ACS Organic & Inorganic Au最新文献_第7页

Substituent Effects Govern the Efficiency of Isoxazole Photoisomerization to Carbonyl‑2H‑Azirines 取代基效应控制异恶唑光异构成羰基- 2H -氮杂化的效率。

IF 5.2

ACS Organic & Inorganic Au Pub Date : 2026-02-04 Epub Date: 2025-12-01 DOI: 10.1021/acsorginorgau.5c00105

Kyra E. Jackson, Isabelle Szeto, Leah M. Seebald, Samuel G. Shepard

{"title":"Substituent Effects Govern the Efficiency of Isoxazole Photoisomerization to Carbonyl‑2H‑Azirines","authors":"Kyra E. Jackson, Isabelle Szeto, Leah M. Seebald, Samuel G. Shepard","doi":"10.1021/acsorginorgau.5c00105","DOIUrl":"10.1021/acsorginorgau.5c00105","url":null,"abstract":"The photoisomerization of isoxazoles is an atom-economicalrouteto carbonyl-2H-azirines, which are valuable in bothsynthetic and biological applications. However, isolation of the carbonyl-2H-azirine is challenged by reverse photoisomerization backto the isoxazole and irreversible rearrangement to an oxazole. Inthis work, we demonstrate that substituent selection on 3,5-disubstitutedisoxazoles plays a critical role in driving the photochemical isoxazole–azirineequilibrium toward the carbonyl-2H-azirine whileavoiding oxazole formation. We find that substituents affect the degreeof overlap in the absorption spectra of isoxazole–azirine pairs,where reducing overlap increases the efficiency of photoisomerization.We use time-dependent density functional theory to predict absorptionspectra for isomer pairs with varied 3,5-disubstituents, identifying tert-butyl- and trifluoromethyl-substituted 5-aminoisoxazolesas promising structures. We then tested these predictions experimentally,revealing efficient formation of carbonyl-2H-azirinesin high yields with minimal oxazole formation. This is in contrastto a phenyl-substituted 5-aminoisoxazole, which was found to readilyform oxazoles, precluding isolation of the carbonyl-2H-azirine. These results demonstrate the utility of substituent-drivendesign for tuning photoisomerization equilibria and provide an atom-economicaloption for generating carbonyl-2H-azirines on syntheticallyuseful scales.","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"6 1","pages":"41–46"},"PeriodicalIF":5.2,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146143555","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

Role of Propionate Side Chain in Heme-Containing Metalloenzymes. 丙酸侧链在含血红素金属酶中的作用。

IF 3.3

ACS Organic & Inorganic Au Pub Date : 2025-10-15 eCollection Date: 2025-12-03 DOI: 10.1021/acsorginorgau.5c00078

Dinesh Singh, Vandana Kardam, Kshatresh Dutta Dubey

引用次数: 0

Recent Advances in C-H Perfluoroalkyl Thiolation and Perfluoroalkyl Sulfonylation. C-H全氟烷基硫代化和全氟烷基磺酰化研究进展。

IF 3.3

ACS Organic & Inorganic Au Pub Date : 2025-10-13 eCollection Date: 2025-12-03 DOI: 10.1021/acsorginorgau.5c00094

Sichang Wang, Liying Zhang, Fei Hong, Weichao Du, Congyu Ke, Jie-Ping Wan

{"title":"Recent Advances in C-H Perfluoroalkyl Thiolation and Perfluoroalkyl Sulfonylation.","authors":"Sichang Wang, Liying Zhang, Fei Hong, Weichao Du, Congyu Ke, Jie-Ping Wan","doi":"10.1021/acsorginorgau.5c00094","DOIUrl":"10.1021/acsorginorgau.5c00094","url":null,"abstract":"This review comprehensively summarizes the recent advances in the direct C-H perfluoroalkyl thiolation and perfluoroalkyl sulfonylation, focusing on the incorporation of -SCF3 and -SO2CF3 motifs. Due to their exceptional lipophilicity, electron-withdrawing nature, and metabolic stability, these fluorine-containing groups are highly valuable in pharmaceutical, agrochemical, and material sciences. The contents of this review are systematically organized according to the hybridization of the central carbon atom (sp, sp2, sp3) and cover both transition-metal-catalyzed and transition metal-free methodologies. Key developments in electrophilic trifluoromethylthiolating reagents, such as hypervalent iodine compounds, N-trifluoromethylthiosaccharin, and related derivatives, are highlighted. The mechanism, scope, limitation, and application of typical reactions are discussed, emphasizing strategies to overcome challenges in regioselectivity and functional group compatibility. The review also explores emerging trends in photocatalytic, electrochemical, and dual catalytic systems, underscoring the move toward more sustainable and efficient synthetic routes. Finally, future perspectives and potential applications in the synthesis of bioactive molecules and functional materials are discussed.","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"5 6","pages":"467-484"},"PeriodicalIF":3.3,"publicationDate":"2025-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12679318/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145701826","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

