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Ruthenium-catalyzed alkenylative cyclization via insertion of alkene into ruthenacyclopentene

A novel rumenium-catalyzed alkenylative cyclization of enyne was developed. When an enyne was reacted with Cp*RuCl(cod) under an atmosphere of ethylene, ethylene was inserted into the ruthenium-sp2 carbon bond of ruthenacyclopentene derived from enyne and the low-valent ruthenium complex to afford ruthenacycloheptene, and beta-hydrogen elimination followed by reductive elimination occurred to give a cyclic compound having a diene moiety. In this reaction, acrylaldehyde could be inserted into ruthenacyclopentene instead of ethylene. Various carbo- and heterocyclic compounds could be obtained in high 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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Gold(I)-catalyzed coupling reactions for the synthesis of diverse small molecules using the build/couple/pair strategy

The build/couple/pair strategy has yielded small molecules with stereochemical and skeletal diversity by using short reaction sequences. Subsequent screening has shown that these compounds can achieve biological tasks considered challenging if not impossible (‘undruggable’) for small molecules. We have developed gold(I)-catalyzed cascade reactions of easily prepared propargyl propiolates as a means to achieve effective intermolecular coupling reactions for this strategy. Sequential alkyne activationof propargyl propiolates by a cationic gold(I) catalyst yields an oxoca rbenium ion that we previously showed is trapped by C-based nucleophilesat an extrannular site to yield alpha-pyrones. Here, we report O-base d nucleophiles react by ring opening to afford a novel polyfunctional product. In addition, by coupling suitable building blocks, we subsequently performed intramolecular pairing reactions that yield diverse and complex skeletons. These pairing reactions include one based on a novel aza-Wittig-6?-electrocyclization sequence and others based on ring-closing metathesis reactions.

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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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246047-72-3, Name is (1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium, molecular formula is C46H65Cl2N2PRu, belongs to ruthenium-catalysts compound, is a common compound. In a patnet, once mentioned the new application about 246047-72-3, Quality Control of: (1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium

Enantioselective organocatalytic asymmetric allylic alkylation. Bis(phenylsulfonyl)methane addition to MBH carbonates

The highly enantioselective asymmetric allylic alkylation of Morita-Baylis-Hillman carbonates with bis(phenylsulfonyl)methane is presented. The reaction is simply catalyzed by cinchona alkaloid derivatives affording the final alkylated products in good yields and enantioselectivities. The Royal Society of Chemistry 2011.

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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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Stereoselective synthesis of the C13-C28 subunit of (-)-laulimalide utilizing an alpha-chlorosulfide intermediate

A stereoselective route to the C13-C28 subunit of (-)-laulimalide is described. l-Tartaric acid is the source of the hydroxy groups at C19 and C20. An alpha-chlorosulfide is employed as the key intermediate for the creation of the C17-C18 bond and the C16-C17 double bond was introduced using the Mislow-Braverman rearrangement and Hutchin’s dexoxygenation with concomitant double bond transposition reaction. The C15 and C23 stereogenic centers were created using catalytic asymmetric reactions. The trisubstituted and trans-disubstituted alkenes were created stereoselectively by taking advantage of ring-closing metathesis and the Julia-Kocienski olefination reaction, respectively. Georg Thieme Verlag Stuttgart, New York.

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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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Stabilisation of a nucleic acid three-way junction by an oligonucleotide containing a single 2?-C to 3?-O-phosphate butylene linkage prepared by a tandem RCM-hydrogenation method

A cyclic dinucleotide with a butylene linker between the upper 2?-C position and the 3?-O-phosphate linkage was synthesised from simple nucleoside building blocks via a tandem ring-closing metathesis and hydrogenation procedure. The major of two phosphorus epimers was incorporated into an oligodeoxynucleotide, as well as into an LNA-DNA mixmer oligonucleotide. These were evaluated as parts in three different secondary structures, a duplex, a bulged duplex and a three-way junction, with both DNA and RNA complements. In the DNA : RNA hybrid molecule, the oligodeoxynucleotide containing this single 2?-C to 3?-O-phosphate butylene linkage was found to stabilise a three-way junction. The Royal Society of Chemistry 2005.

