ACS Organic & Inorganic Au最新文献

{"title":"Beyond Traditional Synthesis: Electrochemical Approaches to Amine Oxidation for Nitriles and Imines","authors":"Zhining Xu, Ervin Kovács","doi":"10.1021/acsorginorgau.4c00025","DOIUrl":"https://doi.org/10.1021/acsorginorgau.4c00025","url":null,"abstract":"The electrochemical oxidation of amines to nitriles and imines represents a critical frontier in organic electrochemistry, offering a sustainable pathway to these valuable compounds. Nitriles and amines are pivotal in various industrial applications, including pharmaceuticals, agrochemicals, and materials science. This review encapsulates the recent advancements in the electrooxidation process, emphasizing mechanistic understanding, electrode material innovations, optimization of reaction conditions, and exploration of solvent and electrolyte systems. Additionally, the review addresses the operational parameters that significantly affect the electrooxidation process, such as current density, temperature, and electrode surface, offering insights into their optimization for enhanced performance. By providing a comprehensive view of the current state and prospects of amine electrooxidation to nitriles and imines, this review aims to inspire further development, innovation, and research in this promising area of green chemistry.","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"162 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-06-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141504821","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":"Inverse Photoemission Spectroscopy of Coinage Metal Corroles: Comparison with Solution-Phase Electrochemistry","authors":"Luca Giovanelli*,&nbsp;Younal Ksari,&nbsp;Hela Mrezguia,&nbsp;Eric Salomon,&nbsp;Marco Minissale,&nbsp;Abraham B. Alemayehu and Abhik Ghosh*,&nbsp;","doi":"10.1021/acsorginorgau.4c0002710.1021/acsorginorgau.4c00027","DOIUrl":"https://doi.org/10.1021/acsorginorgau.4c00027https://doi.org/10.1021/acsorginorgau.4c00027","url":null,"abstract":"<p >A combined direct and inverse photoemission study of coinage metal corroles suggests that the latter technique, in favorable cases, can provide some additional information relative to electrochemical measurements. Thus, whereas inverse photoemission spectroscopy (IPES) provides relative electron affinities for electron addition to different unoccupied orbitals, electrochemical reduction potentials shed light on the energetics of <i>successive</i> electron additions. While all three coinage metal triphenylcorrole (TPC) complexes exhibit similar ionization potentials, they exhibit dramatically different inverse photoemission spectra. For Cu[TPC], the lowest-energy IPES feature (0.74 eV) is found to be exceedingly close to the Fermi level; it is significantly higher for Ag[TPC] (1.65 eV) and much higher for Au[TPC] (2.40 eV). These differences qualitatively mirror those observed for electrochemical reduction potentials and are related to a partially metal-centered LUMO in the case of Cu- and Ag[TPC] and a fully corrole-based LUMO in the case of Au[TPC]; the latter orbital corresponds to the LUMO+1 in the case of Ag[TPC].</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"4 5","pages":"485–491 485–491"},"PeriodicalIF":3.3,"publicationDate":"2024-06-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsorginorgau.4c00027","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142402907","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}

{"title":"Inverse Photoemission Spectroscopy of Coinage Metal Corroles: Comparison with Solution-Phase Electrochemistry","authors":"Luca Giovanelli, Younal Ksari, Hela Mrezguia, Eric Salomon, Marco Minissale, Abraham B. Alemayehu, Abhik Ghosh","doi":"10.1021/acsorginorgau.4c00027","DOIUrl":"https://doi.org/10.1021/acsorginorgau.4c00027","url":null,"abstract":"A combined direct and inverse photoemission study of coinage metal corroles suggests that the latter technique, in favorable cases, can provide some additional information relative to electrochemical measurements. Thus, whereas inverse photoemission spectroscopy (IPES) provides relative electron affinities for electron addition to different unoccupied orbitals, electrochemical reduction potentials shed light on the energetics of <i>successive</i> electron additions. While all three coinage metal triphenylcorrole (TPC) complexes exhibit similar ionization potentials, they exhibit dramatically different inverse photoemission spectra. For Cu[TPC], the lowest-energy IPES feature (0.74 eV) is found to be exceedingly close to the Fermi level; it is significantly higher for Ag[TPC] (1.65 eV) and much higher for Au[TPC] (2.40 eV). These differences qualitatively mirror those observed for electrochemical reduction potentials and are related to a partially metal-centered LUMO in the case of Cu- and Ag[TPC] and a fully corrole-based LUMO in the case of Au[TPC]; the latter orbital corresponds to the LUMO+1 in the case of Ag[TPC].","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"57 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-06-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141504822","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":"Unique Reactivity of Triazolyl Diazoacetates under Photochemical Conditions","authors":"Marzena Wosińska-Hrydczuk,&nbsp;Mohadese Yaghoobi Anzabi,&nbsp;Jakub Przeździecki,&nbsp;Oksana Danylyuk,&nbsp;Wojciech Chaładaj* and Dorota Gryko*,&nbsp;","doi":"10.1021/acsorginorgau.4c0001910.1021/acsorginorgau.4c00019","DOIUrl":"https://doi.org/10.1021/acsorginorgau.4c00019https://doi.org/10.1021/acsorginorgau.4c00019","url":null,"abstract":"<p >Under light irradiation, aryldiazo acetates can generate either singlet or triplet carbenes depending on the reaction conditions, but heteroaryl diazo compounds have remained underexplored in this context. Herein, we found that triazolyl diazoacetates exhibit higher reactivity than their aryl counterparts. They even react with dichloromethane (DCM), a common, inert solvent, for photoreactions involving diazo reagents, giving halogenated products. Theoretical studies show that all reactions involve carbenes but progress via different pathways depending on the solvent used.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"4 4","pages":"418–423 418–423"},"PeriodicalIF":3.3,"publicationDate":"2024-06-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsorginorgau.4c00019","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141959063","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}