Synthesis and Electronic Structure of a Tetraazanaphthalene Radical-Bridged Yttrium Complex. 四氮杂萘自由基桥接钇配合物的合成及电子结构。

IF 3.3

ACS Organic & Inorganic Au Pub Date : 2025-10-09 eCollection Date: 2025-12-03 DOI: 10.1021/acsorginorgau.5c00086

Saroshan Deshapriya, Selvan Demir

{"title":"Synthesis and Electronic Structure of a Tetraazanaphthalene Radical-Bridged Yttrium Complex.","authors":"Saroshan Deshapriya, Selvan Demir","doi":"10.1021/acsorginorgau.5c00086","DOIUrl":"10.1021/acsorginorgau.5c00086","url":null,"abstract":"Taming radical anions with highly electropositive metal ions poses a grand synthetic challenge owing to the high reactivity of such compounds originating from the unpaired electron. A successful synthetic metal radical match elicits a desire to thoroughly understand the electronic structure of a given metal radical pairing, which may inform about the potential physical properties pertaining to spintronics and magnetism relevant for future technologies. Here, the 1,4,5,8-tetraazanaphthalene (tan) ligand was utilized in the synthesis of (Cp*2Y)2(μ-tan), 1, using the doubly reduced version K2tan and Cp*2Y-(BPh4) following a salt metathesis reaction. Chemical oxidation of 1 yielded [(Cp*2Y)2(μ-tan•)]-[BArF20], 2, containing a tan-• radical anion. 2 constitutes the first d-block coordination compound bearing a tan radical. 1 and 2 were studied through X-ray crystallography, electrochemistry, and spectroscopy. The radical nature of 2 was uncovered by cw-EPR spectroscopy and density functional theory (DFT) computations. All findings suggest major changes in the spin and charge distributions of this organic radical ligand when it is metalated. In fact, the results demonstrate that the tan-• radical is more stable when coordinated to a transition metal than in its free nature, and thus, this insight is relevant for the development of future spintronic technologies.","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"5 6","pages":"557-566"},"PeriodicalIF":3.3,"publicationDate":"2025-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12679307/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145702146","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

Co₃O₄‑Promoted Cerium Oxide Catalyst for Efficient Catalytic N‑Alkylation of Amines with Alcohols. Co3O4促进的氧化铈催化剂用于胺与醇的高效N -烷基化催化。

IF 3.3

ACS Organic & Inorganic Au Pub Date : 2025-10-08 eCollection Date: 2025-12-03 DOI: 10.1021/acsorginorgau.5c00069

Jianyao Kou, Guangyao Yang, Zhixin Yu, Jiachao Liu, Yuhang Xu, Zhuo Xin, Yuxing Huang

引用次数: 0

Guest-Induced Conformational Switching in "One Wall" Calix[4]pyrrole Cavitands Functionalized with an Inwardly Directed Carboxylic Acid. 内向羧酸功能化“一壁”杯形[4]吡咯空腔体的客体诱导构象转换。

IF 3.3

ACS Organic & Inorganic Au Pub Date : 2025-10-02 eCollection Date: 2025-12-03 DOI: 10.1021/acsorginorgau.5c00087

