An Expedient Radical Approach for the Decarboxylative Synthesis of Stereodefined All-Carbon Tetrasubstituted Olefins
We report a user-friendly approach for the decarboxylative formation of stereodefined and complex tri- and tetra-substituted olefins from vinyl cyclic carbonates and amines as radical precursors. The protocol relies on easy photo-initiated α-amino-radical formation followed by addition onto the double bond of the substrate resulting in a sequence involving carbonate ring-opening, double bond relay, CO2 extrusion and finally O-protonation. The developed protocol is efficient for both mismatched and matched polarity substrate combinations, and the scope of elaborate stereodefined olefins that can be forged including drug-fu...
Source: Angewandte Chemie - April 15, 2024 Category: Chemistry Authors: Qian Zeng Nirwan Yamini Jordi Benet-Buchholz Arjan Willem Kleij Source Type: research
Detergent Chemistry Modulates the Transgression of Planetary Boundaries including Antimicrobial Resistance and Drug Discovery
Angew Chem Int Ed Engl. 2024 Apr 15:e202403833. doi: 10.1002/anie.202403833. Online ahead of print.ABSTRACTDetergent chemistry enables applications in the world today while harming safe operating spaces that humanity needs for survival. Aim of this review is to support a holistic thought process in the design of detergent chemistry. We harness the planetary boundary concept as a framework for literature survey to identify progresses and knowledge gaps in context with detergent chemistry and five planetary boundaries that are currently transgressed, i.e., climate, freshwater, land system, novel entities, biosphere integrity...
Source: Angewandte Chemie - April 15, 2024 Category: Chemistry Authors: Marc Seewald Lena Nielinger Katharina Alker Jan-Simon Behnke Virginia Wycisk Leonhard Hagen Urner Source Type: research
Halogen-Atom Transfer Enabled Catalytic Enantioselective Coupling to Chiral Trifluoromethylated Alkynes via Dual Nickel and Photocatalysis
Angew Chem Int Ed Engl. 2024 Apr 15:e202406064. doi: 10.1002/anie.202406064. Online ahead of print.ABSTRACTWith halogen-atom transfer as an effective tool, a novel catalytic enantioselective protocol to generate chiral trifluoromethylated alkynes has been established by a cooperative photoredox and nickel catalysis system, providing a straightforward and modular route to access this type of product in good yields and enantioselectivities. The halogen-atom transfer process is essential for the reaction and this novel strategy offers another promising way to utilize alkyl halides with highly negative reduction potentials. It...
Source: Angewandte Chemie - April 15, 2024 Category: Chemistry Authors: Shanya Lu Zihao Hu Dong Wang Tao Xu Source Type: research
Unprecedented POSS-linked 3D Covalent Organic Frameworks with scu or sqc Topology Regulated by Porphyrin Center for Photocatalytic CO2 Reduction
Angew Chem Int Ed Engl. 2024 Apr 15:e202404156. doi: 10.1002/anie.202404156. Online ahead of print.ABSTRACTThe synthesis and characterization of porphyrin center regulated three-dimensional covalent organic frameworks with 2-fold interpenetrated scu or sqc topology have been investigated. These COFs exhibit unique structural features and properties, making them promising candidates for photocatalytic applications in CO2 reduction and artemisinin synthesis. The porphyrin center serves as an anchor for metal ions, allowing precise control over structures and functions of the frameworks. Furthermore, the metal coordination wi...
Source: Angewandte Chemie - April 15, 2024 Category: Chemistry Authors: Ying Gao Senzhi Li Lei Gong Jing Li Dongdong Qi Liu Naifang Yongzhong Bian Jianzhuang Jiang Source Type: research
Divalent Titanium via Reductive N-C Coupling of a TiIV Nitrido with π-Acids
Angew Chem Int Ed Engl. 2024 Apr 15:e202404601. doi: 10.1002/anie.202404601. Online ahead of print.ABSTRACTThe nitrido-ate complex [(PN)2Ti(N){μ2-K(OEt2)}]2 (1) reductively couples CO and isocyanides in the presence of DME or cryptand, to form rare, five-coordinate TiII complexes having a linear cumulene motif, [K(L)][(PN)2Ti(NCE)] (E = O, L = Kryptofix222, (2); E = NAd, L = 3 DME, (3); E = NtBu, L = 3 DME, (4); E = NAd, L = Kryptofix222, (5)). Oxidation of 2-5 with [Fc][OTf] afforded an isostructural TiIII center containing a neutral cumulene [(PN)2Ti(NCE)] (E = O, (6); E = NAd (7), NtBu (8)). Moreover, 1e- reduction of ...
Source: Angewandte Chemie - April 15, 2024 Category: Chemistry Authors: Mrinal Bhunia Christian Sandoval-Pauker Dominik Fehn Lauren Grant Shuruthi Senthil Michael Gau Andrew Ozarowski Jurek Krzystek Joshua Telser Balazs Pinter Karsten Meyer Daniel J Mindiola Source Type: research
Molecular Symmetry and Art: Visualizing the Near-Symmetry of Molecules in Piet Mondrian's De Stijl
Angew Chem Int Ed Engl. 2024 Apr 15:e202403754. doi: 10.1002/anie.202403754. Online ahead of print.ABSTRACTSymmetry and shape are essential aspects of molecular structure and how we interpret molecules and their properties. We, as chemists, are comfortable with pictorial representations of structure, in which some nuance is lost - investigating molecular shape numerically by looking at how closely it fits a reference, such as a plane, or a set of vectors or coordinates, is informative, though far from engaging. Often relationships between chemical structure and derived values are obscured. Taking our inspiration from Piet ...
Source: Angewandte Chemie - April 15, 2024 Category: Chemistry Authors: Christopher J Kingsbury Mathias O Senge Source Type: research
An n-Type Open-Shell Conjugated Polymer with High-Spin Ground-State and High Intrinsic Electrical Conductivity
This study underscores the great potential of electron-deficient quinoidal units in constructing dopant-free n-type conductive polymers with a high-spin ground state and exceptional intrinsic conductivity.PMID:38619528 | DOI:10.1002/anie.202402375 (Source: Angewandte Chemie)
Source: Angewandte Chemie - April 15, 2024 Category: Chemistry Authors: Houji Cai Haoran Tang Tianzuo Wang Chenhui Xu Juxuan Xie Muyi Fu Xi Luo Zhengwei Hu Yi Zhang Yunfeng Deng Guangwu Li Chunchen Liu Fei Huang Yong Cao Source Type: research
Unified Approach to Deamination and Deoxygenation Through Isonitrile Hydrodecyanation: A Combined Experimental and Computational Investigation
Angew Chem Int Ed Engl. 2024 Apr 15:e202405779. doi: 10.1002/anie.202405779. Online ahead of print.ABSTRACTHerein, we describe a general hydrodefunctionalization protocol of alcohols and amines through a common isonitrile intermediate. To cleave the relatively inert C-NC bond, we leveraged dual hydrogen atom transfer (HAT) and photoredox catalysis to generate a nucleophilic boryl radical, which readily forms an imidoyl radical intermediate from the isonitrile. Rapid β-scission then accomplishes defunctionalization. This method has been applied to the hydrodefunctionalization of both amine and alcohol-containing pharmaceut...
Source: Angewandte Chemie - April 15, 2024 Category: Chemistry Authors: Ziqi Jiao Kyle T Jaunich Thomas Tao Olivia Gottschall Maxwell M Hughes Aneta Turlik Alexander Schuppe Source Type: research
One-pot Synthesis of High-capacity Sulfur Cathodes via In-situ Polymerization of a Porous Imine-based Polymer
This study introduces a solution by developing a microporous, covalently-bonded, imine-based polymer network grown in-situ around sulfur particles on the current collector. The polymer network (i) enables selective transport of electrolyte and Li-ions through pores of defined size, and (ii) acts as a robust host to retain the active component of the electrode (sulfur species). The resulting cathode has superior rate performance from 0.1 C (1360 mAh g-1) to 3 C (807 mAh g-1). Demonstrating a high-performance, sustainable sulfur cathode produced via a simple one-pot process, our research underlines the potential of microporo...
Source: Angewandte Chemie - April 15, 2024 Category: Chemistry Authors: Guiping Li Ye Liu Thorsten Schultz Moritz Exner Ruslan Muydinov Hui Wang Kerstin Scheurell Jieyang Huang Norbert Koch Paulina Szymoniak Nicola Pinna Philipp Adelhlem Michael Janus Bojdys Source Type: research
Small Ionic Liquid-based Molecule Drives Strong Adhesives
Angew Chem Int Ed Engl. 2024 Apr 15:e202403220. doi: 10.1002/anie.202403220. Online ahead of print.ABSTRACTNature has inspired scientists to fabricate adhesive materials for applications in many burgeoning areas. However, it is still a significant challenge to develop small-molecule adhesives with high-strength, low-temperature and recyclable properties, although these merits are of great interest in various aspects. Herein, we report a series of strong adhesives based on low-molecular-weight molecular solids driven by the terminal modification of ionic liquids (ILs) and subsequent supramolecular self-assembly. The emergen...
