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841.
Alberto F. Garrido-Castro Yuta Hioki Yoshifumi Kusumoto Kyohei Hayashi Jeremy Griffin Kaid C. Harper Yu Kawamata Phil S. Baran 《Angewandte Chemie (International ed. in English)》2023,62(42):e202309157
A mild, scalable (kg) metal-free electrochemical decarboxylation of alkyl carboxylic acids to olefins is disclosed. Numerous applications are presented wherein this transformation can simplify alkene synthesis and provide alternative synthetic access to valuable olefins from simple carboxylic acid feedstocks. This robust method relies on alternating polarity to maintain the quality of the electrode surface and local pH, providing a deeper understanding of the Hofer-Moest process with unprecedented chemoselectivity. 相似文献
842.
Pietro Franceschi Dr. Sara Cuadros Dr. Giulio Goti Prof. Dr. Luca Dell'Amico 《Angewandte Chemie (International ed. in English)》2023,62(8):e202217210
The synthesis of four membered heterocycles usually requires multi-step procedures and prefunctionalized reactants. A straightforward alternative is the photochemical [2+2]-heterocycloaddition between an alkene and a carbonyl derivative, conventionally based on the photoexcitation of this latter. However, this approach is limited by the absorption profile of the carbonyl, requiring in most of the cases the use of high-energy UV-light, that often results in undesired side reactions and/or the degradation of the reaction components. The development of new and milder visible light-driven [2+2]-heterocycloadditions is, therefore, highly desirable. In this Review, we highlight the most relevant achievements in the development of [2+2]-heterocycloadditions promoted by visible light, with a particular emphasis on the involved reaction mechanisms. The open challenges will also be discussed, suggesting new possible evolutions, and stimulating new methodological developments in the field. 相似文献
843.
Hong-Guen Lee Dr. Avinash Dhamija Dr. Chandan K. Das Prof. Dr. Kyeng Min Park Prof. Dr. Young-Tae Chang Prof. Dr. Lars V. Schäfer Prof. Dr. Kimoon Kim 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2023,135(2):e202214326
Here we report synthetic monosaccharide channels built with shape-persistent organic cages, porphyrin boxes ( PB s), that allow facile transmembrane transport of glucose and fructose through their windows. PB s show a much higher transport rate for glucose and fructose over disaccharides such as sucrose, as evidenced by intravesicular enzyme assays and molecular dynamics simulations. The transport rate can be modulated by changing the length of the alkyl chains decorating the cage windows. Insertion of a linear pillar ligand into the cavity of PB s blocks the monosaccharide transport. In vitro cell experiment shows that PB s transport glucose across the living-cell membrane and enhance cell viability when the natural glucose transporter GLUT1 is blocked. Time-dependent live-cell imaging and MTT assays confirm the cyto-compatibility of PB s. The monosaccharide-selective transport ability of PB s is reminiscent of natural glucose transporters (GLUTs), which are crucial for numerous biological functions. 相似文献
844.
Vandana Jaiswal Soumik Mondal Bandana Singh Prof. Vinod. P. Singh Prof. Dr. Jaideep Saha 《Angewandte Chemie (International ed. in English)》2023,62(30):e202304471
Access to 1,3-functionalized azetidines through a diversity-oriented approach is highly sought-after for finding new applications in drug-discovery. To this goal, strain-release-driven functionalization of azabicyclo[1.1.0]-butane (ABB) has generated significant interest. Through appropriate N-activation, C3-substituted ABBs are shown to render tandem N/C3-fucntionalization/rearrangement, furnishing azetidines; although, modalities of such N-activation vis-à-vis N-functionalization remain limited to selected electrophiles. This work showcases a versatile cation-driven activation strategy of ABBs. And capitalizes on the use of Csp3 precursors amenable to forming reactive (aza)oxyallyl cations in situ. Herein, N-activation leads to formation of a congested C−N bond, and effective C3 activation. The concept was extended to formal [3+2] annulations involving (aza)oxyallyl cations and ABBs, leading to bridged bicyclic azetidines. Besides the fundamental appeal of this new activation paradigm, operational simplicity and remarkable diversity should engender its prompt use in synthetic and medicinal chemistry. 相似文献
845.