{"title":"Direct Organocatalytic Chemoselective Synthesis of Pharmaceutically Active 1,2,3-Triazoles and 4,5′-Bitriazoles","authors":"Badaraita Gorachand,&nbsp;Gundam Surendra Reddy and Dhevalapally B. Ramachary*,&nbsp;","doi":"10.1021/acsorginorgau.4c0003210.1021/acsorginorgau.4c00032","DOIUrl":"https://doi.org/10.1021/acsorginorgau.4c00032https://doi.org/10.1021/acsorginorgau.4c00032","url":null,"abstract":"<p >Carbonyl-containing 1,4,5-trisubstituted- and 1,4-disubstituted-1,2,3-triazoles are well-known for their wide range of applications in pharmaceutical and medicinal chemistry, but their high-yielding metal-free synthesis has always remained challenging, as no comprehensive protocol has been outlined to date. Owing to their structural and medicinal importance, herein, we synthesized various carbonyl-containing 1,4,5-trisubstituted- and 1,4-disubstituted-1,2,3-triazoles and unsymmetrical 4,5′-bitriazoles with high yields and chemo-/regioselectivity from the library of 2,4-diketoesters and azides in a sequential one-pot manner through the combination of organocatalytic enolization, in situ [3 + 2]-cycloaddition, and hydrolysis reactions. The commercial availability of the starting materials/catalysts, diverse substrate scope, performance in a one-pot manner, chemo-/regioselectivity of organo-click reaction, quick synthesis of unsymmetrical 4,5′-bitriazoles, a large number of synthetic applications, and numerous medicinal applications of carbonyl-containing 1,2,3-triazoles are the key attractions of this metal-free organo-click work.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"4 5","pages":"534–544 534–544"},"PeriodicalIF":3.3,"publicationDate":"2024-06-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsorginorgau.4c00032","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142402780","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}

{"title":"Fluorescence Labeling of Peptides: Finding the Optimal Protocol for Coupling Various Dyes to ATCUN-like Structures","authors":"Jordi C. J. Hintzen,&nbsp;Shitanshu Devrani,&nbsp;Andrew J. Carrod,&nbsp;M. Bahadir Bayik,&nbsp;Daniel Tietze and Alesia A. Tietze*,&nbsp;","doi":"10.1021/acsorginorgau.4c0003010.1021/acsorginorgau.4c00030","DOIUrl":"https://doi.org/10.1021/acsorginorgau.4c00030https://doi.org/10.1021/acsorginorgau.4c00030","url":null,"abstract":"<p >Labeling of peptides and proteins with fluorescent dyes is a key step in functionalizing these structures for a wide array of biological assays. However, coupling strategies of such dyes have not been optimized for the most common compounds, while this step is typically the most precious and costly of the whole synthesis. We searched for the best conditions for attachment of the most widely used fluorescent dyes such as 6-carboxyfluorescein, Rhodamine B, and BODIPY-FL to peptides, where amino terminal Cu(II) and Ni(II) binding site (ATCUN) peptides were used as a model system. Surprisingly, conventional methods of dye attachment proved to not be satisfactory and yielded poor efficiency results. We have discovered that when labeling primary amines on peptides, the uncommon synthesis of activated pentafluorophenol (PFP) esters is the most efficient strategy, expedited by microwave irradiation. Coupling to secondary amines is achieved most efficiently through conventional coupling reagents such as HATU and PyBOP. Furthermore, we have employed our fluorescently labeled ATCUN peptides in studies for Cu(II) and Ni(II) sensing, showing that changing the fluorophore does not significantly affect the fluorescence quenching process and discovering the optimal linker length between the ATCUN core and the dye, expanding the repertoire of fluorophores that can be used in this application.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"4 5","pages":"517–525 517–525"},"PeriodicalIF":3.3,"publicationDate":"2024-06-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsorginorgau.4c00030","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142402779","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}

