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Stereoselective synthesis of functionalized cyclic amino acid derivatives via a [2,3]-stevens rearrangement and ring-closing metathesis

Unnatural cyclic amino acids are valuable tools in biomedical research and drug discovery. A two-step stereoselective strategy for converting simple glycine-derived aminoesters into unnatural cyclic amino acid derivatives has been developed. The process includes a palladium-catalyzed tandem allylic amination/[2,3]-Stevens rearrangement followed by a ruthenium-catalyzed ring-closing metathesis. The [2,3]-rearrangement proceeds with high diastereoselectivity through an exo transition state. Oppolzer’s chiral auxiliary was utilized to access an enantiopure cyclic amino acid by this approach, which will enable future biological applications.

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Reference£º
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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Does the rate of competing isomerisation during alkene metathesis depend on pre-catalyst initiation rate?

Experimental studies of the ring-closing metathesis reaction of 1,8-nonadiene and the ROMP reaction of cycloheptene show that the rate of isomerisation is not correlated to the initiation rate of the pre-catalyst, and that the absence of phosphine leads to a greatly increased rate of isomerisation. A range of pre-catalysts and solvents were probed and it is proposed that the isomerisation is mediated by a ruthenium hydride complex; our results are consistent with the rate-determining formation of such a species, which might be trapped in situ by tricyclohexylphosphane.

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Reference£º
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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Evolution of the total synthesis of (-)-Okilactomycin exploiting a tandem oxy-cope rearrangement/oxidation, a petasis-ferrier union/rearrangement, and ring-closing metathesis

An effective, asymmetric total synthesis of the antitumor antibiotic (-)-okilactomycin (1), as well as assignment of the absolute configuration,has been achieved exploiting a convergent strategy. Highlights of the s ynthesis include a diastereoselective oxy-Cope rearrangement/oxidation sequence to install the C(1) and C(13) stereogenic centers, a Petasis-Ferrier union/rearrangement to construct the highly functionalized tetrahydropyranone inscribed within the 13-membered macrocycle ring, employing for the first time a sterically demanding acetal, an intramolecular chemoselective acylation to access an embedded bicyclic lactone, and an efficient ring-closing metathesis (RCM) reaction to generate the macrocyclic ring.

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Reference£º
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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Highly selective metathesis of 1-octene in ionic liquids

The self-metathesis of 1-octene to form 7-tetradecene catalyzed by ruthenium carbene complexes at low concentrations (0.02 mol %) was investigated in ionic liquids as reaction media and as additives. The study showed that the ionic liquid has a significant effect on the selectivity of the metathesis of 1-octene, with conversion to product of greater than 95% being obtained and selectivities of over 98% being realized. The outcomes of the reactions compared well with those performed under solventless conditions, showing improved conversions and selectivittes.

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Reference£º
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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Access to Multisubstituted 2(5 H)-Furanones Using Hydrogen Bonding-Promoted Ring-Closing Metathesis and Polyamine Workup

Structurally complex 2(5H)-furanones are potentially challenging targets for ring-closing metathesis (RCM). A hydrogen bonding-guided RCM strategy was developed in this study to provide 3-substituted and 3,4-disubstituted 2(5H)-furanones in moderate to high yields with broad functional group tolerance. A workup procedure using ethylenediamine-derived polyamines such as tetraethylenepentylamine was also established to effectively remove Ru residues in products.

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Reference£º
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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A catalyst don’t appear in the overall stoichiometry of the reaction it catalyzes, but it must appear in at least one of the elementary reactions in the mechanism for the catalyzed reaction. 301224-40-8, Name is (1,3-Dimesitylimidazolidin-2-ylidene)(2-isopropoxybenzylidene)ruthenium(VI) chloride, molecular formula is C31H38Cl2N2ORu. In a Patent£¬once mentioned of 301224-40-8, Recommanded Product: 301224-40-8

MACROLIDES WITH MODIFIED DESOSAMINE SUGARS AND USES THEREOF

Provided are macrolide compounds for the treatment of infectious diseases. The macrolides disclosed herein include 14-membered ketolides and 14-15-membered azaketolides, and may comprise modified sugars which are desosamine analogues. The disclosed macrolides may have a bicyclic structure. Also provided are pharmaceutical compositions and methods of treating infectious diseases, and in particular, disease which results from Gram negative bacteria using the disclosed macrolides. This disclosure additionally provides methods of preparing the macrolides by a strategy that enables late- stage modification of the 6′-position of the sugar moiety, thereby allowing facile access to previously difficult-to-make macrolide compounds.

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Reference£º
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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RUTHENIUM OLEFIN METATHESIS CATALYSTS BEARING N-HETEROCYCLIC CARBENE LIGANDS WITH SUBSTITUTED BACKBONE

This invention relates generally to olefin metathesis, more particularly, to tri- or tetra-substituted imidazoliniupsilonm salts which are precursors to N-heterocyclic carbene (NHC) ligands with tri- or tetra-substituted irnidazolinium rings, organometallic ruthenium complexes comprising gem di-substituted imidazoiinium NHC ligands, organometallic ruthenium complexes comprising tri- or tetra-substituted imidazoiinium NHC ligands, and to olefin metathesis methods using them. The catalysts and methods of the invention have utility in the fields of catalysis, organic synthesis, and industrial chemistry.

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Reference£º
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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Design, synthesis, and biological evaluation of platensimycin analogues with varying degrees of molecular complexity

The molecular design, chemical synthesis, and biological evaluation of two distinct series of platensimycin analogues with varying degrees of complexity are described. The first series of compounds probes the biological importance of the benzoic acid subunit of the molecule, while the second series explores the tetracyclic cage domain. The biological data obtained reveal that, while the substituted benzoic acid domain of platensimycin is a highly conserved structural motif within the active compounds with strict functional group requirements, the cage domain of the molecule can tolerate considerable structural modifications without losing biological action. These findings refine our present understanding of theplatensimycin pharmacophore and establish certain structure-activity re lationships from which the next generation of designed analogues of thisnew antibiotic may emerge.

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Reference£º
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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Olefin metathesis transformations in thermomorphic multicomponent solvent systems

Homogeneous catalysis is a major actor of modern chemistry with a growing impact on clean and sustainable chemical processes. However, for many industrial applications of homogeneously catalyzed reactions, an easy separation and recovery of the catalyst should be guaranteed. Temperature-dependent multicomponent solvent (TMS) systems have been evaluated in ruthenium catalyzed olefin metathesis transformations. Propylene carbonate was found a suitable solvent for the ruthenium catalyzed ring-closing and cross-metathesis transformations of a variety of substrates including renewable fatty esters. The potential of a TMS system consisting of propylene carbonate/ethyl acetate/cyclohexane was then evaluated in the cross-metathesis of the renewable methyl 10-undecenoate with methyl acrylate and acrylonitrile.

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Reference£º
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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Microwave-assisted telescoped cross metathesis-ring closing aza-Michael reaction sequence: step-economical access to nicotine-lobeline hybrid analogues

A series of 2,5-disubstituted pyrrolidines was synthesized through an efficient telescoped cross-metathesis/cyclizing aza-Michael addition involving N-heteroaromatic olefinic derivatives. This synthetic route was applied to the preparation of original nicotine-lobeline, nicotine-pelletierine and lobeline-nicotine-epibatidine hybrids.

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Reference£º
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI