Chemical Science最新文献_第9页

Self-promoted tumor-targeting nanomedicine activates STING-driven antitumor immunity via photodynamic DNA damage and PARP inhibition 自我推广的肿瘤靶向纳米药物通过光动力DNA损伤和PARP抑制激活sting驱动的抗肿瘤免疫

IF 8.4 1区化学

Chemical Science Pub Date : 2025-05-01 DOI: 10.1039/d5sc01953b

Baixue Yu, Wei Zhang, Zhouchuan Shao, Xiayun Chen, Yi Cen, Yibin Liu, Ying Chen, Xinxuan Li, Ziqi Liang, Shiying Li, Xiaoyuan Chen

{"title":"Self-promoted tumor-targeting nanomedicine activates STING-driven antitumor immunity via photodynamic DNA damage and PARP inhibition","authors":"Baixue Yu, Wei Zhang, Zhouchuan Shao, Xiayun Chen, Yi Cen, Yibin Liu, Ying Chen, Xinxuan Li, Ziqi Liang, Shiying Li, Xiaoyuan Chen","doi":"10.1039/d5sc01953b","DOIUrl":"https://doi.org/10.1039/d5sc01953b","url":null,"abstract":"The activation of antitumor immunity through strategically designed nanomedicine presents a promising approach to overcome the limitations of conventional cancer therapies. In this work, bioinformatic analysis found an abnormal poly(ADP-ribose) polymerase-1 (PARP-1) expression in breast cancer, linked to the cyclic GMP-AMP synthase (cGAS)-stimulator of the interferon gene (STING) pathway and immune suppression. PARP-1 inhibitor screening revealed olaparib (Ola) as a promising candidate, enhancing DNA damage and potentiating the immunotherapeutic response. Consequently, a self-promoted tumor-targeting nanomedicine (designated as PN-Ola) was proposed to activate STING-driven antitumor immunity through photodynamic DNA damage and PARP inhibition. PN-Ola was composed of a programmed death-ligand 1 (PD-L1) targeting amphiphilic peptide-photosensitizer conjugate (C16-K(PpIX)-WHRSYYTWNLNT), which effectively encapsulates Ola. Notably, PN-Ola demonstrated selective accumulation in tumor cells that overexpress PD-L1, while concurrently enhancing PD-L1 expression, thereby establishing a self-promoting mechanism for improved drug accumulation within tumor cells. Meanwhile, the photodynamic therapy (PDT) effects of PN-Ola would result in oxidative DNA damage and subsequent accumulation of DNA fragments. Additionally, the PARP inhibition provided by PN-Ola disrupted the DNA repair pathways in tumor cells, leading to a boosted release of DNA fragments that further stimulated STING-driven antitumor immunity. The synergistic mechanism of PN-Ola effectively activates the immunotherapeutic response by enhancing T cell activation and infiltration, leading to the eradication of metastatic tumors without inducing side effects. This study presents a promising strategy to overcome targeting ligand heterogeneity while activating systemic antitumor immunity for the effective eradication of metastatic tumors.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"33 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143893826","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}

引用次数: 0

From the Synthesis of Wearable Polymer Sensors to their Potential for Reuse and Ultimate Fate 从可穿戴聚合物传感器的合成到它们的再利用潜力和最终命运

IF 8.4 1区化学

Chemical Science Pub Date : 2025-05-01 DOI: 10.1039/d5sc01634g

Arya Ajeev, Theodore Warfle, Sara Maslaczynska-Salome, Saeideh Alipoori, Colton Duprey, Evan K. Wujcik