{"title":"Bioinspired Binding and Conversion of Linear Monoterpenes by Polyaromatic Coordination Capsules","authors":"Ryuki Sumida,&nbsp;Lorenzo Catti and Michito Yoshizawa*,&nbsp;","doi":"10.1021/acsorginorgau.4c0001310.1021/acsorginorgau.4c00013","DOIUrl":"https://doi.org/10.1021/acsorginorgau.4c00013https://doi.org/10.1021/acsorginorgau.4c00013","url":null,"abstract":"<p >Linear monoterpenes, versatile reaction biosubstrates, are bound and subsequently converted to various cyclic monomers and oligomers with excellent selectivity and efficiency, <i>only</i> in natural enzymes. We herein report bioinspired functions of synthetic polyaromatic cavities toward linear monoterpenes in the solution and solid states. The cavities are provided by polyaromatic coordination capsules, formed by the assembly of Pt(II) ions and bent bispyridine ligands with two anthracene panels. By using the capsule cavities, the selective binding of citronellal from mixtures with other monoterpenes and its preferential vapor binding over its derivatives are demonstrated in water and in the solid state, respectively. The capsule furthermore extracts <i>p</i>-menthane-3,8-diol, with high product- and stereoselectivity, from a reaction mixture obtained by the acid-catalyzed cyclization of citronellal in water. Thanks to the inner and outer polyaromatic cavities, the catalytic cyclization-dimerization of vaporized citronellal efficiently proceeds in the acid-loaded capsule solid and product/stereoselectively affords <i>p</i>-menthane-3,8-diol citronellal acetal (∼330% yield based on the capsule) under ambient conditions. The solid capsule reactor can be reused at least 5 times with enhanced conversion. The present study opens up a new approach toward mimicking terpene biosynthesis via synthetic polyaromatic cavities.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"4 4","pages":"410–417 410–417"},"PeriodicalIF":3.3,"publicationDate":"2024-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsorginorgau.4c00013","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141959334","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}

{"title":"Parallel Minisci Reaction of gem-Difluorocycloalkyl Building Blocks","authors":"Serhii Holovach,&nbsp;Illia Poroshyn,&nbsp;Kostiantyn P. Melnykov,&nbsp;Oleksandr S. Liashuk,&nbsp;Olena O. Pariiska,&nbsp;Sergey V. Kolotilov,&nbsp;Alexander B. Rozhenko,&nbsp;Dmytro M. Volochnyuk and Oleksandr O. Grygorenko*,&nbsp;","doi":"10.1021/acsorginorgau.4c0002810.1021/acsorginorgau.4c00028","DOIUrl":"https://doi.org/10.1021/acsorginorgau.4c00028https://doi.org/10.1021/acsorginorgau.4c00028","url":null,"abstract":"<p >Parallel Minisci reactions of nonfluorinated and <i>gem</i>-difluorinated C₄–C₇ cycloalkyl building blocks (trifluoroborates and carboxylic acids) with a series of electron-deficient heterocycles were studied. A comparison of the reaction’s outcome revealed better product yields in the case of carboxylic acids as the radical precursors in most cases, albeit these reagents were used with three-fold excess under optimized conditions. The nature of the heterocyclic core was found to be important for successful incorporation of the cycloalkyl fragment. The impact of the CF₂ moiety on the oxidation potential of fluorinated cycloalkyl trifluoroborates and the reaction outcome, in general, was also evaluated.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"4 4","pages":"424–431 424–431"},"PeriodicalIF":3.3,"publicationDate":"2024-05-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsorginorgau.4c00028","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141959333","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}

