{"title":"Ligand-Controlled Regiodivergent Carbosilylation of 1,3-Dienes via Nickel-Catalyzed Three-Component Coupling Reactions","authors":"Shan Jiang, Tianze Zhang, Xiao-Yuan Luo, Shoucheng Dong, Jin-Tao Ma, Li-Jun Xiao","doi":"10.1002/anie.202504494","DOIUrl":"https://doi.org/10.1002/anie.202504494","url":null,"abstract":"The regiodivergent carbosilylation of 1,3-dienes presents a formidable challenge due to inherently complex selectivity control over multiple potential reaction pathways. Here, we report a ligand-controlled, regiodivergent carbosilylation of 1,3-dienes with aldehydes and silylboranes, achieving unprecedented site-selectivity using nickel catalysts equipped with distinct phosphine ligands. The use of triethylphosphine promotes 4,3-addition selectivity, while employing (2-biphenyl)dicyclohexylphosphine facilitates 4,1-addition selectivity. This method displays excellent regio- and diastereoselectivity, as well as a broad substrate scope and substantial functional group tolerance. Mechanistic studies indicate that the ligand choice is crucial for directing the reaction pathway and stabilizing π-allyl-nickel intermediates. Our protocol provides a practical and efficient approach to synthesizing valuable functionalized allylsilanes, which are important in various synthetic applications.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"58 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143766770","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}
Bin-Qing He, Lu Zhao, Jun Zhang, Wen-Hui Bao, Mingjun Yang, Xuesong Wu
{"title":"Alcohol Activation by Benzodithiolylium for Deoxygenative Alkylation Driven by Photocatalytic Energy Transfer","authors":"Bin-Qing He, Lu Zhao, Jun Zhang, Wen-Hui Bao, Mingjun Yang, Xuesong Wu","doi":"10.1002/anie.202423795","DOIUrl":"https://doi.org/10.1002/anie.202423795","url":null,"abstract":"The 1,3-benzodithiolylium (BDT) cation was identified as an efficient hydroxyl-activating reagent for the photocatalytic deoxygenative radical functionalization of alcohols in the absence of any electron transfer process. A series of unprecedented photocatalytic energy transfer-driven deoxygenative radical coupling reactions of alcohols with bifunctional oxime carbonates have been developed based on the activation by BDT. Nickel-catalyzed radical sorting followed by C(sp3)−C(sp3) bond construction facilitate the heteroselective cross-coupling of two distinct alkyl radicals originating from parallel radical relays. These reactions allow the versatile synthesis of diverse nitrogen-containing molecules, including amino acid derivatives, imines, nitriles, and pyrrolines, by using ubiquitous alcohols as regiodefined alkyl building blocks.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"69 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143766823","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}
Bo-Bo Gou, Wen-Jie Shen, Yuan-Jun Gao, Qing Gu, Shu-Li You
{"title":"Rhodium-Catalyzed Atroposelective Synthesis of Axially Chiral 1-Aryl Isoquinolines via De Novo Isoquinoline Formation","authors":"Bo-Bo Gou, Wen-Jie Shen, Yuan-Jun Gao, Qing Gu, Shu-Li You","doi":"10.1002/anie.202502131","DOIUrl":"https://doi.org/10.1002/anie.202502131","url":null,"abstract":"Axially chiral heterobiaryl serves as a core skeleton for bioactive molecules, chiral ligands and organocatalysts. Enantioselective de novo formation of the heteroaromatic ring is one of the most straightforward approaches to access enantioenriched heterobiaryls. Herein, an enantioselective de novo construction of isoquinolines via rhodium-catalyzed C−H activation/annulation of aromatic imines with alkynes is disclosed. This approach is operationally simple, allowing for rapid access to a variety of axially chiral 1-aryl isoquinolines in excellent yields and enantioselectivity (up to 98% yield and 99:1 er). The synthetic application of the current method was demonstrated by functional group transformations and the compatibility with mmol-scale reaction. The detailed experimental and theoretical studies revealed the turnover-limiting step and provided insights into the origin of the enantioselectivity for this reaction.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"22 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143766869","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}
Bohdan Kozibroda, Jean-Marie Lehn, Andrey S. Klymchenko
{"title":"Frontispiece: Fluorescent Artificial Receptor for Dopamine based on Molecular Recognition-driven Dynamic Covalent Chemistry in a Lipid Nanoreactor","authors":"Bohdan Kozibroda, Jean-Marie Lehn, Andrey S. Klymchenko","doi":"10.1002/anie.202581461","DOIUrl":"https://doi.org/10.1002/anie.202581461","url":null,"abstract":"<p>In their Research Article (e202419905), Andrey S. Klymchenko et al. introduce a dynamic artificial receptor for neurotransmitter dopamine that synergically combines molecular recognition with dynamic imine bond formation of a fluorescent dye inside a lipid nanoreactor, triggering its emission color change. This nanoprobe enables dopamine detection with remarkable selectivity without interference of competing biogenic amines and biological fluids, such as blood serum, plasma, urine and cell lysate.\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure>\u0000 </p>","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"64 14","pages":""},"PeriodicalIF":16.1,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/anie.202581461","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143761971","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}