Mingkai Zhao, Andrés F Sierra, Gemma Aragay, Pablo Ballester

{"title":"Guest-Induced Conformational Switching in \"One Wall\" Calix[4]pyrrole Cavitands Functionalized with an Inwardly Directed Carboxylic Acid.","authors":"Mingkai Zhao, Andrés F Sierra, Gemma Aragay, Pablo Ballester","doi":"10.1021/acsorginorgau.5c00087","DOIUrl":"10.1021/acsorginorgau.5c00087","url":null,"abstract":"We report the design, synthesis, and conformational analysis of two aryl-extended calix[4]-pyrrole (AE-C[4]-P) cavitands that feature a single methylene bridge and an opposed aromatic bridging wall with an inward-facing carboxylic acid. Inspired by Rebek's introverted acid motif, these cavitands were developed to explore guest-induced conformational switching between \"equatorial\" and \"axial\" orientations of the bridging aromatic wall. Binding studies with N-oxide guests, capable of monotopic or ditopic hydrogen bonding, revealed that the nature of the bridging aromatic spacer critically governs the host behavior. The benzimidazole-based cavitand showed strong affinity for DABCO mono-N-oxide but resisted conformational change. In contrast, the quinoxaline-imidazole analogue underwent a solvent-dependent switch from \"equatorial\" to \"axial\" geometry upon binding 4-carboxy-pyridine-N-oxide guest. This switching is driven by the ditopic binding of the guest and stabilized by two intramolecular CH···lone pair interactions in the axial conformer of the complex. DFT calculations supported the experimental results. The reported findings highlight key structure-function relationships in calix[4]-pyrrole cavitands and establish a general strategy for designing guest-responsive molecular containers capable of conformational switching.","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"5 6","pages":"567-581"},"PeriodicalIF":3.3,"publicationDate":"2025-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12679308/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145701843","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

Copper(I)-Anchoring Covalent Organic Polymer for Heterogeneous CuAAC Reaction without Reducing Agents and Copper Leaching. 铜(I)-锚定共价有机聚合物在非还原剂非均相CuAAC反应和铜浸出中的应用。

IF 3.3

ACS Organic & Inorganic Au Pub Date : 2025-09-25 eCollection Date: 2025-12-03 DOI: 10.1021/acsorginorgau.5c00067

Maria Aurora Guarducci, Simone Manetto, Andrea Giacomo Marrani, Francesco Amato, Paolo Guglielmi, Michele Coluccia, Antonella Fontana, Serena Pilato, Claudio Villani, Alessia Ciogli, Giulia Mazzoccanti

引用次数: 0

Electrochemical Halogenation and Etherification of Alcohols Enabled by a Halide-Coupled Phosphine Oxidation. 卤化物偶联膦氧化催化醇类的电化学卤化和醚化反应。

IF 3.3

ACS Organic & Inorganic Au Pub Date : 2025-09-25 eCollection Date: 2025-12-03 DOI: 10.1021/acsorginorgau.5c00091

Emma A Hale, Vincent Tc Ngo, Qilei Zhu

{"title":"Electrochemical Halogenation and Etherification of Alcohols Enabled by a Halide-Coupled Phosphine Oxidation.","authors":"Emma A Hale, Vincent Tc Ngo, Qilei Zhu","doi":"10.1021/acsorginorgau.5c00091","DOIUrl":"10.1021/acsorginorgau.5c00091","url":null,"abstract":"Phosphine-mediated nucleophilic substitution reactions of alcohol substrates, such as the Appel and Mitsunobu reactions, have found widespread applications in chemical synthesis. However, their reliance on stoichiometric chemical oxidants (e.g., carbon tetrachloride and azodicarboxylate reagents) often results in limited functional group tolerance, environmentally hazardous wastes, and unsatisfactory reaction economy. Herein, we describe a user-friendly electrochemical Appel reaction employing readily available tetrabutylammonium halide salts ( n Bu4N+X-, X = Cl, Br, and I) as the halogen source. A survey of alcohol substrates revealed broad functional group tolerance, including complex pharmaceutical and bioactive scaffolds. Electroanalytical voltammetry and control experiments support a halide-coupled phosphine oxidation pathway under mild anodic potentials, affording key alkoxyphosphonium intermediates prior to nucleophilic substitution. Notably, the electrochemical halogenation conditions can also facilitate intramolecular alcohol etherification with oxidation-sensitive phenols and weakly acidic alcohol nucleophiles.","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"5 6","pages":"492-497"},"PeriodicalIF":3.3,"publicationDate":"2025-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12679309/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145701857","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

Stereoselective E‑Carbofunctionalization of Alkynes to Vinyl-Triflates via Gold Redox Catalysis. 通过金氧化还原催化炔烃立体选择性E -碳官能化成三氟乙烯酯。

IF 3.3

ACS Organic & Inorganic Au Pub Date : 2025-09-24 eCollection Date: 2025-12-03 DOI: 10.1021/acsorginorgau.5c00084

