ACS Organic & Inorganic Au最新文献

{"title":"Strategic Synthesis of Sulfinamides as Versatile S(IV) Intermediates","authors":"Subham Das,&nbsp;Amit Dhibar and Basudev Sahoo*,&nbsp;","doi":"10.1021/acsorginorgau.4c0007810.1021/acsorginorgau.4c00078","DOIUrl":"https://doi.org/10.1021/acsorginorgau.4c00078https://doi.org/10.1021/acsorginorgau.4c00078","url":null,"abstract":"<p >Sulfinamides constitute adaptable S(IV) intermediates with a sulfur stereocenter, having emerging interest in divergent synthesis of high-valent S(VI) functional bioisosteres. Recent years have witnessed the strategic development of mild and selective synthetic routes for highly functionalized sulfinamides, employing stable organometallic reagents, carbon-centered radical precursors, and other abundant coupling partners merged with various sulfur reagents in the arena of metal, photoredox, and organocatalysis. Furthermore, asymmetric metal and organocatalysis have enabled the stereoselective synthesis of enantioenriched sulfinamides. In this Perspective, we present the recent (2021 to present) advancement of various synthetic methods toward sulfinamides.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"5 1","pages":"1–12 1–12"},"PeriodicalIF":3.3,"publicationDate":"2024-11-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsorginorgau.4c00078","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143127449","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":"Strategic Synthesis of Sulfinamides as Versatile S(IV) Intermediates.","authors":"Subham Das, Amit Dhibar, Basudev Sahoo","doi":"10.1021/acsorginorgau.4c00078","DOIUrl":"10.1021/acsorginorgau.4c00078","url":null,"abstract":"<p><p>Sulfinamides constitute adaptable S(IV) intermediates with a sulfur stereocenter, having emerging interest in divergent synthesis of high-valent S(VI) functional bioisosteres. Recent years have witnessed the strategic development of mild and selective synthetic routes for highly functionalized sulfinamides, employing stable organometallic reagents, carbon-centered radical precursors, and other abundant coupling partners merged with various sulfur reagents in the arena of metal, photoredox, and organocatalysis. Furthermore, asymmetric metal and organocatalysis have enabled the stereoselective synthesis of enantioenriched sulfinamides. In this Perspective, we present the recent (2021 to present) advancement of various synthetic methods toward sulfinamides.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"5 1","pages":"1-12"},"PeriodicalIF":3.3,"publicationDate":"2024-11-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11803471/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143383468","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":"Effects of Hydrogen Bonding Solvation by Diverse Fluorinated Bulky Alcohols on the Reaction Rate and Selectivity in Crown Ether Mediated Nucleophilic Fluorination in an Aprotic Solvent","authors":"Eloah P. Ávila,&nbsp;Mauro V. de Almeida,&nbsp;Marcelo S. Valle and Josefredo R. Pliego*,&nbsp;","doi":"10.1021/acsorginorgau.4c0008110.1021/acsorginorgau.4c00081","DOIUrl":"https://doi.org/10.1021/acsorginorgau.4c00081https://doi.org/10.1021/acsorginorgau.4c00081","url":null,"abstract":"<p >Solvent effects play a critical role in ionic chemical reactions and have been a research topic for a long time. The solvent molecules in the first solvation shell of the solute are the most important solvating species. Consequently, manipulation of the structure of this shell can be used to control the reactivity and selectivity of ionic reactions. In this work, we report extensive experimental and insightful computational studies of the effects of adding diverse fluorinated bulky alcohols with different solvation abilities to the fluorination reaction of alkyl bromides with potassium fluoride promoted by 18-crown-6. We found that adding a stoichiometric amount of these alcohols to the acetonitrile solution has an important effect on the kinetics and selectivity. The most effective alcohol was 2-trifluoromethyl-2-propanol (TBOH-F3), and the use of 3 equiv of this alcohol to fluorinate a primary alkyl bromide led to a 78% fluorination yield in just 6 h of reaction time at a mild temperature of 82 °C, with 8% of E2 yield. The more challenging secondary alkyl bromide substrate obtained 44% fluorination yield and 56% E2 yield at 18 h of reaction time. More fluorinated alcohols with six or more fluorine atoms have resulted in relatively acidic alcohols, leading to large amounts of the corresponding ethers of these alcohols as side products. The widely used hexafluoroisopropanol (HFIP) was the least effective one for monofluorination, indicating that both acidity and bulkiness are important features of the alcohols for promoting fluorination using KF salt. Nevertheless, the ether of HFIP can be easily formed with the substrate, generating a highly fluorinated ether product. Theoretical calculations predict Δ<i>G</i>^‡ in close agreement with the experiments and explain the higher selectivity induced by the fluorinated bulky alcohols in relation to the use of crown ether alone.