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Chiral amines are prevalent in natural products, pharmaceuticals, and organic catalysts. Their increasing demand has driven the advancement of synthetic methods. In this study, we developed a metalloenzyme-catalyzed asymmetric transfer hydrogenation method for the synthesis of chiral amines. Given the challenges of traditional chemical synthesis, which relies on precious metals and complex synthetic ligands, our approach utilizes base metals derived from natural metalloenzymes for transfer hydrogenation and employs protein scaffolds to achieve stereochemical control. Furthermore, in contrast to natural NAD(P)H-dependent C═N bond reductases, this strategy utilizes silanes as reducing agents and is entirely orthogonal to conventional NAD(P)H-dependent cellular functions. This reactivity highlights the potential to develop new-to-nature enzymatic functions capable of addressing challenges in both organic synthesis and biosynthesis.
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http://dx.doi.org/10.1002/anie.202511298 | DOI Listing |
J Phys Chem Lett
September 2025
Pacific Northwest National Laboratory, Richland, Washington 99354, United States.
Water-ion interactions govern the physicochemical properties of aqueous solutions, impacting the structure of the hydrogen bonding network and ion diffusivities. To elucidate these effects under alkaline conditions relevant to diverse application spaces, we examined NaOD-DO solutions using two-dimensional infrared spectroscopy (2D-IR), small-angle X-ray scattering (SAXS), and nuclear magnetic resonance spectroscopy (NMR). Vibrational energy transfer between the donor anion SeCN, used as a 2D-IR probe, and the acceptor anion OD was used to track the average separation distance of ions in the DO solutions, while SAXS and NMR experiments measured the structure of the bulk DO solvent.
View Article and Find Full Text PDFNanoscale
September 2025
Department of Chemical Sciences, Ariel University, Ariel, Israel.
Electrocatalytic synthesis of ammonia is a sustainable, cost-effective alternative method for producing renewable electricity and can operate under milder conditions than the traditional Haber-Bosch method. We report direct laser-induced synthesis of copper nanocatalysts embedded in graphitic films for the synthesis of ammonia. Laser-induced metal-embedded graphene (m-LIG) offers many advantages, such as fast and simple synthesis, shape design of the electrodes, and direct printing on any substrate, including thermally sensitive plastics.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
September 2025
Institute of Modern Optics and Center of Single-Molecule Science, Tianjin Key Laboratory of Micro-scale Optical Information Science and Technology, Nankai University, Tianjin, 300350, China.
Radical coupling reactions have been widely used in the synthesis of complex organic molecules, materials science, and drug research. However, restricted conditions or special catalysts are required to overcome the energy barrier and trigger the coupling reaction efficiently. In this study, we provide experimental evidence that the C─N radical coupling reactions can be significantly accelerated by an oriented external electric field (OEEF) under synchronous UV irradiation without a catalyst.
View Article and Find Full Text PDFChem Rec
September 2025
Chemical Sciences and Technology Division, CSIR-National Institute for Interdisciplinary Science and Technology (CSIR-NIIST), Thiruvananthapuram, 695019, India.
The Friedländer quinoline synthesis represents a fundamental method for the construction of quinoline derivatives, a versatile class of heterocyclic compounds widely prevalent in pharmaceuticals and materials science. This synthesis traditionally involves the condensation of 2-aminoaryl ketones with carbonyl compounds, typically ketones or aldehydes, in the presence of an acid or base under reflux conditions. However, recent advancements have highlighted indirect approaches (starting from 2-aminobenzyl alcohol) to achieve the same quinoline framework, offering distinct advantages in selectivity, substrate scope, and functional group tolerance.
View Article and Find Full Text PDFFEBS J
September 2025
Neutron Scattering Division, Oak Ridge National Laboratory, USA.
Serine hydroxymethyltransferase (SHMT) is a critical enzyme in the one-carbon (1C) metabolism pathway catalyzing the reversible conversion of L-Ser into Gly and concurrent transfer of 1C unit to tetrahydrofolate (THF) to give 5,10-methylene-THF (5,10-MTHF), which is used in the downstream syntheses of biomolecules critical for cell proliferation. The cellular 1C metabolism is hijacked by many cancer types to support cancer cell proliferation, making SHMT a promising target for the design and development of novel small-molecule antimetabolite chemotherapies. To advance structure-assisted drug design, knowledge of SHMT catalysis is crucial, but can only be fully realized when the atomic details of each reaction step governed by the acid-base catalysis are elucidated by visualizing active site hydrogen atoms.
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