Final Thoughts on Chemistry for (1,3-Dimesitylimidazolidin-2-ylidene)(2-isopropoxybenzylidene)ruthenium(VI) chloride

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Ammonium NHC-tagged olefin metathesis catalysts-influence of counter-ions on catalytic activity

Ruthenium-based catalysts bearing quaternary ammonium groups in their N-heterocyclic carbene (NHC) fragments and different counter-ions were synthesised and tested in various olefin metathesis transformations. Differences in catalytic activity in correlation with the nature of the present counter-ion were revealed. The unique properties of the described catalysts allow for the effective preparation of a variety of metathesis products with low ruthenium contamination and under green chemistry 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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BIO-DERIVED OLEFIN SYNTHESIS

Disclosed is a method for the combined synthesis of at least two vinylic monomers, at least one of which being an acrylic compound, comprising subjecting a monoconjgated alkene-1-carboxylic compound to reaction with a C2-C4 alkene under conditions of olefin cross-metathesis. The invention is particularly useful for extracting value from protein side streams. Upon protein hydrolysis, suitable amino acids (preferably phenylalanine or tyrosine) are subjected to reductive amination so as to form the corresponding alkene-1-carboxylic acid. Preferably after esterification and separation, this is used in cross-metathesis for the concomitant production of styrene resp. hydroxy styrene, and acrylates. The invention is applicable more widely, to the synthesis of olefins on the basis of carbohydrates, naturally occurring phenolic components, natural protein resources, or amino acids obtained from fermentations.

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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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Synthesis of a C-iminoribofuranoside analog of the nicotinamide phosphoribosyltransferase (NAMPT) inhibitor FK866

FK866 (also named APO866 or WK175) is a potent NAMPT inhibitor being evaluated (Phase II) as a potential anticancer drug. The preparation of the C-iminoribofuranoside analog (2E)-N-[4-(1-benzoylpiperidin-4-yl)butyl]-3-{3- [(2S,3S,4R,5R)-3,4-dihydroxy-5-(hydroxymethyl)pyrrolidin-2-yl]phenyl} prop-2-enamide ((-)-1) is reported. Copyright

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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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Metathesis for catalyst design: Metacatalysis

Prior studies have shown an effective way to produce diverse ligand sets for catalyst discovery is by using mixtures of monodentate forms to generate catalysts in situ. Research described here was performed to illustrate that alkene-functionalized monodentate ligands could be used in this way and in another that increases the diversity of the ligand library in an interesting way. Specifically, we hypothesized that as well as being used as monomers, these alkenes could be cross metathesized in situ immediately before the catalysis step. This combination of metathesis to form ligands in situ, then catalysis is referred to here as metacatalysis. In the event, a library of quinidine and quinine alkaloid-derived phosphites were tested as mixtures of monomers and dimers formed via metathesis in situ. The data obtained illustrated that metacatalysis can be used to identify ligands that positively and negatively modulate enantioselectivities in iridium-mediated hydrogenations of alpha,beta-unsaturated carboxylic acid derivatives, relative to the mixtures of the monomeric forms used.

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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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High-Performance Isocyanide Scavengers for Use in Low-Waste Purification of Olefin Metathesis Products

Three isocyanides containing a tertiary nitrogen atom were investigated for use as small-molecule ruthenium scavenging agents in the workup of olefin metathesis reactions. The proposed compounds are odorless, easy to obtain, and highly effective in removing metal residues, sometimes bringing the metal content below 0.0015 ppm. The most successful of the tested compounds, II, performs very well, even with challenging polar products. The performance of these scavengers is compared and contrasted with other known techniques, such as silica gel filtration and the use of self-scavenging catalysts. As a result, a new hybrid purification method is devised, which gives better results than using either a self-scavenging catalyst or a scavenger alone. Additionally, isocyanide II is shown to be a deactivating (reaction quenching) agent for olefin metathesis and superior to ethyl vinyl ether.

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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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Synthesis of siloxy-modified second generation Hoveyda-Grubbs catalysts and their catalytic activity

Efficient syntheses of the first ruthenium alkylidene complexes bearing siloxide ligands are described. Second generation Hoveyda-Grubbs catalyst is shown to undergo efficient functionalization with a number of potassium silanolates to give disiloxy derivatives. The complexes obtained are found catalytically active in selected metathesis transformations.