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"5 1","pages":"69–83 69–83"},"PeriodicalIF":3.3,"publicationDate":"2024-11-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsorginorgau.4c00081","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143127476","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":"Effects of Hydrogen Bonding Solvation by Diverse Fluorinated Bulky Alcohols on the Reaction Rate and Selectivity in Crown Ether Mediated Nucleophilic Fluorination in an Aprotic Solvent.","authors":"Eloah P Ávila, Mauro V de Almeida, Marcelo S Valle, Josefredo R Pliego","doi":"10.1021/acsorginorgau.4c00081","DOIUrl":"10.1021/acsorginorgau.4c00081","url":null,"abstract":"<p><p>Solvent effects play a critical role in ionic chemical reactions and have been a research topic for a long time. The solvent molecules in the first solvation shell of the solute are the most important solvating species. Consequently, manipulation of the structure of this shell can be used to control the reactivity and selectivity of ionic reactions. In this work, we report extensive experimental and insightful computational studies of the effects of adding diverse fluorinated bulky alcohols with different solvation abilities to the fluorination reaction of alkyl bromides with potassium fluoride promoted by 18-crown-6. We found that adding a stoichiometric amount of these alcohols to the acetonitrile solution has an important effect on the kinetics and selectivity. The most effective alcohol was 2-trifluoromethyl-2-propanol (TBOH-F3), and the use of 3 equiv of this alcohol to fluorinate a primary alkyl bromide led to a 78% fluorination yield in just 6 h of reaction time at a mild temperature of 82 °C, with 8% of E2 yield. The more challenging secondary alkyl bromide substrate obtained 44% fluorination yield and 56% E2 yield at 18 h of reaction time. More fluorinated alcohols with six or more fluorine atoms have resulted in relatively acidic alcohols, leading to large amounts of the corresponding ethers of these alcohols as side products. The widely used hexafluoroisopropanol (HFIP) was the least effective one for monofluorination, indicating that both acidity and bulkiness are important features of the alcohols for promoting fluorination using KF salt. Nevertheless, the ether of HFIP can be easily formed with the substrate, generating a highly fluorinated ether product. Theoretical calculations predict Δ<i>G</i> ^‡ in close agreement with the experiments and explain the higher selectivity induced by the fluorinated bulky alcohols in relation to the use of crown ether alone.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"5 1","pages":"69-83"},"PeriodicalIF":3.3,"publicationDate":"2024-11-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11803469/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143383453","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":"Ligand-Functionalized Organometallic Polyoxometalate as an Efficient Catalyst Precursor for Amide Hydrogenation","authors":"Shun Hayashi*,&nbsp;Koichi Momma,&nbsp;Kiyohiro Adachi and Daisuke Hashizume,&nbsp;","doi":"10.1021/acsorginorgau.4c0007110.1021/acsorginorgau.4c00071","DOIUrl":"https://doi.org/10.1021/acsorginorgau.4c00071https://doi.org/10.1021/acsorginorgau.4c00071","url":null,"abstract":"<p >Amide hydrogenation is an important process for producing amines, with the development of efficient heterogeneous catalysts relying on the creation of bimetallic active sites where the two components interact synergistically. In this study, we develop a method for preparing catalysts using ligand-functionalized organometallic polyoxometalates by synthesizing a Rh–Mo organometallic polyoxometalate, [(RhCp^E)₄Mo₄O₁₆] (Cp^E = C₅(CH₃)₃(COOC₂H₅)₂), with Rh–O–Mo interfacial structures and ethoxycarbonyl-functionalized ligands as a catalyst precursor. The activity of supported Rh–Mo catalysts for amide hydrogenation depend on the precursor used, with [(RhCp^E)₄Mo₄O₁₆] showing the highest activity, followed by [(RhCp*)₄Mo₄O₁₆] (Cp* = C₅(CH₃)₅), and then RhCl₃ combined with (NH₄)₆[Mo₇O₂₄]·4H₂O. The catalyst prepared from [(RhCp^E)₄Mo₄O₁₆] effectively hydrogenates tertiary, secondary, and primary amides under mild conditions (0.8 MPa H₂, 353–393 K), demonstrating a high activity and selectivity (conversion: 97%, selectivity: 76%) for primary amide hydrogenation under NH₃-free conditions. Furthermore, we determine that carbonyl oxygen atoms in Cp^E ligands contribute to the electrostatic interaction with Al₂O₃, leading to the high dispersibility of [(RhCp^E)₄Mo₄O₁₆] on the support. We conclude that the high efficiency of [(RhCp^E)₄Mo₄O₁₆] as a catalyst precursor originates from the effective formation of Rh/Mo interfacial active sites, which is assisted by the electrostatic interaction between the Cp^E ligands and support.