{"title":"From the Synthesis of Wearable Polymer Sensors to their Potential for Reuse and Ultimate Fate","authors":"Arya Ajeev, Theodore Warfle, Sara Maslaczynska-Salome, Saeideh Alipoori, Colton Duprey, Evan K. Wujcik","doi":"10.1039/d5sc01634g","DOIUrl":"https://doi.org/10.1039/d5sc01634g","url":null,"abstract":"The objective of this perspective is to review the high-interest field of wearable polymer-based sensors, from synthesis, use, and detection mechanisms---with a focus on their transient nature, potential reuse, and ultimate fate. While many bulk polymers have long been mass-produced, the materials needed to create polymer-based sensors—often with unique properties (e.g., being electronically conductive)—are still highly active areas of research. Polymer-based materials and composites, when investigated as wearable sensors, have a wide range of applications with most falling under the umbrellas of biochemical and environmental sensing (i.e., chemical reactivity-based detection) or physical sensing (e.g., piezoresistive detection). Since the long-term viability of these sensors is a function of not just their initial syntheses, but also their ability to be durable, recyclable, or otherwise renewable, a discussion of the both the technical and societal aspects of the reuse and ultimate fate of these materials will be covered. This discussion will focus on topics such as environmental impact, sterilization and other methods for ensuring continued biocompatibility, as well as methods for the transformation, reclamation, or re-implementation of the sensor devices—a major issue the polymer community is facing.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"56 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143893824","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}

引用次数: 0

Targeted design of organic Janus particles for improved photocatalytic hydrogen evolution. 针对改进光催化析氢的有机Janus颗粒的针对性设计。

IF 7.6 1区化学

Chemical Science Pub Date : 2025-04-30 DOI: 10.1039/d5sc00802f

Khaoula Missaoui, Guillaume Wantz, Thierry Toupance, Sylvain Chambon, Alexander Kuhn

{"title":"Targeted design of organic Janus particles for improved photocatalytic hydrogen evolution.","authors":"Khaoula Missaoui, Guillaume Wantz, Thierry Toupance, Sylvain Chambon, Alexander Kuhn","doi":"10.1039/d5sc00802f","DOIUrl":"https://doi.org/10.1039/d5sc00802f","url":null,"abstract":"Organic bulk heterojunction particles are decorated in a well-controlled way with metals by using light-assisted bipolar electrodeposition to yield Janus particles. Their asymmetric character leads to significantly enhanced photocatalytic hydrogen evolution reaction. The organic particles are first synthesized via miniemulsion, tuning their size by carefully controlling various preparation parameters. Subsequently, the synergistic effect of an electric field and light is explored for the site-selective bipolar electrochemical deposition of different metals (Pt, Au or Pd). Photocatalytic tests reveal that in the case of platinum, the resulting Janus particles significantly outperform particles randomly covered with metal, as well as unmodified particles, showing an increase in hydrogen evolution efficiency by up to 500%. This superior performance is attributed to an enhanced charge carrier separation in the Janus structure, where Pt, confined at one side, facilitates more efficient electron shuttling and transfer. This work constitutes the first study reporting a promising approach for designing novel metal-organic Janus particles to boost photocatalytic hydrogen evolution and opens up new perspectives for optimizing the design of various other hybrid systems for sustainable energy conversion.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":7.6,"publicationDate":"2025-04-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12053469/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143970443","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Azetidinyl Malachite Green: a superior fluorogen-activating protein probe for live-cell and dynamic SIM imaging. Azetidinyl孔雀石绿：用于活细胞和动态SIM成像的优越的氟活化蛋白探针。

IF 7.6 1区化学

Chemical Science Pub Date : 2025-04-30 DOI: 10.1039/d5sc01150g

Fei Deng, Xiangning Fang, Qinglong Qiao, Guoli Han, Lu Miao, Shuangshuang Long, Zhaochao Xu

{"title":"Azetidinyl Malachite Green: a superior fluorogen-activating protein probe for live-cell and dynamic SIM imaging.","authors":"Fei Deng, Xiangning Fang, Qinglong Qiao, Guoli Han, Lu Miao, Shuangshuang Long, Zhaochao Xu","doi":"10.1039/d5sc01150g","DOIUrl":"https://doi.org/10.1039/d5sc01150g","url":null,"abstract":"Malachite Green (MG) and its fluorogen-activating protein (FAP) pair are valuable tools for live-cell and super-resolution fluorescence imaging due to their unique near-infrared absorption and signal enhancement. However, the low brightness and photostability of MG have limited its use in dynamic imaging. In this study, we introduce a novel derivative, azetidinly Malachite Green (Aze-MG), which enhances the brightness of the MG-FAP complex by 2.6-fold. This enhancement is achieved by replacing the N,N-dimethylamino group in MG with an azetidine group, which suppresses the twisted intramolecular charge transfer (TICT) effect, leading to improved quantum yield and photostability. Additionally, the reduced binding affinity of Aze-MG for FAP enables a buffering strategy, allowing the reversible exchange of photobleached fluorogens with free fluorogens, thereby ensuring stable fluorescence over time. This combination of improved brightness and buffering capability makes Aze-MG an ideal probe for live-cell and dynamic SIM imaging.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":7.6,"publicationDate":"2025-04-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12053737/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143982111","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Being a first generation university graduate, the impact on a career in science 作为第一代大学毕业生，这对科学事业的影响

