Journal of the American Chemical Society最新文献

{"title":"Correction to “Discovery of a Natural Ent-Kaurene Diterpenoid Oridonin as an E3 Ligase Recruiter for PROTACs”","authors":"Jie Huang, Xuekun Fu, Fang Qiu, Zhijian Liang, Chunhao Cao, Zhuqian Wang, Hongzhen Chen, Siran Yue, Duoli Xie, Yiying Liang, Aiping Lu, Chao Liang","doi":"10.1021/jacs.5c03656","DOIUrl":"https://doi.org/10.1021/jacs.5c03656","url":null,"abstract":"In Figure S6E, the band of TUBULIN was incorrect. The revised Supporting Information file provided here shows the correct band. This change does not alter the conclusions of the published work. The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/jacs.5c03656. Materials and Methods; Figures S1–S14; Tables S1–S2; and Supporting Notes 1–11 (PDF) Correction to “Discovery\u0000of a Natural Ent-Kaurene\u0000Diterpenoid Oridonin as an E3 Ligase Recruiter for PROTACs” <span> 1 </span><span> views </span> <span> 0 </span><span> shares </span> <span> 0 </span><span> downloads </span> Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html. This article has not yet been cited by other publications.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"35 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723852","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Solvent Medium-Induced Changes to Internal Pressure in the Layered Host VOPO4·2H2O and the Influence on Intercalation Reactions","authors":"Jiahui Liu, Yuan Liu, Timothy Yoo, Miho Itoi, Honggyu Kim, Simon R. Phillpot, Daniel R. Talham","doi":"10.1021/jacs.4c16643","DOIUrl":"https://doi.org/10.1021/jacs.4c16643","url":null,"abstract":"Layered vanadium phosphate dihydrate, VOPO₄·2H₂O, has been chosen as a host for ferrocene intercalation to explore the influence of solvent-guest and solvent-host interactions on rates and product selection. After eliminating solvents that react directly with the VOPO₄·2H₂O host, ferrocene intercalation was evaluated in a series of seven solvents that do not themselves intercalate or otherwise alter the host structure. The intercalation kinetics are analyzed in acetone, butanone, pentanone, acetonitrile, propionitrile, butyronitrile, and DMF. No intercalation is observed in DMF, but all other solvents yield a mixture of stage 1 and stage 2 ferrocenium intercalation products with reaction rates and product ratios varying across the series of solvents. Using <i>ex situ</i> as well as <i>in situ</i> PXRD methods, faster reactions yield more stage 1 product, while a higher degree of stage 2 product is seen for slower kinetics. The results are interpreted in the context of competition between intercalation rates and the buildup of elastic strain between intercalated domains and unintercalated host. To understand solvent effects, both solvent-guest and solvent-host effects are considered. None of the typically considered solvent-guest effects, such as guest desolvation energy, dielectric constant, and guest oxidation potential, correlate with the observed reaction kinetics. On the other hand, different solvent environments are shown to change the internal pressure, <i>P</i>_eff, within the layered hosts, a consequence of changing surface energy and surface tension (stress) in particles with nanometer scale dimensions. The VOPO₄·2H₂O interlayer spacing decreases when particles are suspended in DMF and organonitrile solvents, while the layers separate slightly in acetone, butanone, and pentanone. Using calculated elastic constants, the structural changes correspond to changes in <i>P</i>_eff in the range 0.22 GPa &gt; Δ<i>P</i>_eff &gt; −0.11 GPa across the series of solvents. A density functional theory analysis of the influence of pressure on ferrocene diffusion adds support for the idea that intercalation kinetics are altered by changing internal pressure. The results show solvent environments can be responsible for altering the effective pressure within intercalation hosts, influencing intercalation rates and product selection, even if the solvents do not react directly with the host solids.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"30 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723941","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Extrinsic and Intrinsic Factors Governing the Electrochemical Oxidation of Propylene in Aqueous Solutions","authors":"Tae Gyu Yun, Boqiang Chen, Sarah Wells, Younghwan Lim, Jun Seop Kim, Ana Guilherme Buzanich, Martin Radtke, Matthias M. Waegele, Marcel Risch, Alexis Grimaud","doi":"10.1021/jacs.5c02585","DOIUrl":"https://doi.org/10.1021/jacs.5c02585","url":null,"abstract":"The electrochemical synthesis of commodity chemicals such as epoxides and glycols offers a sustainable alternative to conventional methods that involve hazardous chemicals. Efforts to improve the yield and selectivity of propylene oxidation using Pd-based catalysts have been shown to be highly sensitive to