nevado","doi":"10.1021/acsorginorgau.5c00057","DOIUrl":"10.1021/acsorginorgau.5c00057","url":null,"abstract":"<p><p>A new method for the synthesis of cyclometalated gold-(III) complexes featuring (P^N^C) ligands is reported. This protocol employs a tandem oxidative addition/cycloauration process, enabling the formation of (P^N^C)-gold-(III)-aryl, -alkenyl and -alkynyl derivatives by creating two Au-C bonds in one pot from a structurally diverse range of C-(sp<sup>2</sup>)- and C-(sp)-iodide substrates. Additionally, a complementary two-step method was developed to access (P^N^C)-gold-(III)-alkynyl complexes, which exhibit emission in the blue and green light regions.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"5 5","pages":"322-327"},"PeriodicalIF":3.3,"publicationDate":"2025-08-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12492041/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145233481","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Mariam Abd El Sater, Floriane René, Nicolas Blanchard, Jorge Juan Cabrera-Trujillo, Karinne Miqueu* and Vincent Bizet*,
{"title":"","authors":"Mariam Abd El Sater, Floriane René, Nicolas Blanchard, Jorge Juan Cabrera-Trujillo, Karinne Miqueu* and Vincent Bizet*, ","doi":"","DOIUrl":"","url":null,"abstract":"","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"5 4","pages":"XXX-XXX XXX-XXX"},"PeriodicalIF":3.3,"publicationDate":"2025-08-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acsorginorgau.5c00042","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144779251","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}