Catalytic Kinetic Resolution of Monohydrosilanes via Rhodium-Catalyzed Enantioselective Intramolecular Hydrosilylation
Angew Chem Int Ed Engl. 2024 Apr 11:e202404732. doi: 10.1002/anie.202404732. Online ahead of print.ABSTRACTThe catalytic access of silicon-stereogenic organosilanes remains a big challenge, and largely depends on the desymmetrization of the symmetric precursors with two identical substitutes attached to the silicon atom. Here we report the construction of silicon-stereogenic organosilanes via catalytic kinetic resolution of racemic monohydrosilanes with good to excellent selectivity factors. Both Si-stereogenic dihydrobenzosiloles and Si-stereogenic monohydrosilanes could be efficiently accessed in one single operation via...
Source: Angewandte Chemie - April 12, 2024 Category: Chemistry Authors: Fei-Hu Gou Fei Ren Yichen Wu Peng Wang Source Type: research
Stabilization of Pd0 by Cu Alloying: Theory-Guided Design of Pd3Cu Electrocatalyst for Anodic Methanol Carbonylation
Angew Chem Int Ed Engl. 2024 Apr 12:e202401311. doi: 10.1002/anie.202401311. Online ahead of print.ABSTRACTElectrocatalytic carbonylation of CO and CH3OH to dimethyl carbonate (DMC) on metallic palladium (Pd) electrode offers a promising strategy for C1 valorization at the anode. However, its broader application is limited by the high working potential and the low DMC selectivity accompanied with severe methanol self-oxidation. Herein, our theoretical analysis of the intermediate adsorption interactions on both Pd0 and Pd4+ surfaces revealed that inevitable reconstruction of Pd surface under strongly oxidative potential di...
Source: Angewandte Chemie - April 12, 2024 Category: Chemistry Authors: Yunru Shi Yi-Fan Hu Jinyu Ye Gang Zhong Chungu Xia Zhi-Pan Liu Yang Huang Lin He Source Type: research
Circularly Polarized Luminescence Induced by Hydrogen-Bonding Networks in a One-Dimensional Hybrid Manganese(II) Chloride
Angew Chem Int Ed Engl. 2024 Apr 12:e202405310. doi: 10.1002/anie.202405310. Online ahead of print.ABSTRACTChiral hybrid metal halides hold great potential as the circularly polarized luminescence light sources. Herein, we have obtained two enantiomeric pairs of one-dimensional hybrid chiral-manganese(II) chloride single crystals, R/S-(3-methyl piperidine)MnCl3 (R/S-1) and R/S-(3-hydroxy piperidine)MnCl3 (R/S-2), crystallizing in non-centrosymmetric space group P212121. In comparison to R/S-1, R/S-2 single crystals not only show red emission with near-unity photoluminescence quantum yield and high resistance to thermal que...
Source: Angewandte Chemie - April 12, 2024 Category: Chemistry Authors: Jing Li Qiulian Luo Jianwu Wei Liya Zhou Peican Chen Binbin Luo Yibo Chen Qi Pang Jin Zhong Zhang Source Type: research
The CF3 Group as a Synthon of the CF+ Unit in Palladium Chemistry
Angew Chem Int Ed Engl. 2024 Apr 12:e202403108. doi: 10.1002/anie.202403108. Online ahead of print.ABSTRACTThe homoleptic trifluoromethyl-palladium(II) complex [Pd(CF3)4]2- (1) is shown to be highly active towards amines. Thus, when treated with primary amines RNH2, it readily undergoes aminolysis of one of the CF3 ligands affording the isocyanide complexes [(CF3)3Pd(CNR)]- (R = aryl). In this process the original CF3 group undergoes total defluorination. Interestingly, the reaction of 1 with secondary amines R2NH proceeds with loss of just two F-substituents, whereby the Fischer-type fluoroaminocarbene complexes [(CF3)3Pd...
Source: Angewandte Chemie - April 12, 2024 Category: Chemistry Authors: Daniel Joven-Sancho Miguel Baya Antonio Mart ín Jes ús Orduna Babil Menj ón Source Type: research
On the Mechanisms of Hypohalous Acid Formation and Electrophilic Halogenation by Non-Native Halogenases
Angew Chem Int Ed Engl. 2024 Apr 12:e202403858. doi: 10.1002/anie.202403858. Online ahead of print.ABSTRACTEnzymatic electrophilic halogenation is a mild tool for functionalization of diverse organic compounds. Only a few groups of native halogenases are capable of catalyzing such a reaction. Here, we used a mechanism-guided strategy to discover the electrophilic halogenation activity catalyzed by non-native halogenases. As the ability to form a hypohalous acid (HOX) is key for halogenation, flavin-dependent monooxygenases/oxidases capable of forming C4a-hydroperoxyflavin (FlC4a-OOH) such as dehalogenase, hydroxylases, luc...