applied potential, pH, and electrochemical cell design. Record efficiencies and yields were obtained by substitution of PdO by 4d or 5d transition metals, including Pt, with thus far little rationale regarding the origin for the improvement. Through electrochemical analysis, scanning transmission electron microscopy, X-ray absorption spectroscopy, and surface-enhanced infrared absorption spectroscopy, we investigated the mechanism of propylene oxidation on Pd-based catalysts. We demonstrate that adsorbates forming on PdO, where Pd adopts a square-planar coordination [PdO₄], differ from that forming on the surface of oxidized metallic Pd catalysts with an oxo intermediate mediating propylene oxidation on PdO. We further show that Pt substitution in PdO does not modify this oxo intermediate. Varying pH, we found that the onset for propylene oxidation is pH independent, indicating a potential-determining step where the proton is not involved in and similar reaction pathway in acidic and near-neutral conditions. Finally, our work undoubtedly demonstrates that high Faradaic efficiency toward propylene glycol and propylene oxide formation, such as those previously reported in the literature, can be achieved by means of electrode engineering and mastery of mass transport and local pH. Notably, we achieved ≈100% faradaic efficiency for propylene glycol at 1.7 V vs RHE in acidic media using a Pt-substituted PdO catalyst loaded onto a gas diffusion electrode.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"58 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143734383","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A Systematic Approach for Incorporating Structural Flexibility in High-Throughput Computational Screening of Metal–Organic Frameworks for Xylene Separation","authors":"Saad Aldin Mohamed, Rui Zheng, Nengxiu Zhu, Dan Zhao, Jianwen Jiang","doi":"10.1021/jacs.5c01749","DOIUrl":"https://doi.org/10.1021/jacs.5c01749","url":null,"abstract":"Separation of xylene isomers poses a significant challenge due to their similar physicochemical properties. Currently, zeolites are utilized as adsorbents for this purpose in the chemical industry despite suboptimal separation performance. With tunable pore size and chemical functionality, metal–organic frameworks (MOFs) are promising adsorbents for separation. By virtue of high-throughput computational screening (HTCS), the adsorption performance of a large collection of MOFs can be evaluated <i>in silico</i> by using Monte Carlo (MC) simulations. Unlike prior studies assuming rigid structures of MOFs during screening, we develop a systematic approach for incorporating flexibility in HTCS for xylene separation. First, MOFs are judiciously classified with external flexibility (volume/shape changes) and internal flexibility (intraframework fluctuations), respectively, based on the nature and extent of structural deformation from molecular dynamics (MD) simulations. Afterward, adsorption in MOFs with external flexibility is simulated by hybrid MC/MD method, the flexible snapshot method is used for MOFs with a sort of internal flexibility, and grand-canonical MC (GCMC) method is employed for MOFs with negligible flexibility. Finally, top-performing MOFs are identified for xylene separation. While substantially reducing computational cost, this study also delivers more reliable results compared to the assumption of rigid structures. The HTCS approach is versatile and can be extended beyond MOFs, offering a robust tool for the virtual screening of other soft-porous materials for a wide range of important applications.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"215 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723851","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Rational Design Principles for De Novo α-Helical Peptide Barrels with Dynamic Conductive Channels","authors":"Ai Niitsu, Andrew R. Thomson, Alistair J. Scott, Jason T. Sengel, Jaewoon Jung, Kozhinjampara R. Mahendran, Mikiko Sodeoka, Hagan Bayley, Yuji Sugita, Derek N. Woolfson, Mark I. Wallace","doi":"10.1021/jacs.4c13933","DOIUrl":"https://doi.org/10.1021/jacs.4c13933","url":null,"abstract":"Despite advances in peptide and protein design, the rational design of membrane-spanning peptides that form conducting channels remains challenging due to our imperfect understanding of the sequence-to-structure relationships that drive membrane insertion, assembly, and conductance. Here, we describe the design and computational and experimental characterization of a series of coiled coil-based peptides that form transmembrane α-helical barrels with conductive channels. Through a combination of rational and computational design, we obtain barrels with 5 to 7 helices, as characterized in detergent micelles. In lipid bilayers, these peptide assemblies exhibit two conductance states with relative populations dependent on the applied potential: (i) low-conductance states that correlate with variations in the designed amino-acid sequences and modeled coiled-coil barrel geometries, indicating stable transmembrane α-helical barrels; and (ii) high-conductance states in which single channels change size in discrete steps. Notably, the high-conductance states are similar for all peptides in contrast to the low-conductance states. This indicates the formation of large, dynamic channels, as observed in natural barrel-stave peptide channels. These findings establish rational routes to design and tune functional membrane-spanning peptide channels with specific conductance and geometry.