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Stereoselective synthesis of macrocyclic peptides via a dual olefin metathesis and ethenolysis approach

Macrocyclic compounds occupy an important chemical space between small molecules and biologics and are prevalent in many natural products and pharmaceuticals. The growing interest in macrocycles has been fueled, in part, by the design of novel synthetic methods to these compounds. One appealing strategy is ring-closing metathesis (RCM) that seeks to construct macrocycles from acyclic diene precursors using defined transition-metal alkylidene catalysts. Despite its broad utility, RCM generally gives rise to a mixture of E- and Z-olefin isomers that can hinder efforts for the large-scale production and isolation of such complex molecules. To address this issue, we aimed to develop methods that can selectively enrich macrocycles in E- or Z-olefin isomers using an RCM/ethenolysis strategy. The utility of this methodology was demonstrated in the stereoselective formation of macrocyclic peptides, a class of compounds that have gained prominence as therapeutics in drug discovery. Herein, we report an assessment of various factors that promote catalyst-directed RCM and ethenolysis on a variety of peptide substrates by varying the olefin type, peptide sequence, and placement of the olefin in macrocycle formation. These methods allow for control over olefin geometry in peptides, facilitating their isolation and characterization. The studies outlined in this report seek to expand the scope of stereoselective olefin metathesis in general RCM.

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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. 246047-72-3, Name is (1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium, molecular formula is C46H65Cl2N2PRu. In a Article£¬once mentioned of 246047-72-3, Recommanded Product: 246047-72-3

Propargylic cation-induced intermolecular electrophilic addition-semipinacol rearrangement

A novel propargylic electrophile-induced tandem intermolecular addition-semipinacol rearrangement was developed efficiently under mild conditions. Various allylic silylether substrates as well as Co-complexed propargylic species were applicable to this protocol and gave a series of synthetically useful beta-propargyl spirocyclic ketones in moderate to good yields. Its synthetic application was also demonstrated by an efficient construction of the key tricyclic moiety of daphlongamine E. the Partner Organisations 2014.

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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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Facile synthesis of fluorovinyl-containing lactams via ring-closing metathesis of N-substituted 2-fluoroallylamides

A cost-efficient method for the preparation of a series of N-substituted 2-fluoroallylamines and their application in the synthesis of fluoroalkene-containing lactams are described. N-substituted 2-fluoroallylamine could be readily synthesized from methyl 2-fluoroacrylate via aminolysis and subsequently selective reduction of the amide group. These amines were further converted into the corresponding amides with diverse acids bearing a terminal double bond. The Ring-Closing Metathesis (RCM) of the resulting amides led to the formation fluorovinyl-containing lactams in good yields.

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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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The reactant in an enzyme-catalyzed reaction is called a substrate. Enzyme inhibitors cause a decrease in the reaction rate of an enzyme-catalyzed reaction.I hope my blog about 246047-72-3 is helpful to your research., COA of Formula: C46H65Cl2N2PRu

The reaction rate of a catalyzed reaction is faster than the reaction rate of the uncatalyzed reaction at the same temperature.246047-72-3, Name is (1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium, molecular formula is C46H65Cl2N2PRu. In a Article£¬once mentioned of 246047-72-3, COA of Formula: C46H65Cl2N2PRu

Divergent Approach to a Family of Tyrosine-Derived Ru-Alkylidene Olefin Metathesis Catalysts

A simple and generic approach to access a new family of Ru-alkylidene olefin metathesis catalysts with specialized properties is reported. This strategy utilizes a late stage, utilitarian Hoveyda-type ligand derived from tyrosine, which can be accessed via a multigram-scale synthesis. Further functionalization allows the catalyst properties to be tuned, giving access to modified second-generation Hoveyda-Grubbs-type catalysts. This divergent synthetic approach can be used to access solid-supported catalysts and catalysts that function under solvent-free and aqueous conditions.

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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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Reference of 246047-72-3, Catalysts are substances that increase the reaction rate of a chemical reaction without being consumed in the process. 246047-72-3, Name is (1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium, molecular formula is C46H65Cl2N2PRu. In a Article£¬once mentioned of 246047-72-3

A salt metathesis route to ruthenium carbene complex isomers with pyridine dicarboxamide-derived chelate pincer ligands

Reaction of the doubly deprotonated pyridine 2,6-dicarboxamido ligand (1) with (PCy3)2Cl2 Ru=CHPh (3a) in THF gave a mixture of (Hg)(PCy3)Ru=CHPh isomers (4). The pentane soluble N,N,O-4 isomer was isolated by extraction and characterized by X-ray diffraction. The O,N, O-4 isomer was identified in the residue. Single crystals of the closely related complex (Hg)(NHC) Ru=CHPh, O,N,O-5, were obtained from the reaction of 1 with (NHC)(PCy3)Cl2Ru=CHPh (3b) and used for the X-ray crystal structure analysis of the system.

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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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Sometimes chemists are able to propose two or more mechanisms that are consistent with the available data.Recommanded Product: (1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium, If a proposed mechanism predicts the wrong experimental rate law, however, the mechanism must be incorrect.Welcome to check out more blogs about 246047-72-3, in my other articles.