Source: Angewandte Chemie - April 15, 2024 Category: Chemistry Authors: Kai Liu Peiyi Wu Source Type: research
Indocyanine Green-based Nanoprobe for In Vivo Detection of Cellular Senescence
Angew Chem Int Ed Engl. 2024 Apr 15:e202404885. doi: 10.1002/anie.202404885. Online ahead of print.ABSTRACTThere is an urgent need to improve conventional cancer-treatments by preventing detrimental side effects, cancer recurrence and metastases. Recent studies have shown that presence of senescent cells in tissues treated with chemo- or radiotherapy can be used to predict the effectiveness of cancer treatment. However, although the accumulation of senescent cells is one of the hallmarks of cancer, surprisingly little progress has been made in development of strategies for their detection in vivo. To address a lack of dete...
Source: Angewandte Chemie - April 15, 2024 Category: Chemistry Authors: Andrew G Baker Muhamad Hartono Hui-Ling Ou Andrea Bistrovi ć Popov Emma L Brown James Joseph Monika Golinska Estela Gonz ález-Gualda David Marcias Jianfeng Ge Mary Denholm Samir Morsli Chandan Sanghera Thomas R Else Heather F Greer Aude Vernet Sarah E B Source Type: research
Alveoli-Inspired Carbon Cathodes with Interconnected Porous Structure and Asymmetric Coordinated Vanadium Sites for Superior Li-S Batteries
Angew Chem Int Ed Engl. 2024 Apr 15:e202404019. doi: 10.1002/anie.202404019. Online ahead of print.ABSTRACTAccelerating sulfur conversion catalysis to alleviate the shuttle effect has become a novel paradigm for effective Li-S batteries. Although nitrogen-coordinated metal single-atom (M-N4) catalysts have been investigated, further optimizing its utilization rate and catalytic activities is urgently needed for practical applications. Inspired by the natural alveoli tissue with interconnected structure and well-distributed enzyme catalytic sites on the wall for the simultaneously fast diffusion and in-situ catalytic conver...
Source: Angewandte Chemie - April 15, 2024 Category: Chemistry Authors: Rui Yan Zhenyang Zhao Ran Zhu Min Wu Xu Liu Mohsen Adeli Bo Yin Chong Cheng Shuang Li Source Type: research
Regulating Sulfur Redox Kinetics by Coupling Photocatalysis for High-Performance Photo-Assisted Lithium-Sulfur Batteries
Angew Chem Int Ed Engl. 2024 Apr 15:e202402624. doi: 10.1002/anie.202402624. Online ahead of print.ABSTRACTChallenges such as shuttle effect have hindered the commercialization of lithium-sulfur batteries (LSBs), despite their potential as high-energy-density storage devices. To address these issues, we explore the integration of solar energy into LSBs, creating a photo-assisted lithium-sulfur battery (PA-LSB). The PA-LSB provides a novel and sustainable solution by coupling the photocatalytic effect to accelerate sulfur redox reactions. Herein, a perovskite quantum dot-loaded MOF material serves as a cathode for the PA-LS...
Source: Angewandte Chemie - April 15, 2024 Category: Chemistry Authors: Yuhao Liu Feng Wu Zhengqiang Hu Fengling Zhang Ke Wang Li Li Renjie Chen Source Type: research
Development of an FeII Complex Exhibiting Intermolecular Proton Shifting Coupled Spin Transition
In this study, we investigated reversible intermolecular proton shifting (IPS) coupled with spin transition (ST) in a novel FeII complex. The host FeII complex and the guest carboxylic acid anion were connected by intermolecular hydrogen bonds (IHBs). We extended the intramolecular proton transfer coupled ST phenomenon to the intermolecular system. The dynamic phenomenon was confirmed by variable-temperature single-crystal X-ray diffraction, neutron crystallography, and infrared spectroscopy. The mechanism of IPS was further validated using density functional theory calculations. The discovery of IPS-coupled ST in crystall...
Source: Angewandte Chemie - April 15, 2024 Category: Chemistry Authors: Tianchi Ji Shengqun Su Shuqi Wu Yuta Hori Yasuteru Shigeta Yubo Huang Wenwei Zheng Wenhuang Xu Xiaopeng Zhang Ryoji Kiyanagi Koji Munakata Takashi Ohhara Takumi Nakanishi Osamu Sato Source Type: research
Photoswitching Reagent for Super-resolution Fluorescence Microscopy
This study contributes to a broader understanding of the molecular photoswitching mechanism in SMLM imaging and provides a basis for designing improved photoswitching reagents with potential applications extending to materials science and chemistry.PMID:38622700 | DOI:10.1002/anie.202405246 (Source: Angewandte Chemie)
Source: Angewandte Chemie - April 15, 2024 Category: Chemistry Authors: Ga-Eun Go Uidon Jeong Hyunbum Park Seokran Go Doory Kim Source Type: research
