ACS Organic & Inorganic Au最新文献_第7页

Diversification of Bipyridines and Azaheterocycles via Nucleophilic Displacement of Trimethylammoniums 通过三甲基铵的亲核置换实现联吡啶和氮杂环的多样化

IF 3.3

ACS Organic & Inorganic Au Pub Date : 2024-07-17 DOI: 10.1021/acsorginorgau.4c0003110.1021/acsorginorgau.4c00031

Jenny Y. Yang, and , Ryan P. King*,

引用次数: 0

Diversification of Bipyridines and Azaheterocycles via Nucleophilic Displacement of Trimethylammoniums 通过三甲基铵的亲核置换实现联吡啶和氮杂环的多样化

ACS Organic & Inorganic Au Pub Date : 2024-07-17 DOI: 10.1021/acsorginorgau.4c00031

Jenny Y. Yang, Ryan P. King

引用次数: 0

Controlling Redox and Wirelike Charge-Delocalization Properties of Dinuclear Mixed-Valence Complexes with MCp*(dppe) (M = Fe, Ru) Termini Bridged by Metalloporphyrin Linkers 控制具有金属卟啉连接体桥接的 MCp*(dppe)（M = Fe、Ru）双核混合价配合物的氧化还原和线状电荷迁移特性

IF 3.3

ACS Organic & Inorganic Au Pub Date : 2024-07-15 DOI: 10.1021/acsorginorgau.4c0002110.1021/acsorginorgau.4c00021

Masahito Murai, Masanori Ono, Yuya Tanaka and Munetaka Akita*,

{"title":"Controlling Redox and Wirelike Charge-Delocalization Properties of Dinuclear Mixed-Valence Complexes with MCp*(dppe) (M = Fe, Ru) Termini Bridged by Metalloporphyrin Linkers","authors":"Masahito Murai, Masanori Ono, Yuya Tanaka and Munetaka Akita*, ","doi":"10.1021/acsorginorgau.4c0002110.1021/acsorginorgau.4c00021","DOIUrl":"https://doi.org/10.1021/acsorginorgau.4c00021https://doi.org/10.1021/acsorginorgau.4c00021","url":null,"abstract":"Four dinuclear organometallic molecular wire complexes with diethynylmetalloporphyrin linkers 1MM’, [5,15-bis{MCp*(dppe)ethynyl}-10,20-diarylporphinato]M’ (Cp* = η5-C5Me5; dppe = 1,2-bis(diphenylphosphino)ethane; M/M’ = Fe/Zn (1FeZn), Ru/Zn (1RuZn), Fe/Ni (1FeNi), Ru/Ni (1RuNi); aryl = 3,5-di-tert-butylphenyl), are synthesized and characterized by NMR, CV, UV–vis-NIR, and ESI-TOF mass spectrometry techniques. Electrochemical investigations combined with electronic absorption spectroscopic studies reveal strong interactions among the electron-donating, redox-active MCp*(dppe) termini and the metalloporphyrin moieties. The monocationic species of the four complexes obtained by chemical oxidation have been characterized as mixed-valence Class II/III or Class III compounds according to the Robin-Day classification despite the long molecular dimension (>1.5 nm), as demonstrated by their intense intervalence charge transfer bands (IVCT) in the near IR region. DFT calculations indicate large spin densities on the metalloporphyrin moieties. Furthermore, the wirelike performance can be finely tuned by coordination of appropriate nitrogen donors to the axial sites of the metalloporphyrin.","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"4 5","pages":"504–516 504–516"},"PeriodicalIF":3.3,"publicationDate":"2024-07-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsorginorgau.4c00021","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142403029","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}

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Beyond Traditional Synthesis: Electrochemical Approaches to Amine Oxidation for Nitriles and Imines 超越传统合成：腈和胺的胺氧化电化学方法

IF 3.3

ACS Organic & Inorganic Au Pub Date : 2024-06-21 DOI: 10.1021/acsorginorgau.4c0002510.1021/acsorginorgau.4c00025

Zhining Xu, and , Ervin Kovács*,

{"title":"Beyond Traditional Synthesis: Electrochemical Approaches to Amine Oxidation for Nitriles and Imines","authors":"Zhining Xu,  and , Ervin Kovács*, ","doi":"10.1021/acsorginorgau.4c0002510.1021/acsorginorgau.4c00025","DOIUrl":"https://doi.org/10.1021/acsorginorgau.4c00025https://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":"4 5","pages":"471–484 471–484"},"PeriodicalIF":3.3,"publicationDate":"2024-06-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsorginorgau.4c00025","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142402775","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}