IF 8.4 1区化学

Chemical Science Pub Date : 2025-04-30 DOI: 10.1039/d5sc00205b

Mariam Yacoub, Sarah Koops, Panagiota Axelithioti, Claudia Caltagirone, Emily Rose Draper, Cally Jo Elizabeth Haynes, Charlotte K Hind, Marion Kieffer, Larissa K. S. von Krbek, Anna McConnell, Sarah Pike, Anna Grace Slater, Jennifer Ruth Hiscock, Jennifer S. Leigh

引用次数: 0

Simultaneous electron and proton conduction in a stable metal organic material with highly selective electrocatalytic oxygen reduction reaction to water. 在稳定的金属有机材料中同时进行电子和质子传导，具有高选择性的电催化氧还原反应。

IF 7.6 1区化学

Chemical Science Pub Date : 2025-04-30 DOI: 10.1039/d5sc02474a

Rajat Saha, Amitosh Sharma, Anjila I Siddiqui, Samia Benmansour, Joaquín Ortega-Castro, Antonio Frontera, Biswajit Mondal, Myoung Soo Lah, Carlos J Gómez García

{"title":"Simultaneous electron and proton conduction in a stable metal organic material with highly selective electrocatalytic oxygen reduction reaction to water.","authors":"Rajat Saha, Amitosh Sharma, Anjila I Siddiqui, Samia Benmansour, Joaquín Ortega-Castro, Antonio Frontera, Biswajit Mondal, Myoung Soo Lah, Carlos J Gómez García","doi":"10.1039/d5sc02474a","DOIUrl":"https://doi.org/10.1039/d5sc02474a","url":null,"abstract":"Proton coupled electron transfer (PCET) is considered as the elementary step of several chemical, electrochemical and biological processes and thus the development of dual conducting materials has recently become a major focus in Chemical Science. Herein, we report the highly selective electrocatalytic oxygen reduction to water by the stable dual conducting metal-organic material (MOM) [Cu(INA)2(H2O)4] (INA = isonicotinate). Structural analysis reveals the important role of both, hydrogen bonding and π-interactions, in the formation of a supramolecular 3D network. Theoretical calculations show that hydrogen bonding interactions among the coordinated water molecules and deprotonated carboxylate oxygen atoms induce proton transport (2.26 ± 0.10 × 10-5 S cm-1 at 98% RH) while weak intermolecular π-interactions (π-π and anion-π) provide the pathway for electron transport (1.4 ± 0.1 × 10-7 S cm-1 at 400 K). Such dual proton and electron conductivity leads to a selective oxygen reduction reaction (ORR) to water in an alkaline medium. To the best of our knowledge, this is the first report on electrocatalytic ORR by a dual-conducting metal-organic material.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":7.6,"publicationDate":"2025-04-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12041934/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143978849","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Colloidal CuInS₂ quantum well nanostructures with II-VI semiconductors as barrier layers. 以II-VI半导体为势垒层的胶体CuInS2量子阱纳米结构。