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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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Making insoluble polymer networks malleable via olefin metathesis

Covalently cross-linked polymers have many technological applications for their excellent properties, but they suffer from the lack of processability and adaptive properties. We report a simple, efficient method of generating adaptive cross-linked polymers via olefin metathesis. By introducing a very low level of the Grubbs’ second-generation Ru metathesis catalyst, a chemically cross-linked polybutadiene network becomes malleable at room temperature while retaining its insolubility. The stress relaxation capability increases with increasing level of catalyst loading. In sharp contrast, catalyst-free control samples with identical network topology and cross-linking density do not show any adaptive properties. This chemistry should offer a possibility to combine the dimensional stability and solvent resistance of cross-linked polymers and the processability/adaptibility of thermoplastics.

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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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Tandem enyne metathesis and Claisen rearrangement: A versatile approach to conjugated dienes of variable substitution patterns

To extend the versatility of the ruthenium carbene-promoted enyne metathesis, it was combined with an Ireland ester enolate Claisen rearrangement. This reaction sequence provided conjugated dienes of higher substitution pattern than that obtained through a cross-enyne metathesis alone. The Ireland-Claisen was conducted across both acyclic and cyclic dienes produced from cross-metathesis and methylene-free enyne metathesis, respectively. In the case of cyclodienes, the Ireland-Claisen rearrangement produced s-trans locked dienes which underwent mode-selective ene reaction. The tandem, sequential use of the Ireland-Claisen rearrangement also proved suitable for chirality transfer originating from chiral propargylic alcohols. Last, the tandem metathesis/Ireland-Claisen was utilized to access 4-substituted-3,5- cyclohexadiene diol derivatives, which are valuable chiral intermediates for natural product synthesis. The combination of this pericyclic reaction with a catalytic metathesis reaction extends the versatility of cross-metathesis since additional diene motifs can be accessed.

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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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Formal synthesis of (+)-catharanthine

(Chemical Equation Presented) Madagascan periwinkle is the current source of (+)-catharanthine, the crucial building block of the major antitumor agent vinorelbine. In the formal synthesis of this natural product, the key intermediate 1 described by Buechi and coworkers was obtained in virtually optically pure form from L-serine. The strategy presented may be viewed as a general synthetic approach to optically active isoquinuclidines.

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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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Structure Determination of a Chloroenyne from Laurencia majuscula Using Computational Methods and Total Synthesis

Despite numerous advances in spectroscopic methods through the latter part of the 20th century, the unequivocal structure determination of natural products can remain challenging, and inevitably, incorrect structures appear in the literature. Computational methods that allow the accurate prediction of NMR chemical shifts have emerged as a powerful addition to the toolbox of methods available for the structure determination of small organic molecules. Herein, we report the structure determination of a small, stereochemically rich natural product from Laurencia majuscula using the powerful combination of computational methods and total synthesis, along with the structure confirmation of notoryne, using the same approach. Additionally, we synthesized three further diastereomers of the L. majuscula enyne and have demonstrated that computations are able to distinguish each of the four synthetic diastereomers from the 32 possible diastereomers of the natural product. Key to the success of this work is to analyze the computational data to provide the greatest distinction between each diastereomer, by identifying chemical shifts that are most sensitive to changes in relative stereochemistry. The success of the computational methods in the structure determination of stereochemically rich, flexible organic molecules will allow all involved in structure determination to use these methods with confidence.

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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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Alternating copolymerizations using a grubbs-type initiator with an unsymmetrical, chiral n-heterocyclic carbene ligand

(Chemical Equation Presented) Good for a ROMP: Initiators 1 and 2, which both contain an unsymmetric, chiral N-heterocyclic carbene (NHC) ligand, mediate the alternating copolymerization of norborn-2-ene with other cyclic olefins including cyclopentene and cyclooctene. The selectivity of the copolymerizationis explained by the steric interaction of the growing polymer chain with the 1-phenylethyl substituent and the nitrogen atom of the NHC ligand.

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