Li-Wen Hui, Yee Lin Phang, Chen-Yang Ye, Jin-Yu Lai, Feng-Lian Zhang, Yao Fu, Yi-Feng Wang
{"title":"Remote Spin-Center Shift Enables Activation of Distal Benzylic C–O and C–N Bonds","authors":"Li-Wen Hui, Yee Lin Phang, Chen-Yang Ye, Jin-Yu Lai, Feng-Lian Zhang, Yao Fu, Yi-Feng Wang","doi":"10.1002/anie.202506771","DOIUrl":"https://doi.org/10.1002/anie.202506771","url":null,"abstract":"A spin-center shift (SCS) is a radical process that commonly involves a 1,2-radical shift along with the elimination of an adjacent leaving group by a two-electron ionic movement. The conventional SCS process is largely limited to 1,2-radical translocation, while a remote SCS event involving 1,n-radical translocation over a greater distance to enable distal bond functionalization remains largely underexplored. Herein, we report the boryl radical-promoted distal deoxygenation and deamination of free benzylic alcohols and simple benzylic amines, respectively, through a remote SCS event. The reaction was initiated by the addition of a 4-dimethylaminopyridine (DMAP)-boryl radical to the carbonyl oxygen atom of a benzoate or benzamide. Then, radical translocation took place across the aromatic ring to promote benzylic C−O or C−N bond cleavage. The resulting radical intermediate subsequently coupled with various alkenes to afford a wide range of alkylated products. The proposed mechanistic pathway was supported by experimental investigations.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"146 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143766773","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}
Huan-Huan Chen, Xiao-Gang Chen, Zhe-Kun Xu, Hang Peng, Yan Qin, Hui-Peng Lv, Xian-Jiang Song, Sheng-Qian Hu, Luan-Ying Ji, Jun-Si Zhou, Ren-Gen Xiong, Wei-Qiang Liao
{"title":"A 3D Hybrid Perovskite Ferroelastic with Triclinic-to-Cubic Phase Transition Boosts Temperature/Pressure Dual On/Off Switchable Birefringence","authors":"Huan-Huan Chen, Xiao-Gang Chen, Zhe-Kun Xu, Hang Peng, Yan Qin, Hui-Peng Lv, Xian-Jiang Song, Sheng-Qian Hu, Luan-Ying Ji, Jun-Si Zhou, Ren-Gen Xiong, Wei-Qiang Liao","doi":"10.1002/anie.202503681","DOIUrl":"https://doi.org/10.1002/anie.202503681","url":null,"abstract":"Birefringent crystals have gained enormous attention for decades due to their unique ability to manipulate polarization light. However, achieving the fascinating on/off (active/inactive) switchable birefringence under external stimuli in crystals remains a huge challenge, and the stimuli employed have been constrained predominantly to temperature. Here, through H/F substitution, we designed a three-dimensional hybrid double perovskite ferroelastic [C3H5FNH2]2[(NH4)Fe(CN)6] (1-F), which undergoes a mmF ferroelastic transition at 296 K, with the highest possible orientation states of 24 among ferroelastic crystals. Notably, the ferroelastic phase transition of 1-F can also be triggered by pressure with a low critical pressure of ~0.3 GPa. More importantly, 1-F shows the unprecedented temperature/pressure dual stimuli induced on/off switching of birefringence between the birefringence-active state in the anisotropic triclinic ferroelastic P phase and the birefringence-inactive state in the isotropic cubic paraelastic Fmm phase during the mmF ferroelastic transition. To the best of our knowledge, this is the first report of dual stimuli-induced switchable birefringence in crystals. Our work paves a new way for the switching of birefringence and shed light on the further exploration of switchable birefringence in ferroelastics.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"30 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143767146","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":"Bio-Inspired Self-Activating Polydimethylsiloxane-Modified CrOx/Al2O3 Catalyst for Acetylene Semi-Hydrogenation","authors":"Weiping Ding, Chenyang Shen, Yibo Wang, Jun Yao, Fengfeng Li, Feifei Mei, Zhewei Zhang, Huili Lu, Xuefeng Guo, Luming Peng, Nianhua Xue, Yan Zhu, Zhaoxu Chen","doi":"10.1002/anie.202504399","DOIUrl":"https://doi.org/10.1002/anie.202504399","url":null,"abstract":"Biomimetic approach is a nature-driven strategy for designing functional materials to meet the industrial challenges. Here we demonstrate the bio-inspired discovery of a self-activating catalyst, with polydimethylsiloxane anchored over the surface of CrOx/Al2O3, exhibiting comparable performance with noble metallic catalysts for acetylene semi-hydrogenation. In addition, the dynamic movement of polymer chains with high flexibility renders the catalyst to impose proactive perturbation to the undesired coke precursors generated in reaction, analogous to the function of hair-like cilia on the surface of respiratory epithelial cells, thus avoiding the site-blocking induced by carbonaceous deposits and sustaining the catalyst stable for 1000 h without any deactivation. This study paves the way to the develop other heterogeneous catalysts with high efficiency and durability via mimicking the innate defense mechanism of natural organism.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"109 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143766824","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}
Guochao Liu, Min Lin, Yali Xing, Shuqi Cheng, Han Wang, Daohao Li, Xiaojing Long, Qianrong Fang