{"title":"Perspective on the Development of Monomer Recovery Technologies from Plastics Designed to Last","authors":"Steffan K. Kristensen,&nbsp;Alexander Ahrens,&nbsp;Bjarke S. Donslund and Troels Skrydstrup,&nbsp;","doi":"10.1021/acsorginorgau.4c0000910.1021/acsorginorgau.4c00009","DOIUrl":"https://doi.org/10.1021/acsorginorgau.4c00009https://doi.org/10.1021/acsorginorgau.4c00009","url":null,"abstract":"<p >In order to prevent the current unsustainable waste handling of the enormous volumes of end-of-use organic polymer material sent to landfilling or incineration, extensive research efforts have been devoted toward the development of appropriate solutions for the recycling of commercial thermoset polymers. The inability of such cross-linked polymers to be remelted once cured implies that mechanical recycling processes used for thermoplastic materials do not translate to the recycling of thermoset polymers. Moreover, the structural diversity within the materials from the use of different monomers as well as the use of such polymers for the fabrication of fiber-reinforced polymer composites make recycling of these materials highly challenging. In this Perspective, depolymerization strategies for thermoset polymers are discussed with an emphasis on recent advancements within our group on recovering polymer building blocks from polyurethane (PU) and epoxy-based materials. While these two represent the largest thermoset polymer groups with respect to the production volumes, the recycling landscapes for these classes of materials are vastly different. For PU, increased collaboration between academia and industry has resulted in major advancements within solvolysis, acidolysis, aminolysis, and split-phase glycolysis for polyol recovery, where several processes are being evaluated for further scaling studies. For epoxy-based materials, the molecular skeleton has no obvious target for chemical scission. Nevertheless, we have recently demonstrated the possibility of the disassembly of the epoxy polymer in fiber-reinforced composites for bisphenol A (BPA) recovery through catalytic C–O bond cleavage. Furthermore, a base promoted cleavage developed by us and others shows tremendous potential for the recovery of BPA from epoxy polymers. Further efforts are still required for evaluating the suitability of such monomer recovery strategies for epoxy materials at an industrial scale. Nonetheless, recent advancements as illustrated with the presented chemistry suggest that the future of thermoset polymer recycling could include processes that emphasize monomer recovery in an energy efficient manner for closed-loop recycling.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"4 4","pages":"373–386 373–386"},"PeriodicalIF":3.3,"publicationDate":"2024-05-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsorginorgau.4c00009","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141957246","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}

{"title":"Perspective on the Development of Monomer Recovery Technologies from Plastics Designed to Last","authors":"Steffan K. Kristensen, Alexander Ahrens, Bjarke S. Donslund, Troels Skrydstrup","doi":"10.1021/acsorginorgau.4c00009","DOIUrl":"https://doi.org/10.1021/acsorginorgau.4c00009","url":null,"abstract":"In order to prevent the current unsustainable waste handling of the enormous volumes of end-of-use organic polymer material sent to landfilling or incineration, extensive research efforts have been devoted toward the development of appropriate solutions for the recycling of commercial thermoset polymers. The inability of such cross-linked polymers to be remelted once cured implies that mechanical recycling processes used for thermoplastic materials do not translate to the recycling of thermoset polymers. Moreover, the structural diversity within the materials from the use of different monomers as well as the use of such polymers for the fabrication of fiber-reinforced polymer composites make recycling of these materials highly challenging. In this Perspective, depolymerization strategies for thermoset polymers are discussed with an emphasis on recent advancements within our group on recovering polymer building blocks from polyurethane (PU) and epoxy-based materials. While these two represent the largest thermoset polymer groups with respect to the production volumes, the recycling landscapes for these classes of materials are vastly different. For PU, increased collaboration between academia and industry has resulted in major advancements within solvolysis, acidolysis, aminolysis, and split-phase glycolysis for polyol recovery, where several processes are being evaluated for further scaling studies. For epoxy-based materials, the molecular skeleton has no obvious target for chemical scission. Nevertheless, we have recently demonstrated the possibility of the disassembly of the epoxy polymer in fiber-reinforced composites for bisphenol A (BPA) recovery through catalytic C–O bond cleavage. Furthermore, a base promoted cleavage developed by us and others shows tremendous potential for the recovery of BPA from epoxy polymers. Further efforts are still required for evaluating the suitability of such monomer recovery strategies for epoxy materials at an industrial scale. Nonetheless, recent advancements as illustrated with the presented chemistry suggest that the future of thermoset polymer recycling could include processes that emphasize monomer recovery in an energy efficient manner for closed-loop recycling.","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"149 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-05-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140887135","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}