The synthesis of a macrocyclic Ru carbene catalyst for selective cross alkene metathesis is reported. The new catalyst showed different reactivity for various type 1 alkenes in homodimerization which correlated with the aggregrate size of the allylic substituent. The altered reactivity profile allowed for selective product formation in competition cross alkene metathesis between two different type 1 alkenes and -butyl acrylate. Selectivity in these reactions is attributed to the ability of the macrocyclic catalyst to differentiate alkenes based on their size. Two preparative examples of cross metathesis with the macrocyclic catalyst are also provided.
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http://dx.doi.org/10.1021/jacs.0c00081 | DOI Listing |
Angew Chem Int Ed Engl
January 2025
CSIR National Chemical Laboratory, Polymer Science and Engineering Division, INDIA.
Synthesis of value-added products from post-consumer waste polyolefins is fascinating as well as challenging. Here we report ruthenium-catalyzed up-cycling of the polyethylene to long-chain alkene derivatives. The developed methodology mainly involves two steps i.
View Article and Find Full Text PDFPhys Chem Chem Phys
January 2025
Department of Chemistry, Visva-Bharati University, Santiniketan, West Bengal-731235, India.
First-principles analyses were performed for understanding the mechanistic details of Fe-catalysed asymmetric hydrogenation of alkenes in the presence of silane that has recently been experimentally realized. The catalytic hydrogenation is expected to proceed through initial hydride transfer from Fe-H to the CC bond of alkene, followed by σ-bond metathesis of hydrosilane to afford a chiral alkane product and an iron silyl species, which then reacts with H to regenerate the iron hydride species another σ-bond metathesis. The mechanistic details and the origin of the regioselectivity and stereoselectivity of these reactions are understood on the basis of detailed potential energy surface analysis, charge transfer and noncovalent interactions involved therein, strain energy and isodesmic studies in the solvated stage.
View Article and Find Full Text PDFNature
December 2024
Department of Chemistry, University of Basel, Basel, Switzerland.
Aromatic compounds are used across chemistry and materials science as a result of their stability, characteristic interactions, defined molecular shape and the numerous synthetic approaches for their synthesis by a diversity of cyclization reactions. In contrast, the cleavage of inert aromatic carbon-carbon bonds remained largely unfeasible due to the unfavourable energetics of disrupting aromaticity on ring opening. For non-aromatic structures, alkene metathesis catalysed by transition metal alkylidenes is established as one of the most versatile carbon-carbon bond-forming and breaking reactions.
View Article and Find Full Text PDFJ Am Chem Soc
December 2024
Department of Chemistry and Applied Biosciences, Laboratory of Organic Chemistry, ETH Zurich, Zurich 8093, Switzerland.
Methyltrioxorhenium (MTO) supported on AlO or SiO-AlO is an efficient heterogeneous alkene metathesis catalyst that works at room temperature and tolerates various functional groups. Surface studies found that MTO interacts with highly Lewis-acidic aluminum centers and that its methyl group is probably C-H activated resulting in rhenium-methylidene species. The exact structure of the catalyst resting state and the active species is subject to scientific debate.
View Article and Find Full Text PDFChem Sci
November 2024
KTH Royal Institute of Technology, Department of Chemistry Teknikringen 30 10044 Stockholm Sweden
We report on the synthesis of [2]rotaxanes from vicinal diols through dynamic covalent boronic ester templates, as well as the use of the boronic ester for rotaxane post-functionalisation. A boronic acid pincer ligand with two alkene-appended arms was condensed with a linear diol-containing thread, and ring-closing metathesis established a pre-rotaxane architecture along with a non-entangled isomer. Advanced NMR spectroscopy and mass spectrometry unambiguously assigned the isomers and revealed that the pre-rotaxane was in equilibrium with its hydrolyzed free [2]rotaxane form.
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