Jeffrey Bruffaerts Inbar Kesten Keren Buhnik-Rosenblau Anthony Cohen Nurit Edri Morgan Cormier Yuanfei Zhang Guo-Ming Ho Itai Massad Hila Halfon-Verner Yechezkel Kashi Ilan Marek 《Angewandte Chemie (International ed. in English)》2023,62(30):e202306343
A two-step sequential strategy involving a biocatalytic dehydrogenation/remote hydrofunctionalization, as a unified and versatile approach to selectively convert linear alkanes into a large array of valuable functionalized aliphatic derivatives is reported. The dehydrogenation is carried out by a mutant strain of a bacteria Rhodococcus and the produced alkenes are subsequently engaged in a remote functionalization through a metal-catalyzed hydrometalation/migration sequence that subsequently react with a large variety of electrophiles. The judicious implementation of this combined biocatalytic and organometallic approach enabled us to develop a high-yielding protocol to site-selectively functionalize unreactive primary C−H bonds. 相似文献
846.
Dr. Marat Meleshin Lukas Koch Dr. Christoph Wiedemann Prof. Dr. Mike Schutkowski 《Angewandte Chemie (International ed. in English)》2023,62(25):e202301543
Herein we report a mild, efficient, and epimerization-free method for the synthesis of peptide-derived 2-thiazolines and 5,6-dihydro-4H-1,3-thiazines based on a cyclodesulfhydration of N-thioacyl-2-mercaptoethylamine or N-thioacyl-3-mercaptopropylamine derivatives. The described reaction can be easily carried out in aqueous solutions at room temperature and it is triggered by change of the pH, leading to complex thiazoline or dihydrothiazine derivatives without epimerization in excellent to quantitative yields. The new method was applied in the total synthesis of the marine metabolite mollamide F, resulting in the revision of its stereochemistry. 相似文献
847.
Cheuk Yin Li Zhenghua Liang Lejian Liu Prof. Yi Kuang 《Angewandte Chemie (International ed. in English)》2023,62(37):e202306533
Synthetic messenger RNA (mRNA) switches are powerful tools for in situ cell purification, especially for cells derived from stem cells. However, the retention effectiveness of the target cells is limited by the leaky expression of toxic protein. The elimination efficiency of non-target cells is also constrained due to the lack of signal amplification. In this study, we designed a novel approach that uses synthetic mRNA switch to convey intracellular marker molecule information into spatially controlled extracellular toxic assembly formation. The approach bypasses the use of toxic protein to ensure high target cell recovery effectiveness. Meanwhile, the marker molecule information is amplified at multiple levels to ensure high non-target cell elimination effectiveness. Our approach can be tailored to meet various in situ cell purification needs, promising high-quality in situ cell purification for a wide range of biomedical applications. 相似文献
848.
Yen-Chu Lu Prof. Julian G. West 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2023,135(3):e202213055
Decarboxylative protonation is a general deletion tactic to replace polar carboxylic acid groups with hydrogen or its isotope. Current methods rely on the pre-activation of acids, non-sustainable hydrogen sources, and/or expensive/highly oxidizing photocatalysts, presenting challenges to their wide adoption. Here we show that a cooperative iron/thiol catalyst system can readily achieve this transformation, hydrodecarboxylating a wide range of activated and unactivated carboxylic acids and overcoming scope limitations in previous direct methods. The reaction is readily scaled in batch configuration and can be directly performed in deuterated solvent to afford high yields of d-incorporated products with excellent isotope incorporation efficiency; characteristics not attainable in previous photocatalyzed approaches. Preliminary mechanistic studies indicate a radical mechanism and kinetic results of unactivated acids (KIE=1) are consistent with a light-limited reaction. 相似文献