98%
921
2 minutes
20
Olefin metathesis, as a powerful metal-catalysed carbon-carbon bond-forming method, has achieved considerable progress in recent years. However, the complexity originating from multicomponent interactions has long impeded a complete mechanistic understanding of olefin metathesis, which hampers further optimization of the reaction. Here, we clarify both productive and hidden degenerate pathways of ring-closing metathesis by focusing on one individual catalyst, using a sensitive single-molecule electrical detection platform. In addition to visualizing the full pathway, we found that the conventionally unwanted degenerate pathways have an unexpected constructive coupling effect on the productive pathway, and both types of pathway can be regulated by an external electric field. We then pushed forward this ability to ring-opening metathesis polymerization involving more interactive components. With single-monomer-insertion-event resolution, precise on-device synthesis of a single polymer was achieved by online manipulation of monomer insertion dynamics, intramolecular chain transfer, stereoregularity, degree of polymerization and block copolymerization. These results offer a comprehensive mechanistic understanding of olefin metathesis, exemplifying infinite opportunities for practical precise manufacturing.
Download full-text PDF |
Source |
---|---|
http://dx.doi.org/10.1038/s41565-024-01814-y | DOI Listing |
Org Biomol Chem
September 2025
Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai 400076, Maharashtra, India.
We report the stereoselective synthesis of (17,18,36)-tonkinelin and its diastereomer (17,18,36)-tonkinelin a convergent strategy involving the stepwise construction of two key fragments: a chiral ester-derived phosphonium salt and a requisite aldehyde for a convergent Wittig olefination. Key transformations in the sequence include asymmetric dihydroxylation, Wittig olefination, ring-closing metathesis (RCM) and chemoselective diimide olefin reduction. The synthesized tonkinelins were fully characterized, and their spectroscopic data were found to be consistent with previously reported data.
View Article and Find Full Text PDFChem Bio Eng
August 2025
College of Chemical and Biological Engineering, State Key Laboratory of Chemical Engineering and Low-carbon Technology, Zhejiang University, Hangzhou 310058, China.
Tungstate-based catalysts for olefin metathesis generally suffer from insufficient reaction rates, which require relatively high temperatures for the satisfied activities. This issue is mainly due to the shortage of active WO species related to intrinsic low adsorption and poor activation of olefin molecules. Herein, we found that the silanol nests in dealuminated Beta zeolite (DeAl-Beta) were favorable for high dispersion of tungsten species, forming active WO species on the zeolite, which was helpful for the adsorption and activation of olefin molecules, thus facilitating the generation of metallocycle intermediates.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
August 2025
Department of Materials Science and Engineering, Korea Advanced Institute of Science and Technology (KAIST), 291 Daehak-ro, Yuseong-gu, Daejeon, 34141, Republic of Korea.
High-resolution patterning of colloidal perovskite nanocrystals (PNCs) is essential for next-generation display technologies, yet conventional approaches relying on exogenous photosensitive ligands or additives often compromise optical properties and colloidal stability. Here, we present a nondestructive ligand modification strategy based on olefin metathesis, in which original oleic acid and oleylamine ligands are converted into metathesized ligands featuring dual anchoring groups and shortened chains. This structural transformation enhances colloidal stability through stronger chelation and reduced conformational entropy of possible ligand configurations.
View Article and Find Full Text PDFJ Am Chem Soc
August 2025
Instituto de Tecnología Química (UPV-CSIC), Universitat Politècnica de València-Agencia Estatal Consejo Superior de Investigaciones Científicas, Avda. de los Naranjos s/n, 46022 Valencia, Spain.
Metal-, organo-, and proton-catalyzed carbonyl-olefin/alkyne metathesis reactions have gained relevance in organic synthesis during the past decade, but their potential implementation in high-volume processes (i.e., in flow) is severely hampered by the lack of a general, robust, easily separable, and nontoxic solid catalyst.
View Article and Find Full Text PDFChemistry
August 2025
Institut des Biomolécules Max Mousseron, IBMM, Univ. Montpellier, CNRS, ENSCM, 1919 route de Mende, Montpellier, 34293, France.
Neuroprostanes (NeuroPs) are bioactive oxylipins formed in vivo from docosahexaenoic acid (DHA), the main polyunsaturated fatty acid of the human brain, by a nonenzymatic auto-oxidative process as mixtures of regio- and diastereoisomers. Thus, synthetic material is necessary to unlock their potential as oxidative stress biomarkers as well as to investigate the biological properties of individual NeuroP molecules. Despite recent advances in the field, cyclopentenone-type NeuroPs have received limited attention.
View Article and Find Full Text PDF