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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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Depolymerization of Bottlebrush Polypentenamers and Their Macromolecular Metamorphosis

The depolymerization of bottlebrush (BB) polymers with varying lengths of polycyclopentene (PCP) backbone and polystyrene (PS) grafts is investigated. In all cases, ring closing metathesis (RCM) depolymerization of the PCP BB backbone appears to occur through an end-to-end depolymerization mechanism as evidenced by size exclusion chromatography. Investigation on the RCM depolymerization of linear PCP reveals a more random chain degradation process. Quantitative depolymerization occurs under thermodynamic conditions (higher temperature and dilution) that drives RCM into cyclopentenes (CPs), each bearing one of the original PS grafts from the BB. Catalyst screening reveals Grubbs’ third (G3) and second (G2) generation catalyst depolymerize BBs significantly faster than Grubbs’ first generation (G1) and Hoveyda-Grubbs’ second generation (HG2) catalyst under identical conditions while solvent (toluene versus CHCl3) plays a less significant role. The length of the BB backbone and PS side chains also play a minor role in depolymerization kinetics, which is discussed. The ability to completely deconstruct these BB architectures into linear grafts provides definitive insights toward the ATRP “grafting-from” mechanism originally used to construct the BBs. Core-shell BB block copolymers (BBCPs) are shown to quantitatively depolymerize into linear diblock polymer grafts. Finally, the complete depolymerization of BBs into alpha-cyclopentenyl-PS allows further transformation to other architectures, such as 3-arm stars, through thiol-ene coupling onto the CP end group. These unique materials open the door to stimuli-responsive reassembly of BBs and BBCPs into new morphologies driven by macromolecular metamorphosis.

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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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Amino acids as chiral anionic ligands for ruthenium based asymmetric olefin metathesis

Several amino acid ligands were introduced into the Hoveyda-Grubbs 2nd generation complex by a facile anionic ligand exchange. The chiral pre-catalysts obtained displayed enantioselectivity in asymmetric ring-closing and ring-opening cross-metathesis reactions. Reduction of the lability of the carboxylate ligands was found to be cardinal for improving the observed enantiomeric product enrichment.

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

Final Thoughts on Chemistry for (1,3-Dimesitylimidazolidin-2-ylidene)(2-isopropoxybenzylidene)ruthenium(VI) chloride

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Total Synthesis of Leupyrrins A1 and B1, Highly Potent Antifungal Agents from the Myxobacterium Sorangium cellulosum

Full details on the design, elaboration, and application of efficient strategies for the high-yielding total syntheses of leupyrrins A1 and B1, unique antifungal agents from the myxobacterium Sorangium cellulosum, are reported. A sequential zirconocene-mediated diyne-cyclization, and regioselective opening of the zirconacyclopentadiene intermediate enabled a concise entry into the unique dihydrofuran fragment, whereas another domino reaction was developed for the butyrolactone involving a one-pot lactol opening, stereoselective aldehyde addition and in situ lactonization. Furthermore, an innovative sp2-sp3-cross-coupling for pyrrole functionalization and an optimized HATU-mediated amide coupling protocol of two elaborate fragments were established. In addition, an unusual protective group strategy, involving a Teoc-acetonide protected amine in combination with tert-butyl and acetate esters, was successfully elaborated. These tactics and strategies are generally useful and may be also applied in the synthesis of other functionalized compounds. It is expected that the material which was obtained by these total syntheses will enable the further exploration of the biological profile of these potent antifungal agents.

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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 dictyostatin and synthesis of two dictyostatin analogues

A formal convergent synthesis of dictyostatin from (R)-Roche ester is described. Synthetic highlights include a Ni-catalyzed Nozaki-Hiyama-Kishi coupling between an aldehyde and a Z vinyl iodide to assemble the two main fragments, a diastereoselective Myers alkylation, a stereoselective Evans aldolization, two asymmetric Duthaler crotyltitanations, and a stereoselective Pd-catalyzed Marshall allenylindium addition to install the stereogenic centers of dictyostatin. The synthesis of (9R)-epi-dictyostatin and a new ring-contracted dictyostatin isomer were also achieved. Copyright

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