引用次数: 0

Beyond Traditional Synthesis: Electrochemical Approaches to Amine Oxidation for Nitriles and Imines 超越传统合成：腈和胺的胺氧化电化学方法

ACS Organic & Inorganic Au Pub Date : 2024-06-21 DOI: 10.1021/acsorginorgau.4c00025

Zhining Xu, Ervin Kovács

引用次数: 0

Inverse Photoemission Spectroscopy of Coinage Metal Corroles: Comparison with Solution-Phase Electrochemistry 硬币金属腐蚀的反向光发射光谱学：与溶液相电化学的比较

IF 3.3

ACS Organic & Inorganic Au Pub Date : 2024-06-19 DOI: 10.1021/acsorginorgau.4c0002710.1021/acsorginorgau.4c00027

Luca Giovanelli*, Younal Ksari, Hela Mrezguia, Eric Salomon, Marco Minissale, Abraham B. Alemayehu and Abhik Ghosh*,

{"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 and Abhik Ghosh*, ","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":"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 successive 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":"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}

引用次数: 0

Inverse Photoemission Spectroscopy of Coinage Metal Corroles: Comparison with Solution-Phase Electrochemistry 硬币金属腐蚀的反向光发射光谱学：与溶液相电化学的比较

ACS Organic & Inorganic Au Pub Date : 2024-06-19 DOI: 10.1021/acsorginorgau.4c00027

Luca Giovanelli, Younal Ksari, Hela Mrezguia, Eric Salomon, Marco Minissale, Abraham B. Alemayehu, Abhik Ghosh

{"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 successive 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}

引用次数: 0

Unique Reactivity of Triazolyl Diazoacetates under Photochemical Conditions 三唑基重氮乙酸酯在光化学条件下的独特反应活性

IF 3.3

ACS Organic & Inorganic Au Pub Date : 2024-06-12 DOI: 10.1021/acsorginorgau.4c0001910.1021/acsorginorgau.4c00019

Marzena Wosińska-Hrydczuk, Mohadese Yaghoobi Anzabi, Jakub Przeździecki, Oksana Danylyuk, Wojciech Chaładaj* and Dorota Gryko*,

引用次数: 0

Direct Organocatalytic Chemoselective Synthesis of Pharmaceutically Active 1,2,3-Triazoles and 4,5′-Bitriazoles 直接有机催化化学选择性合成具有药用活性的 1,2,3-三唑和 4,5′-三氮唑

IF 3.3

ACS Organic & Inorganic Au Pub Date : 2024-06-05 DOI: 10.1021/acsorginorgau.4c0003210.1021/acsorginorgau.4c00032

Badaraita Gorachand, Gundam Surendra Reddy and Dhevalapally B. Ramachary*,

{"title":"Direct Organocatalytic Chemoselective Synthesis of Pharmaceutically Active 1,2,3-Triazoles and 4,5′-Bitriazoles","authors":"Badaraita Gorachand, Gundam Surendra Reddy and Dhevalapally B. Ramachary*, ","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":"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.","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}

引用次数: 0

Fluorescence Labeling of Peptides: Finding the Optimal Protocol for Coupling Various Dyes to ATCUN-like Structures 多肽的荧光标记：寻找将各种染料与 ATCUN 类结构耦合的最佳方案

IF 3.3

ACS Organic & Inorganic Au Pub Date : 2024-06-04 DOI: 10.1021/acsorginorgau.4c0003010.1021/acsorginorgau.4c00030

Jordi C. J. Hintzen, Shitanshu Devrani, Andrew J. Carrod, M. Bahadir Bayik, Daniel Tietze and Alesia A. Tietze*,

{"title":"Fluorescence Labeling of Peptides: Finding the Optimal Protocol for Coupling Various Dyes to ATCUN-like Structures","authors":"Jordi C. J. Hintzen, Shitanshu Devrani, Andrew J. Carrod, M. Bahadir Bayik, Daniel Tietze and Alesia A. Tietze*, ","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":"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.","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}

引用次数: 0