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"183 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723940","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Enantioselective Dearomative [2π + 2σ] Photocycloaddition of Naphthalene Derivatives with Bicyclo[1.1.0]butanes Enabled by Gd(III) Catalysis","authors":"Wen-Jie Shen, Xin-Xuan Zou, Muzi Li, Yuan-Zheng Cheng, Shu-Li You","doi":"10.1021/jacs.5c01506","DOIUrl":"https://doi.org/10.1021/jacs.5c01506","url":null,"abstract":"The cycloaddition reactions of bicyclo[1.1.0]butanes with alkenes, imines, nitrones, or aziridines have served as an efficient platform to create conformationally restricted saturated bicyclic scaffolds. However, the use of readily available aromatics in such reactions, especially in an asymmetric manner, remains underexplored. Herein, we report a highly regio- and enantioselective dearomative [2π + 2σ] photocycloaddition reaction between naphthalene derivatives and bicyclo[1.1.0]butanes, enabled by Gd(III) catalysis. Bicyclo[1.1.0]butanes and naphthalenes adorned with a diverse array of functional groups are well-tolerated under mild conditions, affording enantioenriched pharmaceutically important bicyclo[2.1.1]hexanes in 30–96% yields with 81–93% ee and 12:1 → &gt;20:1 rr. The synthetic versatility of this reaction is further demonstrated by the facile removal of directing group and derivatizations of the dearomatized product. UV–vis absorption spectroscopy studies suggest the involvement of an excited naphthalene species in the reaction process.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"27 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723850","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Construction of C4-Spirocyclic Chiral Covalent Organic Frameworks Via Asymmetric Multicomponent Povarov Reaction for Enantioselective Sensing","authors":"Zhi Chen, Zi-Ran Liu, Jun Zhang, Wen-Ting Yang, Jing-Lan Kan, Jianzhong Fan, Wen-Yan Li, Jian-Cheng Wang, Yu-Bin Dong","doi":"10.1021/jacs.4c18474","DOIUrl":"https://doi.org/10.1021/jacs.4c18474","url":null,"abstract":"Although many chiral covalent organic frameworks (CCOFs) have been synthesized, the rapid development of this field has been severely restricted by the limitations of CCOFs synthesis methods and the scarcity of their chiral structural unit types. Herein we report, for the first time, the construction of C4-spirocyclic CCOFs via the asymmetric multicomponent Povarov reaction under ambient conditions. The obtained <b>C4</b>-<b>spiro</b>-(2<i>S</i>, 4<i>R</i>)-<b>TMTT</b>-<b>COF</b> can be as a novel chiral fluorescent sensor to discriminate D/L-PAL enantiomers. This finding will provide a simple and universal method for constructing CCOFs with novel chiral structural groups and might open new insights into the construction of the CCOFs featuring multiple distinct types of carbon chiral centers.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"72 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723942","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Transfer Learning-Enabled Ligand Prediction for Ni-Catalyzed Atroposelective Suzuki–Miyaura Cross-Coupling Based on Mechanistic Similarity: Leveraging Pd Knowledge for Ni Discovery","authors":"Xin-Yuan Xu, Li-Gao Liu, Li-Cheng Xu, Shuo-Qing Zhang, Xin Hong","doi":"10.1021/jacs.5c00838","DOIUrl":"https://doi.org/10.1021/jacs.5c00838","url":null,"abstract":"The rational design of novel molecular catalysts often confronts challenges due to complex structure–performance relationships. Emerging data-driven approaches provide revolutionary solutions, yet the application of machine learning to new catalyst development inevitably faces a low-data regime with limited effective structure–performance modelings available. In this study, we present a transfer learning strategy to facilitate knowledge transfer from well-documented Pd catalysis to a novel, underexplored Ni system. By synergistically modeling extensive Pd catalysis data with limited Ni/Sadphos data, our approach accurately predicted novel Sadphos ligands, enabling the first atroposelective Ni-catalyzed Suzuki–Miyaura cross-coupling reaction. The synthetic utility of the machine learning-predicted ligand was further demonstrated in its broad synthetic scope, gram-scale synthesis, and precise control of dual axial chiralities in ternaphthalene through the sequential coupling under Ni and Pd catalysis. Additionally, density functional theory calculations were employed to reveal the reaction mechanism and stereochemical model of this new Ni catalyst, validating the proposed mechanistic connection between Ni and Pd. This work demonstrates how machine learning models can effectively leverage mechanistic connectivity, applying extensive structure–performance relationship data from the literature to predict new catalysts, providing a novel strategy for the rational design of molecular catalysts from a few-shot learning perspective.