Source: Angewandte Chemie - April 12, 2024 Category: Chemistry Authors: Kridsadakorn Prakinee Narin Lawan Aisaraphon Phintha Surawit Visitsatthawong Penchit Chitnumsub Watcharapa Jitkaroon Pimchai Chaiyen Source Type: research
Deciphering Anion-Modulated Solvation Structure for Calcium Intercalation into Graphite for Ca-Ion Batteries
This study, for the first time, elucidates the pivotal role of anions in modulating the Ca ion solvation structures and their subsequent intercalation into graphite. Specifically, the electrostatic interactions between Ca ion and anions govern the configurations of solvated-Ca-ion in dimethylacetamide-based electrolytes and graphite intercalation compounds. Among the anions considered (BH4-, ClO4-, TFSI- and [B(hfip)4]-), the coordination of four solvent molecules per Ca ion (CN=4) leads to the highest reversible capacities and the fastest reaction kinetics in graphite. Our study illuminates the origins of the distinct Ca ...
Source: Angewandte Chemie - April 12, 2024 Category: Chemistry Authors: Yuyang Yi Youdong Xing Hui Wang Zhihan Zeng Zhongti Sun Renjie Li Huijun Lin Yiyuan Ma Xiangjun Pu Molly Meng-Jung Li Kyu-Young Park Zheng-Long Xu Source Type: research
Efficient Tandem Cu-Catalyzed Click Synthesis of Multi-Sugar-Modified Oligonucleotides
Angew Chem Int Ed Engl. 2024 Apr 12:e202405161. doi: 10.1002/anie.202405161. Online ahead of print.ABSTRACTNucleic acids in the form of siRNA, antisense oligonucleotides or mRNA are currently explored as new promising modalities in the pharmaceutical industry. Particularly, the success of mRNA-vaccines against SARS-CoV-2, along with the successful development of the first sugar-modified siRNA therapeutics has inspired the field. The development of nucleic acid therapeutics requires efficient chemistry to link oligonucleotides to chemical structures that can improve stability, boost cellular uptake, or enable specific targe...
Source: Angewandte Chemie - April 12, 2024 Category: Chemistry Authors: Annika J T ölke Julia F Gaisbauer Yasmin V G ärtner Barbara Steigenberger Anna Holovan Filipp Streshnev Sabine Schneider Markus M üller Thomas Carell Source Type: research
A 2D Acridine-Based Covalent Organic Framework for Selective Detection and Efficient Extraction of Gold from Complex Aqueous-Based Matrices
Angew Chem Int Ed Engl. 2024 Apr 12:e202402205. doi: 10.1002/anie.202402205. Online ahead of print.ABSTRACTDeveloping candidate materials which possess the ability of both selective detection and efficient capture of precious metal gold is highly desirable for environment and economy. However, most of reported materials only focus on single function, which seriously restricts their practical application as probes or adsorbents. Herein, a two dimensional (2D) acridine-based covalent organic framework (TpDa-COF) is prepared via the linkage of imine bonds for gold detection and adsorption. The synthesized COF can achieve both...
Source: Angewandte Chemie - April 12, 2024 Category: Chemistry Authors: D C Mei Bing Yan Source Type: research
Confined-Coordination Induced Intergrowth of Metal-Organic Framework into Precise Molecular Sieving Membranes
Angew Chem Int Ed Engl. 2024 Apr 12:e202405676. doi: 10.1002/anie.202405676. Online ahead of print.ABSTRACTMetal-organic framework (MOF) membranes with rich functionality and tunable pore system are promising for precise molecular separation; however, it remains a challenge to develop defect-free high-connectivity MOF membrane with high water stability owing to uncontrollable nucleation and growth rate during fabrication process. Herein, we report on a confined-coordination induced intergrowth strategy to fabricate lattice-defect-free Zr-MOF membrane towards precise molecular separation. The confined-coordination space pro...
Source: Angewandte Chemie - April 12, 2024 Category: Chemistry Authors: Guozhen Liu Binyu Mo Yanan Guo Zhenyu Chu Xiao-Ming Ren Kecheng Guan Renjie Miao Zhenggang Wang Yaxin Zhang Wenqi Ji Gongping Liu Hideto Matsuyama Wanqin Jin Source Type: research
Regulating the Topology of Covalent Organic Frameworks for Boosting Overall H2O2 Photogeneration
Angew Chem Int Ed Engl. 2024 Apr 12:e202405763. doi: 10.1002/anie.202405763. Online ahead of print.ABSTRACTPhotocatalytic oxygen reduction reactions and water oxidation reactions are extremely promising green approaches for massive H2O2 production. Nonetheless, constructing effective photocatalysts for H2O2 generation is critical and still challenging. Since the network topology has significant impacts on the electronic properties of two dimensional (2D) polymers, herein, for the first time, we regulated the H2O2 photosynthetic activity of 2D covalent organic frameworks (COFs) by topology. Through designing the linking sit...