IF 7.6 1区化学

Chemical Science Pub Date : 2025-04-30 DOI: 10.1039/d5sc00657k

Yue Qin, Xuerong Song, Hanzhuang Zhang, Wenyu Ji, Jiajia Ning

{"title":"Colloidal CuInS2 quantum well nanostructures with II-VI semiconductors as barrier layers.","authors":"Yue Qin, Xuerong Song, Hanzhuang Zhang, Wenyu Ji, Jiajia Ning","doi":"10.1039/d5sc00657k","DOIUrl":"https://doi.org/10.1039/d5sc00657k","url":null,"abstract":"Quantum well (QW) structures have been successfully produced and utilized in high-performance optoelectronic devices. By designing QW structures at the nanoscale, it is possible to combine the advantages of both QW structures and nanostructures, resulting in extraordinary properties. In this study, a CuInS2 (CIS) quantum well layer was successfully constructed within a single nanostructure using a colloidal method. Various QW nanostructures were synthesized, including CdS/CIS/CdS, CdS/CIS/ZnS, ZnS/CIS/CdS, and Cd-free ZnS/CIS/ZnS configurations. The shapes of these QW nanostructures were precisely tuned to form tetrahedrons, hexagonal columns, and rods. Importantly, the morphology and crystal structure of the CIS layer play a crucial role in determining the final morphologies of the QW nanostructures. These QW nanostructures exhibit fluorescence emission in the near-infrared range (NIR), achieving a maximum quantum yield of 37% at 783 nm. This work demonstrates the successful construction of a CIS quantum well layer within a single colloidal nanoparticle, providing a valuable research model for fundamental studies and offering promising materials for optoelectronic devices.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":7.6,"publicationDate":"2025-04-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12056669/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143987878","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Inhibitions imposed by kinetic constraints of membranes in all-solid-state ion-selective electrodes: characteristics of interfacial capacitances in solid contacts 全固态离子选择电极中膜的动力学约束所施加的抑制作用：固体接触界面电容的特性

IF 8.4 1区化学

Chemical Science Pub Date : 2025-04-30 DOI: 10.1039/d5sc01241d

Rui-Ze Xia, Xin Cai, Jing-Yi Lin, Yong-Huan Zhao, Zi-Hao Liu, Chen-Lu Wang, Shi-Hua Chen, Meng Yang, Zong-Yin Song, Pei-Hua Li, Xing-Jiu Huang

{"title":"Inhibitions imposed by kinetic constraints of membranes in all-solid-state ion-selective electrodes: characteristics of interfacial capacitances in solid contacts","authors":"Rui-Ze Xia, Xin Cai, Jing-Yi Lin, Yong-Huan Zhao, Zi-Hao Liu, Chen-Lu Wang, Shi-Hua Chen, Meng Yang, Zong-Yin Song, Pei-Hua Li, Xing-Jiu Huang","doi":"10.1039/d5sc01241d","DOIUrl":"https://doi.org/10.1039/d5sc01241d","url":null,"abstract":"Although various materials as solid contacts have been extensive studied in all-solid-state ion-selective electrodes, there is still a lack in the study regarding kinetic phenomena at solid-solid and solid-liquid interfaces. This may lead to confusion between the performance of capacitors and that of electrical analysis systems, then finally misjudge material properties. While there are established methodologies for investigating capacitive mechanisms, they all center on the energy storage properties of particular materials and lack the capability to analyze real detected systems involving membranes. This study proposed an algorithm to investigate electrode interfaces with complex structures and uncovered the impact of membranes on the capacitance of solid contacts through experimental data and simulations. The electrochemical impedance spectroscopy is clustered using a machine learning algorithm and then distribution of relaxation time analysis is utilized to simulate results and generate multiple models of electrode interfaces. The step potential electrochemical spectroscopy is simulated based on the electrode interface model to quantitatively analyze specific charge storage processes. Simulated results revealed that the symmetry of primary charge processes under varying overpotentials for different solid contacts is proportional to the conversion ratios of each material’s capacitance, which is attributed to the Inhibition on electrode interfaces of ion-selective membranes. This work highlights the importance of considering interactions between membranes and materials in the development of transduction materials and can also be extended to investigate electrode interfaces not merely all-solid-state ion-selective electrodes.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"52 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143893971","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}

引用次数: 0

Probing the Ferredoxin:Hydrogenase Electron Transfer Complex by Infrared Difference Spectroscopy 红外差谱法探测铁氧还蛋白-氢化酶电子转移配合物

IF 8.4 1区化学

Chemical Science Pub Date : 2025-04-30 DOI: 10.1039/d5sc00550g

Selmihan Sahin, Johanna Brazard, Kilian Zuchan, Takuji B. M. Adachi, Ulrich Mühlenhoff, Ross D. Milton, Sven Timo Stripp

