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

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Emerald ash borer (EAB), Agrilus planipennis Fairmaire, is an invasive insect that has killed millions of ash trees in Canada and the USA. (3Z)-Dodecen-12-olide is a known female-produced pheromone of this insect, and a concise, three-step synthesis of a 2:1 blend of (3Z)-dodecen-12-olide and (3E)-dodecen-12-olide starting from commercially available (2-carboxyethyl) triphenylphosphonium bromide and 10-bromo-1-decene is described. The key steps in this synthesis are a lithium-salt-free Wittig reaction and an intramolecular SN2 esterification. Both of these macrocyclic lactones are behaviorally active toward EAB, and the 2:1 blend whose synthesis is described here has the potential to be a detection agent, mating disruptor, or mass trapping agent, which could be used in the control of EAB.

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

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The vacuolar-type (H+)-adenosine triphosphatase inhibitor oximidine III and its enamide and epoxide stereoisomers have been synthesized enantioselectively. A relay ring-closing metathesis (RCM) strategy was employed to facilitate the macrocyclization of a well-defined substrate possessing two differentially functionalized RCM alkene partners (see scheme).

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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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Cycloisomerization is a totally atom economic procedure which converts dienes and enynes into cyclic molecules. Modification of Grubbs’ 2nd generation catalysts by reaction with dimethylformamide provides a new species able to catalyse this transformation. Selection of suitable conditions allowed high yields and selectivity. Studies performed in order to identify the catalytic species point to a non-carbenic ruthenium complex that has lost the phosphine. No hydride signals appeared. In addition, the reaction works with enynes and the new species catalyses efficiently crossed cyclotrimerizations of alkynes with diynes.

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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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(Z)-1,8-Di(pyren-1-yl)oct-4-ene (1) was prepared as a probe for olefin metathesis. The conversions of substrate by olefin metathesis under various conditions were calculated using the ratiometric fluorescence intensity change of 1. The conversions calculated by 1 and gas chromatography were consistent. These results show that conversions of olefin metathesis can be simply obtained from the fluorescence change of 1 and this method can be applied to the high-throughput screening (HTS) method for various olefin metathesis.

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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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Cross metathesis between silylalkynes and various functionalized alkenes catalyzed by Grubbs carbene complex produced, in most cases, single regio- and stereoisomers of the resultant 1,3-dienes. Polar heteroatom substituents at the propargylic site are important for high reactivity and selectivity. An important mechanistic insight regarding the initiation event and the key propagating alkylidene in this reaction was obtained by employing a tandem cross metathesis ring-closing metathesis between a terminal alkene and a silylated alkyne possessing an alkene tether. 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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A bulky binol-based ligand is the key structural feature of the ruthenium complex 1, which displays an unprecedented metathesis activity combined with high stability. For a range of dienes, ring-closing metathesis reactions catalyzed by 1 lead to near quantitative yields of cycloalkenes after a few minutes.

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

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The translation of olefin metathesis reactions from the laboratory to process scale has been challenging with traditional batch techniques. In this contribution, we describe a continuous membrane reactor design that selectively permeates the ethylene byproduct from metathetical processes, thereby overcoming the mass-transport limitations that have negatively influenced the efficiency of this transformation in batch vessels. The membrane sheet-in-frame pervaporation module yielded turnover numbers of >7500 in the case of diethyl diallylmalonate ring-closing metathesis. The preparation of more challenging, low-effective-molarity substrates, a cyclooctene and a 14-membered macrocyclic lactone, was also effective. A comparison of optimal membrane reactor conditions to a sealed tubular reactor revealed that the benefits of ethylene removal are most apparent at low reaction concentrations.

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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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Initiation rates for Grubbs and Grubbs-Hoveyda second generation pre-catalysts have been measured accurately in a range of solvents. Solvatochromic fitting reveals different dependencies on key solvent parameters for the two pre-catalysts, consistent with different mechanisms by which the Grubbs and Grubbs-Hoveyda pre-catalysts initiate.

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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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Block copolymers of regioregular poly(3-hexylthiophene) (P3HT) and polyethylene (PE) were synthesized through the chain transfer of olefin-terminated P3HT in the presence of cyclooctene via ring-opening metathesis polymerization (ROMP). Subsequent hydrogenation of the poly(cyclooctene) block yielded high molecular weight, crystalline-crystalline P3HT-PE block copolymers, which are thermally stable and resistant to solvents under ambient conditions. These copolymers were characterized by 1H NMR, DSC, and WAXS and represent the first materials of a class of crystalline-crystalline semiconducting-insulating block copolymers. 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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A concise and convergent route to combretastatin D2 is described together with some preliminary biological data. The Royal Society of Chemistry 2006.

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