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"59 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723943","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"3-Center-3-Electron σ-Adduct Enables Silyl Radical Transfer below the Minimum Barrier for Silyl Radical Formation","authors":"Zihang Qiu, Paolo Cleto Bruzzese, Zikuan Wang, Hao Deng, Markus Leutzsch, Christophe Farès, Sonia Chabbra, Frank Neese, Alexander Schnegg, Constanze N. Neumann","doi":"10.1021/jacs.4c18445","DOIUrl":"https://doi.org/10.1021/jacs.4c18445","url":null,"abstract":"Transition-metal-catalyzed cleavage of the Si–H bond in silanes to yield silyl radicals requires substantial amounts of energy, which are commonly supplied by photons. For Rh(II) porphyrins, efficient hydrosilylation catalysis becomes accessible only upon site isolation in a metal–organic framework (MOF), and the formation of free silyl radicals likewise requires irradiation. Within the MOF, however, an uncommonly facile direct silyl radical transfer to olefin substrates is also possible, which makes thermal olefin hydrosilylation accessible at room temperature. The ability of MOF-supported Rh(II) metalloradicals to furnish an unprecedented 3-center-3-electron (3c-3e) Rh(II)-silane σ-adduct enables the assembly of a tricomponent transition state that is comprised of Rh(II), silane, and ethylene. The tricomponent transition state bypasses the high-energy silyl radical species and enables silyl radical transfer with an activation free energy ∼15 kcal·mol^–1 below the minimum energy barrier for silyl radical formation. We report direct observation of the 3c-3e silane σ-adduct, which is a stable species in the absence of light and olefins. Furthermore, a combination of experiments and quantum chemical calculations shows that direct silyl radical transfer to ethylene is promoted by the temporary oxidation of the transition structure by a proximal Rh(II) center. Thus, the crucial role of the MOF matrix is to fix the inter-Rh separation in our catalyst at a value large enough for 3c-3e silane adduct formation but short enough for facile electron transfer.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"33 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723856","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Bilayer Kagome Ferrimagnet Exhibiting Exceptional Spontaneous Exchange Bias in TbMn6(Ge,Ga)6","authors":"Hankun Xu, Wenjie Li, Junjie Chen, Sergii Khmelevskyi, Dmitry Khalyavin, Pascal Manuel, Chuanying Xi, Shogo Kawaguchi, Jing Chen, Wanda Yang, Qinghua Zhang, Yili Cao, Chengyi Yu, Yang Ren, Kun Lin, Xianran Xing","doi":"10.1021/jacs.4c17505","DOIUrl":"https://doi.org/10.1021/jacs.4c17505","url":null,"abstract":"Manipulating interlayer interactions in two-dimensional (2D) materials has led to intriguing behaviors. Borrowing these 2D signatures to bulk materials is likely to unlock exceptional properties. Here, we report an emergent 2D-like bilayer Kagome ferrimagnet through reducing the interbilayer magnetic interaction to nearly zero. This concept is realized within bulk TbMn₆(Ge,Ga)₆ compounds, characterized by an isolated and pure Mn Kagome lattice, simply by the chemical substitution of Ge with Ga. Specifically, the targeted compound TbMn₆Ge₅Ga₁ exhibits a giant spontaneous exchange bias (SEB) of approximately 1.6 T, which is more than twice that observed in known materials. Field-dependent neutron diffraction reveals the robust nature of the compensated ferrimagnetic (FiM), characterized by almost two-thirds of the moments being pinned and irreversible under fields up to 9 T. Through magnetic and structural analysis, alongside theoretical calculations, we demonstrate that the substantial SEB is related to the intense competition between local robust and weak FiM states within the bilayer Kagome configuration, which are stabilized by an incommensurate spin arrangement. The concept of a bilayer Kagome magnet offers new opportunities for discovering attractive properties in 2D-like materials.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"16 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713722","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}