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"4 6","pages":"705–711 705–711"},"PeriodicalIF":3.3,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsorginorgau.4c00071","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142761226","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":"Ligand-Functionalized Organometallic Polyoxometalate as an Efficient Catalyst Precursor for Amide Hydrogenation.","authors":"Shun Hayashi, Koichi Momma, Kiyohiro Adachi, Daisuke Hashizume","doi":"10.1021/acsorginorgau.4c00071","DOIUrl":"10.1021/acsorginorgau.4c00071","url":null,"abstract":"<p><p>Amide hydrogenation is an important process for producing amines, with the development of efficient heterogeneous catalysts relying on the creation of bimetallic active sites where the two components interact synergistically. In this study, we develop a method for preparing catalysts using ligand-functionalized organometallic polyoxometalates by synthesizing a Rh-Mo organometallic polyoxometalate, [(RhCp^E)₄Mo₄O₁₆] (Cp^E = C₅(CH₃)₃(COOC₂H₅)₂), with Rh-O-Mo interfacial structures and ethoxycarbonyl-functionalized ligands as a catalyst precursor. The activity of supported Rh-Mo catalysts for amide hydrogenation depend on the precursor used, with [(RhCp^E)₄Mo₄O₁₆] showing the highest activity, followed by [(RhCp*)₄Mo₄O₁₆] (Cp* = C₅(CH₃)₅), and then RhCl₃ combined with (NH₄)₆[Mo₇O₂₄]·4H₂O. The catalyst prepared from [(RhCp^E)₄Mo₄O₁₆] effectively hydrogenates tertiary, secondary, and primary amides under mild conditions (0.8 MPa H₂, 353-393 K), demonstrating a high activity and selectivity (conversion: 97%, selectivity: 76%) for primary amide hydrogenation under NH₃-free conditions. Furthermore, we determine that carbonyl oxygen atoms in Cp^E ligands contribute to the electrostatic interaction with Al₂O₃, leading to the high dispersibility of [(RhCp^E)₄Mo₄O₁₆] on the support. We conclude that the high efficiency of [(RhCp^E)₄Mo₄O₁₆] as a catalyst precursor originates from the effective formation of Rh/Mo interfacial active sites, which is assisted by the electrostatic interaction between the Cp^E ligands and support.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"4 6","pages":"705-711"},"PeriodicalIF":3.3,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11621951/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142802377","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":"Purine-Functionalized Ferrocene Derivatives: Efficient Redox Catalysts for Oxidation of Methyl Blue and Reduction of Trinitrophenol","authors":"Sagar R. Sangani,&nbsp;Dax Patel,&nbsp;Ranjitsinh C. Dabhi,&nbsp;Tushar R. Sutariya,&nbsp;Sarfaraz Ahmed and Rakesh Kumar Ameta*,&nbsp;","doi":"10.1021/acsorginorgau.4c0006310.1021/acsorginorgau.4c00063","DOIUrl":"https://doi.org/10.1021/acsorginorgau.4c00063https://doi.org/10.1021/acsorginorgau.4c00063","url":null,"abstract":"<p >Herein, we report a novel organometallic series of potent purine-functionalized ferrocene derivatives (PFD) as redox catalysts. The synthesized PFDs were characterized through FTIR, ^H/CNMR, and liquid chromatography–mass spectrometry (LCMS). Their thermogravimetric analysis (TGA) revealed the thermal stability up to 250 °C, and degradation was noted in the range of 300–500 °C. Their catalytic performance was tested and found for oxidative degradation of methyl blue (MB) up to 99% and reductive conversion of trinitrophenol (TNP) into triaminophenol (TAP) up to 92%, which is supported by their band gap analysis (2.7 eV). The highest unoccupied molecular orbital (HUMO) and lowest unoccupied molecular orbital (LUMO) calculations confirmed the stable geometry of PFDs, and negative values of HOMO and LUMO have supported the oxidation and reduction performance of PFDs as they were noted as Vb &gt; Va &gt; Vc &gt; Vd &gt; Ve due functions of variable substitution. The analysis of the Lagergren pseudo-first-order kinetic model, in support of catalytic performance, revealed that the mobility of dye/phenol molecules with the PFD is what regulates the catalytic conversion rate.