{"title":"Oligoether Chain Engineering in Covalent Organic Frameworks: Enhancing Transport Pathways and Oxygen Reduction Activity for Efficient Electrocatalytic Hydrogen Peroxide Production","authors":"Guochao Liu, Min Lin, Yali Xing, Shuqi Cheng, Han Wang, Daohao Li, Xiaojing Long, Qianrong Fang","doi":"10.1002/anie.202500945","DOIUrl":"https://doi.org/10.1002/anie.202500945","url":null,"abstract":"Oligoethers with various numbers of ethylene oxide (EO) units, known for their flexibility, electronegativity, and hydrophilicity, can be leveraged to construct complex molecular architectures with broad applicability. In this study, we present the synthesis of two-dimensional covalent organic frameworks incorporating oligoethers with EO segments of varying lengths (2D-COF-EOs) to explore the role of EO units in modulating the two-electron (2e−) oxygen reduction reaction (ORR) pathway for electrocatalytic hydrogen peroxide (H2O2) production. By embedding hydrophilic EO side chains into the hydrophobic COF frameworks, intermolecular interactions are promoted through hydrogen bonding, leading to the self-assembly and spatial aggregation of these side chains. The high crystallinity of the COFs facilitates orderly stacking of the skeleton, creating hydrophilic nanoscale transport channels that enhance ORR kinetics. Among the synthesized COFs, 2D-COF-EO1, which contains one EO group, exhibits a remarkable H2O2 production rate of 5820 mmol gcat−1 h−1 and an ORR selectivity of 89.2%. Theoretical calculations and in situ electrocatalytic experiments reveal that the elongation of the EO units significantly alters the electronic structure of carbon atoms adjacent to oxygen atoms, lowering the energy barriers associated with the formation of OOH* intermediates and thus promoting the 2e− ORR pathway.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"216 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143767147","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":"Short Lifetime Radical Metal Cluster Scintillator","authors":"Jia-Wang Yuan, Qiu-Chen Peng, Ruo-Yu Cao, Qi Yang, Ying-Ying Lei, Zi-Ying Gao, Zhao-Yang Wang, Kai Li, Shuang-Quan Zang","doi":"10.1002/anie.202503457","DOIUrl":"https://doi.org/10.1002/anie.202503457","url":null,"abstract":"Metal clusters, an emerging class of scintillator materials, have attracted much attention owing to their inherently high X-ray absorption, mild synthesis conditions, low toxicity, strong luminescence, and large Stokes shift. However, the decay lifetime of metal clusters is usually on the order of microseconds, which is unfavorable for safety inspection, nondestructive testing, and medical imaging. Here, the open-shell luminescent radical ligand was used to construct the first radical cluster scintillator Cu2I2(L)4. The spin-allowed doublet emission of Cu2I2(L)4 theoretically enabled 100% exciton utilization and exhibited a short radiation decay lifetime on the nanosecond scale. Cu2I2(L)4 can be fabricated into a flexible scintillator screen for X-ray imaging, achieving a high resolution of 30.7 LP mm-1. More importantly, the Cu2I2(L)4 scintillator screen has no residual images during X-ray imaging. This work reports the first luminescent metal cluster with a radical ligand and presents a new strategy for constructing short lifetime X-ray scintillators.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"62 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143766772","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 Capping-assisted Strategy for Synthesis of Glass-like Carboxylate-based Coordination Polymers","authors":"Bo Liu, Mohamed Albolkany, Songlin Cui, Yuan Zhao","doi":"10.1002/anie.202500266","DOIUrl":"https://doi.org/10.1002/anie.202500266","url":null,"abstract":"The direct preparation of glass-like carboxylate-based coordination polymers (CPs) possessing continuous internal structure and transparency is challenging due to the lack of control on coordination kinetics and subsequently the range of order. Herein, a capping-assisted strategy was presented to control the molecular assembly during the metal-ligand coordination in the solution and to inhibit the long-range of order hence building glass-like CPs (g-CPs) mimicking the polymerization process. 1,3,5-benzene tricarboxylate (BTC) ligand was used to connect the copper cations (Cu2+) into metal-organic complexes of different Cu: BTC ratios (metal-organic pool) in presence of an excess of triethyl amine as a capping agent. Concentrating the Cu-BTC complexes and further drying under mild conditions induced the decapping process which triggered the random crosslinking between the free carboxylate and Cu2+ to form a boundary-free continuous internal structure. The as-prepared Cu-BTC g-CP exhibited an approximately similar fine structure like its crystalline counterpart (HKUST-1), which facilitated solvent and thermal-induced crystallization. Due to the internal structure continuity, the g-CP possesses ceramic-like hardness and wear resistance and plastic-like resilience. This capping-assisted strategy has been successfully extended to Ni-BTC and Fe-BTC systems under mild conditions and thus presenting a general method for the formation of glass-like carboxylate-based CPs.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"37 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143766825","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}