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. 246047-72-3, Name is (1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium, molecular formula is C46H65Cl2N2PRu. In a Article£¬once mentioned of 246047-72-3, Recommanded Product: (1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium

Synthesis and properties of fluorescent dyes conjugated to hyperbranched polyglycerols

Convergent syntheses of polyglycerol hyperbranched polymers containing fluorescent labels (fluorescein or perylene diimide (PDI)) at their core are presented. The hyperbranched polyglycerol (HPG) precursors were synthesized using a one step polymerization reaction wherein the initiator leaves a single reactive group for dye functionalization. For further site isolation, allylated HPG was synthesized allowing cross-linking via ring closing metathesis and subsequent dihydroxylation to produce water-soluble, fluorescent nanoparticles. The dyes produced showed improvements in photostability, water solubility, or quantum yield, depending on both the dye used and cross-linking. These fluorescent nanoparticles outperformed similar dyes that incorporated linear polyethylene glycol (PEG) polymers.

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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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Gold-catalyzed intermolecular addition of alcohols toward the allenic bond of 4-vinylidene-2-oxazolidinones

Gold catalyzed intermolecular addition of alcohols toward the proximal allenic double bond of 4-vinylidene-2-oxazolidinones gives hydroalkoxylation products, which can be easily converted into the corresponding novel spiro dihydrofuran or dihydropyran derivatives in high yield.

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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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Balanced chemical reaction does not necessarily reveal either the individual elementary reactions by which a reaction occurs or its rate law.HPLC of Formula: C46H65Cl2N2PRu. In my other articles, you can also check out more blogs about 246047-72-3

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. 246047-72-3, Name is (1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium, molecular formula is C46H65Cl2N2PRu. In a Article£¬once mentioned of 246047-72-3, HPLC of Formula: C46H65Cl2N2PRu

Cyclodextrin ketones as oxidation catalysts: Investigation of bridged derivatives

A series of alpha-cyclodextrin derivatives containing a 3, 4 or 5 membered ether-linked bridge between the 6A and 6D oxygen atoms, with and without a ketone, were prepared. The synthesis used perbenzylated alpha-cyclodextrin A,D-diol as a starting material upon which O-alkylation and further modifications led to the di-O-(buta-1,4-diyl), the di-O-(penta-1,5- diyl) and the di-O-(buta-2-on-1,4-diyl) derivatives, which were debenzylated, and compared with the previously reported di-O-(propa-2-on-1,3-diyl) derivative. Permethylated derivatives of the di-O-(propa-2-on-1,3-diyl) and the buta-1,4-diyl derivatives were also made. The 6A,6D-di-O-(propa-2-on-1,3-diyl)- 6C,6F-di-O-methyl and di-O-pivaloyl derivatives were also prepared. The new compounds were analysed for catalysis of the oxidation of amines and alcohols.

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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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The stereocontrolled total synthesis of spirastrellolide A methyl ester. Expedient construction of the key fragments

Due to a combination of their promising anticancer properties, limited supply from the marine sponge source and their unprecedented molecular architecture, spirastrellolides represent attractive and challenging synthetic targets. A modular strategy for the synthesis of spirastrellolide A methyl ester, which allowed for the initial stereochemical uncertainties in the assigned structure was adopted, based on the envisaged sequential coupling of a series of suitably functionalised fragments; in this first paper, full details of the synthesis of these fragments are described. The pivotal C26-C40 DEF bis-spiroacetal was assembled by a double Sharpless asymmetric dihydroxylation/acetalisation cascade process on a linear diene intermediate, configuring the C31 and C35 acetal centres under suitably mild acidic conditions. A C1-C16 alkyne fragment was constructed by application of an oxy-Michael reaction to introduce the A-ring tetrahydropyran, a Sakurai allylation to install the C9 hydroxyl, and a 1,4-syn boron aldol/directed reduction sequence to establish the C11 and C13 stereocentres. Two different coupling strategies were investigated to elaborate the C26-C40 DEF fragment, involving either a C17-C25 sulfone or a C17-C24 vinyl iodide, each of which was prepared using an Evans glycolate aldol reaction. The remaining C43-C47 vinyl stannane fragment required for introduction of the unsaturated side chain was prepared from (R)-malic acid.

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

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A Gentler Touch: Synthesis of Modern Ruthenium Olefin Metathesis Catalysts Sustained by Mechanical Force

Mechanochemical synthesis of nine contemporary ruthenium catalysts used for olefin metathesis is described, being the first reported example of formation of Ru carbene organometallic complexes in solid state. Three key organometallic transformations commonly used in the synthesis of the second and third generations of Ru catalysts in solution?phosphine ligand (PCy3) exchange with in situ formed N-heterocyclic carbene (NHC) ligand, PCy3 to pyridine ligand replacement, and benzylidene ligands interchange?were proved to work under mechanochemical conditions, affording the targets in high purity. Mechanochemical approach not only requires less amounts of organic solvent (null for synthesis, only for purification) and is scalable, but also allows for transformations that were reported impossible in the solution phase.

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