{"title":"Probing the Ferredoxin:Hydrogenase Electron Transfer Complex by Infrared Difference Spectroscopy","authors":"Selmihan Sahin, Johanna Brazard, Kilian Zuchan, Takuji B. M. Adachi, Ulrich Mühlenhoff, Ross D. Milton, Sven Timo Stripp","doi":"10.1039/d5sc00550g","DOIUrl":"https://doi.org/10.1039/d5sc00550g","url":null,"abstract":"Ferredoxins are small iron-sulfur proteins that engage in one-electron transfer with oxidoreductases across all domains of life. The catalyzed reactions often include multiple electrons, e.g., in the two-electron reduction of NADP+ during photosynthesis or the reduction of protons to H2 by the metalloenzyme hydrogenase. To date, the microscopic details of how ferredoxins facilitate multiple electron redox chemistry are unknown. Ferredoxins of the Allochromatium vinosum subfamily contain two [4Fe-4S] clusters, which allows for two one-electron transfer reactions. However, the iron-sulfur clusters of 2[4Fe-4S]-type ferredoxins typically have very similar reduction potentials and conclusive evidence for the transfer of two electrons during a single protein-protein interaction (PPI) has not been reported. In this work, the electron transfer complexes between clostridial 2[4Fe-4S] ferredoxin, CpFd, and [FeFe]-hydrogenases from both Clostridium pasteurianum (CpI) and Chlamydomonas reinhardtii (CrHydA) were investigated. Introducing a non-canonical amino acid near to one of the iron-sulfur clusters of CpFd permitted the quantification of electric field changes via the vibrational Stark effect by Fourier-transform infrared (FTIR) spectroscopy. Upon reduction, in situ FTIR difference spectroscopy reported on protein structural changes and microscale thermophoresis revealed that the affinity between ferredoxin and hydrogenase is modulated by redox-dependent PPIs. Prompted by these findings, we suggest a model how ferredoxin efficiently facilitates multiple electron redox chemistry based on individual one-electron transfer reactions.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"33 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143890233","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}

引用次数: 0

Isothiourea Catalysed Enantioselective Generation of Point and Axially Chiral Iminothia- and Iminoselenazinanones 异硫脲催化点手性和轴向手性亚氨基壬烯酮和亚氨基硒壬烯酮的对映选择性生成

IF 8.4 1区化学

Chemical Science Pub Date : 2025-04-30 DOI: 10.1039/d5sc02435h

Alastair Nimmo, Alister S. Goodfellow, Jacob T. Guntley, Aidan P McKay, David Bradford Cordes, Michael Buehl, Andrew D Smith

{"title":"Isothiourea Catalysed Enantioselective Generation of Point and Axially Chiral Iminothia- and Iminoselenazinanones","authors":"Alastair Nimmo, Alister S. Goodfellow, Jacob T. Guntley, Aidan P McKay, David Bradford Cordes, Michael Buehl, Andrew D Smith","doi":"10.1039/d5sc02435h","DOIUrl":"https://doi.org/10.1039/d5sc02435h","url":null,"abstract":"Symmetrical and unsymmetrical thioureas, as well as unsymmetrical selenoureas, are used in an isothiourea-catalysed Michael addition-lactamisation protocol using α,β-unsaturated pentafluorophenyl esters to generate iminothia- and iminoselenazinanone heterocycles with high enantioselectivity (up to 99:1 er). The scope and limitations of this process have been widely investigated (40 examples in total) with unsymmetrical thio- and selenoureas containing ortho-substituted N-aryl substituents giving atropisomeric products, leading to an effective process for iminothia- and iminoselenazinanones heterocyclic products containing both point and axially chiral stereogenic elements with excellent stereocontrol (up to >95:5 dr and 98:2 er). Mechanistic investigation showed that (i) the catalytically liberated aryloxide could deprotonate an electron-deficient thiourea; (ii) in the absence of an isothiourea catalyst, this leads to formation of racemic product; (iii) a crossover experiment indicates the reversibility of the thia-Michael addition. Computational analysis has identified the factors leading to enantioselectivity within this process, with stereocontrol arising from the lactamisation step within the catalytic cycle.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"104 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143890236","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}

引用次数: 0