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The (alkylidene) ruthenium complexes 1 and 2b were examined as catalysts for the ring-closing metathesis of the homologous series of ene-dienes 16 to ascertain the extent to which a divergence in product distribution would be observed. In each case, the levels of cyclic alkene and conjugated diene were determined (see Table 1). Double bond geometric assignments were made on the basis of vinyl proton 1H-NMR chemical shifts and coupling constants. MM3 Calculations were undertaken to gauge the levels of steric strain in end products of varying ring size. The global ensemble of facts, including key control experiments, demonstrate the striking differences between 1 and 2b. Finally, the steric energies are seen not to correlate with the product distributions, most probably due to the distinctive reactivity patterns of the metathesis reagents.

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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 variety of bridged metallocenes of Fe(II), Ru(II), Zr(IV), or Hf(IV) were prepared in good yield by the interannular ring-closing metathesis reaction of 1,1?-diallylmetallocenes using the Ru-carbene catalyst, and the present method was extended to diastereoselective reaction to give dl- or meso-bridged metallocenes with excellent stereoselectivity. 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 hexameric disaccharide cluster bearing the terminal Galalpha related xenotransplantation antigen was constructed using a sequence of ruthenium carbenoid catalyzed olefin self-metathesis of monoallylated tribenzyl pentaerythritol followed, after interconversion of benzyl ethers into paraiodobenzyl ethers, by a single step Sonogashira cross-coupling of six prop-2-ynyl glycosides onto a hexameric aryl iodide scaffold.

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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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We present the synthesis of five- and six-membered cyclic phenylalanine mimics (1, 9, 16 and 17) that are constrained in a proline-like conformation. The five-membered mimetic 16 was prepared by Ring Closing Metathesis (RCM) of diene 15, itself prepared by alpha-benzylation of the L-methionine derived oxazolidinone 10, followed by oxidative elimination, ring hydrolysis and N-allylation. The six-membered mimetic 1 was prepared by allylating the L-phenylalanine-derived oxazolidinone 5, followed by hydrolysis, N-allylation and RCM. Olefins 1 and 16 were catalytically hydrogenated to give 9 and 17, respectively. The solid state structures of 9 and 16 were determined by X-ray crystallography and their conformations compared with that of 1.

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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 wide range of bicyclic beta-lactam systems have been prepared via the enyne metathesis reaction using catalytic quantities of trans-(Cy3P)2Cl2Ru=CHPh (Cy = cyclohexyl).

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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 new stereocenter is formed by ring-rearrangement metathesis (RRM), which has now been extended to diastereoselective processes. Selectivities are catalyst- and substrate-dependent. In these conversions yielding carbo- and heterocycles, d.r. values of up to 14:1 were obtained. For example, cyclooctadiene 1 was converted into piperideine 2 at room temperature and with high diastereoselectivity (Ts = toluene-4-sulfonyl). (Chemical Equation Presented).

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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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In aqueous media, two well-defined ruthenium carbene complexes [(Cy3P)2Cl2Ru=CHCH=CPh2 (1) and (Cy3P)2Cl2Ru=CHPh (2), Cy = cyclohexyl] catalyzed living ring-opening metathesis polymerization (ROMP) of functionalized norbornenes and 7-oxanorbornenes. Monomers were dispersed in water using a cationic surfactant, and polymerization was initiated by injection of a catalyst solution to yield a polymer latex. The polymerization of hydrophilic 7-oxanorbornene monomer and a hydrophobic norbornene monomer displayed similar behavior in aqueous media, with the resultant polymers having lower molecular weights relative to polymerization in anhydrous organic solution on a similar time scale. The polydispersity indices (PDIs) of polymers prepared from the hydrophilic monomer using catalyst 1 in the presence of water (PDI = 1.20) were narrower than those obtained by solution polymerization (PDI = 2.11), while PDIs for polymers prepared using catalyst 2 remained low in both the presence of water and in anhydrous solution (PDI ? 1.13). The linear relationship between molecular weight and monomer/catalyst ratios and the absence of chain transfer and termination processes indicated that these systems are indeed living. Furthermore, this new ROMP technique was shown to be an efficient method for the preparation of well-defined block copolymers.

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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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Ring closing metathesis employing the well-known Grabbs’ ruthenium catalyst has been used as the key step in the synthesis of piperidine alkaloids, (-)-coniine and (-)-pipecoline, and the asymmetric induction has been performed by using (R)-alpha-methyl benzylamine as an auxiliary.

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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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Treatment of the hydrido(dihydrogen) compound [RuHCl(H2) (PCy3)2] 1 with alkynes RC?CH (R = H, Ph) afforded the hydrido(vinylidene) complexes [RuHCl(=C=CHR)(PCy3)2] 2, 3 which react with HCl or [HPCy3]Cl to give the corresponding Grubbs-type ruthenium carbenes [RuCl2(=CHCH2R)(PCy 3)2] 4, 5. The reaction of 2 (R = H) with DCl, or D 2O in the presence of chloride sources, led to the formation of [RuCl2(=CHCH2D)(PCy3)2] 4-d 1. Based on these observations, a one-pot synthesis of compounds 4 and 5 was developed using RuCl3·3H2O as the starting material. The hydrido(vinylidene) derivative 2 reacted with CF 3CO2H and HCN at low temperatures to yield the carbene complexes [RuCl(X)(=CHCH3)(PCy3)2] 6,7, of which 7 (X = CN) was characterized crystallographically. Salt metathesis of 2 with CF3CO2K and KI led to the formation of [RuH(X)(=C=CH2)(PCy3)2] 8, 9. The bis(trifluoracetato) and the diiodo compounds [RuX2(=CHCH 3)(PCy3)2] 10,11 as well as the new phosphine P(thp)3 12 (thp = 4-tetrahydropyranyl) and the corresponding complex [RuCl2(=CHCH3){P(thp)3}2] 14 were also prepared. The catalytic activity of the ruthenium carbenes 4-7, 10, 11 and 14 in the olefin cross-metathesis of cyclopentene and allyl alcohol was investigated. The Royal Society of Chemistry 2005.

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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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Got a light? An efficient method for the synthesis of phosphorus- functionalized bis(acyl)phosphaneoxides (BAPOs) was developed, which allows the preparation of photoactive polymers or grafting of these photoinitiators to various surfaces. Irradiation in the presence of polymerizable monomers leads to coatings that can be deposited imagewise. Copyright

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