Source: Angewandte Chemie - April 12, 2024 Category: Chemistry Authors: Jie-Yu Yue Jing-Xian Luo Zi-Xian Pan Rui-Zhi Zhang Peng Yang Qing Xu Bo Tang Source Type: research
A Stapled Peptide Inhibitor Targeting the Binding Interface of N6-Adenosine-Methyltransferase Subunits METTL3 and METTL14 for Cancer Therapy
In this study, we targeted protein-protein interactions at the METTL3-METTL14 binding interface to inhibit complex formation and subsequent catalysis of RNA m6A modification. Among candidate peptides, RM3 exhibited the highest anti-cancer potency, inhibiting METTL3 activity while also facilitating its proteasomal degradation. We then designed a stapled peptide inhibitor (RSM3) with enhanced peptide stability and formation of the α-helical secondary structure required for METTL3 interaction. Functional and transcriptomic analysis in vivo indicated that RSM3 induced upregulation of programmed cell death-related genes while ...
Source: Angewandte Chemie - April 12, 2024 Category: Chemistry Authors: Zenghui Li Yuqing Feng Hong Han Xingyue Jiang Weiyu Chen Xuezhen Ma Yang Mei Dan Yuan Dingxiao Zhang Junfeng Shi Source Type: research
Disaggregation-Activated pan-COX Imaging Agents for Human Soft Tissue Sarcoma
Angew Chem Int Ed Engl. 2024 Apr 12:e202405525. doi: 10.1002/anie.202405525. Online ahead of print.ABSTRACTCancer stem cells are pivotal players in tumors initiation, growth, and metastasis. While several markers have been identified, there remain challenges particularly in heterogeneous malignancies like adult soft tissue sarcomas, where conventional markers are inherently overexpressed. Here, we designed BODIPY scaffold fluorescence probes (BD-IMC-1, BD-IMC-2) that activate via disaggregation targeting for cyclooxygenase (COX), a potential marker for CSCs in sarcoma in clinical pathology. Based on their structures, BD-IM...
Source: Angewandte Chemie - April 12, 2024 Category: Chemistry Authors: Kyung Tae Hong Seung Bin Park Dhiraj P Murale Jung Hoon Lee Jangsun Hwang Woo Young Jang Jun-Seok Lee Source Type: research
DOTA-based plectin-1 targeted contrast agent enables detection of pancreatic cancer in human tissue
Angew Chem Int Ed Engl. 2024 Apr 12:e202318485. doi: 10.1002/anie.202318485. Online ahead of print.ABSTRACTPancreatic ductal adenocarcinoma (PDAC) is a highly aggressive and lethal malignancy with extremely poor patient survival rates. A key reason for the poor prognosis is the lack of effective diagnostic tools to detect the disease at curable, premetastatic stages. Tumor surgical resection is PDAC first-line treatment, however distinguishing between cancerous and healthy tissue with current imaging tools remains a challenge. In this work, we report a DOTA-based fluorescent probe targeting plectin-1 for imaging PDAC with ...
Source: Angewandte Chemie - April 12, 2024 Category: Chemistry Authors: Thais Gazzi Marina Lesina Qinghua Wang Alexandra Berninger Silke Radetzki Ihsan Ekin Demir Larissa Heinemann Waldemar Meiser Sebastian Wilke Jens Peter von Kries Hana Alg ül Hai-Yu Hu Marc Nazar é Source Type: research
Imidazole-Intercalated Cobalt Hydroxide Enabling the Li+ Desolvation/Diffusion Reaction and Flame Retardant Catalytic Dynamics for Lithium Ion Batteries
In this study, we introduce a unique approach to synthesize anode materials for lithium-ion batteries, specifically imidazole-intercalated cobalt hydroxide. This innovative material significantly enhances the Li+ desolvation/diffusion reaction and flame-retardant dynamics through complexing and catalytic synergetic effects. The lithium-ion batteries incorporating these materials demonstrate exceptional performance, boasting an impressive capacity retention of 997.91 mAh g-1 after 500 cycles. This achievement can be attributed to the optimization of the solid electrolyte interphase (SEI) interface engineering, effectively m...
Source: Angewandte Chemie - April 11, 2024 Category: Chemistry Authors: Liu Yang Yisha Wang Jingwen Wang Yapeng Zheng Edison Huixiang Ang Yuan Hu Jixin Zhu Source Type: research
Large Libraries of Structurally Diverse Macrocycles Suitable for Membrane Permeation
Angew Chem Int Ed Engl. 2024 Apr 11:e202400350. doi: 10.1002/anie.202400350. Online ahead of print.ABSTRACTMacrocycles offer an attractive format for drug development due to their good binding properties and potential to cross cell membranes. To efficiently identify macrocyclic ligands for new targets, methods for the synthesis and screening of large combinatorial libraries of small cyclic peptides were developed, many of them using thiol groups for efficient peptide macrocyclization. However, a weakness of these libraries is that invariant thiol-containing building blocks such as cysteine are used, resulting in a region t...
Source: Angewandte Chemie - April 11, 2024 Category: Chemistry Authors: Alexander L Nielsen Zsolt Bognar Ganesh K Mothukuri Anne Zarda Mischa Schuttel Manuel L Merz Xinjian Ji Edward Will Monica Chinellato Christian R O Bartling Kristian Stromgaard Laura Cendron Alessandro Angelini Christian Heinis Source Type: research
