Archives for Chemistry Experiments of (1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium

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A novel fluorous tagging-detagging strategy has been developed featuring a fluorination as the detagging process; fluorous allylsilanes were prepared by cross-metathesis and subsequently subjected to electrophilic fluorodesilylation; Selectfluor was used as the detagging reagent; the resulting allylic fluorides were successfully purified by fluorous solid phase extraction. The Royal Society of Chemistry.

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

Discovery of (1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium

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A series of Ru-based olefin metathesis catalysts containing N,N?-diamidocarbenes (DACs) were synthesized and studied. X-ray crystallographic analysis revealed that the Ru-Ccarbene distances (1.938(5)-1.984(4) A) measured in the DAC-supported complexes were relatively short, particularly in comparison to the range of Ru-C carbene distances typically observed in analogous N-heterocyclic carbene (NHC) supported complexes (1.96-2.03 A). While the Tolman electronic parameters (TEP) of various DACs (2056-2057 cm-1) were calculated to be similar to that of PCy3 (2056 cm-1), the ring-closing metathesis (RCM) of diethyl diallylmalonate facilitated by DAC-supported Ru complexes proceeded at a relatively slow rate. However, unlike the phosphine-containing complexes, the DAC analogues catalyzed the RCM of diethyl dimethallylmalonate to its respective tetrasubstituted olefin. A series of electrochemical experiments revealed that the Ru complexes bearing a DAC ligand underwent oxidation at significantly higher potentials (DeltaE pa > 0.5 V) than analogous complexes containing phosphines and various N-heterocyclic carbenes (NHCs), including a tetrahydropyrimidinylidene, a saturated and strongly donating NHC analogue of the DAC. The relative catalytic activities observed were attributed to the steric properties of the aforementioned ligands.

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

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The present invention provides tricyclic fused thiophene derivatives, as well as their compositions and methods of use, that modulate the activity of Janus kinase (JAK) and are useful in the treatment of diseases related to the activity of JAK including, for example, inflammatory disorders, autoimmune disorders, cancer, and other diseases.

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

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New oxygen chelated ruthenium carbene complex containing carbonyl oxygen and ether oxygen has been developed. The X-ray structure of the complex showed that the carbonyl oxygen of the amide and the terminal oxygen of the benzylidene ether are both coordinated to the metal to give an octahedral structure. The catalytic activities of this new complex for olefin metathesis reactions were investigated and it exhibited excellent performances for the ring-closing metathesis (RCM) of diethyl diallymalonate at 30 C and even at 0 C. The initiation rate of the catalyst was higher than that for the Hoveyda catalyst ((H2IMes)(Cl)2Ru = C(H)(C6H 4-2-OiPr)) and it was also active for cross metathesis (CM).

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

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The synthesis of new poly(alkyl)-precision oligomers and polymers displaying different types of amino acids (chiral/achiral, polar/non-polar) placed at every 19th carbon atom are presented. Placing omega-alkenyl moieties onto appropriately N- and C-terminus functionalized amino acids successfully enabled ADMET-polymerization of these monomers. Grubbs 1st catalyst under melt-polycondensation-conditions was found to be the most effective with respect to the obtained molecular weights of the polymers, the isomerization of the olefins and their final yield, yielding molecular weights up to ?22 kDa. The obtained polymers and the subsequent hydrogenation of the double bonds with p-toluenesulfonhydrazide (TsNHNH2) was proven by NMR, GPC, MALDI-ToF-MS and IR measurements. Investigation of the thermal behavior of the monomers and polymers via DSC measurements displays amorphous structures for monomers and polymers with unpolar amino acid side chains, whereas for polymers bearing the polar glutamic- and aspartic acid moieties crystalline morphologies are observed. An ordered lamellar crystal phase is observed where the amino acid branches are either incorporated or excluded from the unit cell, as proven by WAXS data.

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

Discovery of (1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium

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Novel alkenylative cyclization of enyne was developed using Cp*RuCl(cod) under ethylene gas at room temperature. Copyright

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

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Full details of the total syntheses of the initially reported and revised structures of the neuroprotective agent palmyrolide A are reported. The key macrocyclization step was achieved using a sequential ring-closing metathesis/olefin isomerization reaction. Furthermore, the total synthesis of the related macrolide (2S)-sanctolide A is reported. The synthesis used key elements from the synthesis of palmyrolide A, including the RCM/olefin isomerization sequence. The synthetic work described herein serves to facilitate the assignment of stereochemistry of the natural product sanctolide A and demonstrates the utility of this approach for the synthesis of macrocyclic tertiary enamide natural products.

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

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[Figure not available: see fulltext.] Double bond isomerization by in situ generated ruthenium hydride catalyst in 6- to 9-membered hydrazine heterocycles including an endocyclic N?N bond was investigated. Based on the results of the experiments, a conclusion was made that the generation of resonance-stabilized enehydrazides is generally favored, but in some cases, the reaction pathway is presumably also highly dependent of steric interactions. With the current method, two novel enehydrazide heterocycles and one enehydrazine heterocycle were produced and characterized.

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

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A deuterium labeling study was undertaken to determine the mechanism of olefin isomerization during the metathesis reactions catalyzed by a second-generation Grubbs catalyst (2). The reaction of allyl-1,1-d2 methyl ether with 2 at 35C was followed by 1H and 2H NMR spectroscopy. The evidence of deuterium incorporation at the C-2 position of the isomerized product, trans-propenyl methyl ether, led to the conclusion that a metal hydride addition – elimination mechanism was operating under these conditions. Consequently, complex 8, an analogue of 2 bearing deuterated o-methyl groups on the aromatic rings of the NHC ligand, was synthesized to investigate the role of the NHC ligand in the formation of hydride species. Thermal decomposition of benzylidene 8 and methylidene 8? was monitored by 2H NMR spectroscopy; no deuteride complex was detected in either case. The decomposition mixtures were tested for isomerization activity with benchmark 1-octene but did not match the isomerization rates observed with 2 under similar metathesis conditions. Reaction of complex 8 with various olefmic substrates not only confirmed the formation of a deuteride complex but also revealed the existence of a competitive H/D exchange process between the CD 3 groups on the NHC ligand and the C-H bonds of the substrate. We propose that the exchange is promoted by a ruthenium dihydride intermediate whose formation is closely related to the methylidene decomposition.

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

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Quantitative energy-resolved collision-induced dissociation cross-sections by tandem ESI-MS provide absolute thermochemical data for phosphine binding energies in first- and second-generation ruthenium metathesis catalysts of 33.4 and 36.9 kcal/mol, respectively. Furthermore a study of the ring-closing metathesis in the second-generation system to liberate norbornene by forming the 14-electron reactive intermediate from the intramolecular pi-complex gives an estimate of the olefin binding energy to the 14-electron complex of around 18 kcal/mol, assuming a loose transition state. The results reported here are in remarkably good agreement with the latest DFT calculations using the M06-L functional.

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