Filippo Campagnolo, Lorenza Armando, Elisa Boccalon, Alessandra Cicolella, Manfred Bochmann, Giovanni Talarico, Luca Rocchigiani

{"title":"Stereoselective E‑Carbofunctionalization of Alkynes to Vinyl-Triflates via Gold Redox Catalysis.","authors":"Filippo Campagnolo, Lorenza Armando, Elisa Boccalon, Alessandra Cicolella, Manfred Bochmann, Giovanni Talarico, Luca Rocchigiani","doi":"10.1021/acsorginorgau.5c00084","DOIUrl":"10.1021/acsorginorgau.5c00084","url":null,"abstract":"Carbofunctionalization of alkynes with trifluoromethylsulfonate nucleophiles is a powerful strategy for the synthesis of vinyl triflates with diverse molecular complexity. However, stereoselective protocols are challenging to realize, and the development of novel strategies for controlling the selectivity is highly desirable. In this work, we show that gold complexes bearing the hemilabile MeDalPhos ligand (MeDalPhos = di-(1-adamantyl)-2-dimethylamino-phenylphosphine) catalyze the E-stereoselective carbofunctionalization of internal alkynes using aryl/vinyl iodides and AgOTf as simple starting reagents. Based on the outer-sphere nature of this reaction and the beneficial effect of the MeDalPhos ligand, the Z-selective attack is practically suppressed, leading to an ideal kinetic selectivity. Mechanistic studies, both experimental and theoretical, revealed that the interplay between kinetics and thermodynamics is crucial in determining the final E/Z ratios for each substrate.","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"5 6","pages":"548-556"},"PeriodicalIF":3.3,"publicationDate":"2025-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12679304/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145701969","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

The Role of 1,2-Palladium Migration/Insertion on C(sp³)-H Functionalization. 1,2-钯在C(sp3)-H官能化中的迁移/插入作用。

IF 3.3

ACS Organic & Inorganic Au Pub Date : 2025-09-19 eCollection Date: 2025-10-01 DOI: 10.1021/acsorginorgau.5c00085

Mohammad Sadegh Karimtabar, Yasin Mohammadkhani, Mohammad Mahdavi, Parviz Rashidi Ranjbar

{"title":"The Role of 1,2-Palladium Migration/Insertion on C(sp3)-H Functionalization.","authors":"Mohammad Sadegh Karimtabar, Yasin Mohammadkhani, Mohammad Mahdavi, Parviz Rashidi Ranjbar","doi":"10.1021/acsorginorgau.5c00085","DOIUrl":"10.1021/acsorginorgau.5c00085","url":null,"abstract":"Selective functionalization of C-(sp3)-H bonds remains challenging yet crucial for researchers. A frequently used approach by chemists to tackle this challenge involves leveraging 1,2-metal migration/insertion, which enables the selective activation and cleavage of a specific C-(sp3)-H bond adjacent to or distant from the directing group. Palladium is among the most commonly employed catalysts for C-(sp3)-H functionalization through metal migration/insertion, with Pd-(OAc)2 being the predominant palladium complex utilized in these processes. 1,2-Palladium migration is a key strategy for achieving selective C-(sp3)-H functionalization. After palladium coordinates to a directing group, its migration can activate the nearby C-(sp3)-H bond. With subsequent migrations, more distant C-(sp3)-H bonds can be targeted and transformed into C-(sp3)-functional groups. During the 1,2-insertion of palladium, the migration of palladium takes place following the activation of the C-(sp3)-H bond. This migration step typically involves the palladium inserting into a double bond, which links the C-(sp3)-H bond to a C-(sp2)-H bond, thereby progressing the reaction. Ultimately, this review highlights that C-(sp3)-H functionalization via 1,2-palladium migration/insertion has the potential to selectively modify both proximal and remote C-H bonds in organic molecules, offering a valuable tool for researchers to synthesize a wide range of organic compounds in future studies. This account encompasses all types of 1,2-palladium migration/insertion and examines their impact on C-(sp3)-H functionalization. It provides a detailed analysis of the mechanisms involved and explores how these migrations enable the activation of both remote and proximal C-(sp3)-H bonds with the directing group.","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"5 5","pages":"299-321"},"PeriodicalIF":3.3,"publicationDate":"2025-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12492045/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145233508","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