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"5 1","pages":"47–61 47–61"},"PeriodicalIF":3.3,"publicationDate":"2024-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsorginorgau.4c00063","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143127609","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":"Purine-Functionalized Ferrocene Derivatives: Efficient Redox Catalysts for Oxidation of Methyl Blue and Reduction of Trinitrophenol.","authors":"Sagar R Sangani, Dax Patel, Ranjitsinh C Dabhi, Tushar R Sutariya, Sarfaraz Ahmed, Rakesh Kumar Ameta","doi":"10.1021/acsorginorgau.4c00063","DOIUrl":"10.1021/acsorginorgau.4c00063","url":null,"abstract":"<p><p>Herein, we report a novel organometallic series of potent purine-functionalized ferrocene derivatives (PFD) as redox catalysts. The synthesized PFDs were characterized through FTIR, ^H/CNMR, and liquid chromatography-mass spectrometry (LCMS). Their thermogravimetric analysis (TGA) revealed the thermal stability up to 250 °C, and degradation was noted in the range of 300-500 °C. Their catalytic performance was tested and found for oxidative degradation of methyl blue (MB) up to 99% and reductive conversion of trinitrophenol (TNP) into triaminophenol (TAP) up to 92%, which is supported by their band gap analysis (2.7 eV). The highest unoccupied molecular orbital (HUMO) and lowest unoccupied molecular orbital (LUMO) calculations confirmed the stable geometry of PFDs, and negative values of HOMO and LUMO have supported the oxidation and reduction performance of PFDs as they were noted as Vb > Va > Vc > Vd > Ve due functions of variable substitution. The analysis of the Lagergren pseudo-first-order kinetic model, in support of catalytic performance, revealed that the mobility of dye/phenol molecules with the PFD is what regulates the catalytic conversion rate.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"5 1","pages":"47-61"},"PeriodicalIF":3.3,"publicationDate":"2024-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11803470/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143383463","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":"The Future of Electro-organic Synthesis in Drug Discovery and Early Development","authors":"H. R. Stephen,&nbsp; and ,&nbsp;J. L. Röckl*,&nbsp;","doi":"10.1021/acsorginorgau.4c0006810.1021/acsorginorgau.4c00068","DOIUrl":"https://doi.org/10.1021/acsorginorgau.4c00068https://doi.org/10.1021/acsorginorgau.4c00068","url":null,"abstract":"<p >Electro-organic chemistry presents a promising frontier in drug discovery and early development, facilitating novel reactivity aligned with green chemistry principles. Despite this, electrochemistry is not widely used as a synthesis and manufacturing tool in drug discovery or development. This overview seeks to identify key areas that require additional research to make synthetic electrochemistry more accessible to chemists in drug discovery and early development and provide potential solutions. This includes expanding the reaction scope, simplifying rapid scale-up, developing electrode materials, and improving knowledge transfer to aid reproducibility and increase the awareness of electrochemistry. The integration of electro-organic synthesis into drug discovery and development holds the potential to enable efficient, sustainable routes toward future medicines faster than ever.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"4 6","pages":"571–578 571–578"},"PeriodicalIF":3.3,"publicationDate":"2024-11-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsorginorgau.4c00068","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142761190","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":"The Future of Electro-organic Synthesis in Drug Discovery and Early Development.","authors":"H R Stephen, J L Röckl","doi":"10.1021/acsorginorgau.4c00068","DOIUrl":"10.1021/acsorginorgau.4c00068","url":null,"abstract":"<p><p>Electro-organic chemistry presents a promising frontier in drug discovery and early development, facilitating novel reactivity aligned with green chemistry principles. Despite this, electrochemistry is not widely used as a synthesis and manufacturing tool in drug discovery or development. This overview seeks to identify key areas that require additional research to make synthetic electrochemistry more accessible to chemists in drug discovery and early development and provide potential solutions. This includes expanding the reaction scope, simplifying rapid scale-up, developing electrode materials, and improving knowledge transfer to aid reproducibility and increase the awareness of electrochemistry. The integration of electro-organic synthesis into drug discovery and development holds the potential to enable efficient, sustainable routes toward future medicines faster than ever.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"4 6","pages":"571-578"},"PeriodicalIF":3.3,"publicationDate":"2024-11-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11621954/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142801395","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}