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Ru-catalyzed olefin metathesis has been successfully applied to the synthesis of biscardanol derivatives and cardanol-based porphyrins. Using Hoveyda-Grubbs catalyst (C627), the reactions were performed with various cardanol derivatives (2, 5, 7, and 9) to make novel biscardanol derivatives. With the use of the second-generation Grubbs catalyst (C848) and Ti(OiPr)4, the ring-closing metathesis of cardanol-based porphyrin 11 was carried out to afford cyclic cardanol-based porphyrin derivative 12.

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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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Applicability of 2-methyltetrahydrofuran for olefin metathesis was examined with a set of ruthenium Hoveyda-type second generation catalysts. Influence of temperature was studied and the results were compared with those obtained in classical solvents for metathesis: dichloromethane and toluene.

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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 use of the ring-closing enyne metathesis (RCEYM) as a methodology for the synthesis of the azonino[5,4-b]indole system, featuring the tricyclic substructure of the alkaloids cleavamine and quebrachamine, has been explored. Three series of enyne substrates were studied for their compatibility with the RCEYM reaction. In addition to the usual substrates bearing either a terminal or an internal alkyne, for the first time enynes with an alkynyl halide moiety were also considered. Although the metathesis cyclization allowed for assembly of the azoninoindole nucleus in all three series, an effective catalytic cycle was only noted for internal alkyne substrates. On the basis of the experimental results, the “yne-then-ene” pathway seems to be the mechanism at play in these reactions. The use of ring-closing enyne metathesis (RCEYM) as a methodology for the construction of the nine-membered ring of the 2,3,4,7-tetrahydro-1H-azonino[5,4-b]indole system has been explored.

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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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Synthesis of novel polyhydroxylated derivatives of decalin is described. The presented methodology consists in a one-pot copper-catalyzed 1,4-addition of vinylmagnesium bromide to sugar-derived cyclohexenone, followed by an aldol reaction with a derivative of but-3-enal. The obtained diene is then subjected to an assisted tandem catalytic sequence: ring-closing metathesis with the subsequent reuse of the Ru-catalyst in the syn-dihydroxylation. The stereochemical outcome of these reactions is discussed.

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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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Thiolate-coordinated ruthenium alkylidene complexes can give high Z-selectivity and stereoretentivity in olefin metathesis. To investigate their applicability as heterogeneous catalysts, we have successfully developed a methodology to easily immobilize prototype ruthenium alkylidenes onto hybrid mesostructured silica via a thiolate tether. In contrast, the preparation of the corresponding molecular complexes appeared very challenging in solution. These prototype supported complexes contain small thiolates but still, they are slightly more Z-selective than their molecular analogues. These results open the door to more active and selective heterogeneous catalysts by supporting more advanced thiolate Ru-complexes.

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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 in situ preparation of highly stereoretentive ruthenium-based metathesis catalysts is reported. This approach completely avoids the isolation of intermediates and air-sensitive catalysts, thus allowing for the rapid access and evaluation of numerous dithiolate Ru catalysts. A procedure was established to perform cross-metathesis reactions without the use of a glovebox, and on a small scale even Schlenk techniques are not required. Consequently, the chemistry displayed in this report is available to every practicing organic chemist and presents a powerful approach for the identification of new stereoretentive catalysts.

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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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Method of making a second olefin using a first olefin, comprising steps (A) and (B): (A) performing a metathesis reaction with the first olefin in the presence of a metal complex configured to catalyse said metathesis reaction; (B) epoxidizing an olefin contained in the reaction mixture obtained in step (A) to form an epoxide; and deoxygenizing said epoxide to form said second olefin.

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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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Acetylene to butadiene direct synthesis, via enyne cross-metathesis, is demonstrated with commercial ruthenium carbene catalysts. Using excess of ethylene, yields greater than 50% are obtained. High activity is observed in the first minute of the reaction (TOF > 800 h-1 based on butadiene). Catalyst reusability and poisoning are discussed. This journal is

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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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Reactions of the Grubbs 3rd generation complexes [RuCl2(NHC) (Ind)(Py)] (N-heterocyclic carbene (NHC)=1,3-bis(2,4,6- trimethylphenylimidazolin)-2-ylidene (SIMes), 1,3-bis(2,6- diisopropylphenylimidazolin)-2-ylidene (SIPr), or 1,3-bis(2,6- diisopropylphenylimidazol)-2-ylidene (IPr); Ind=3-phenylindenylid-1-ene, Py=pyridine) with 2-ethenyl-N-alkylaniline (alkyl=Me, Et) result in the formation of the new N-Grubbs-Hoveyda-type complexes 5 (NHC=SIMes, alkyl=Me), 6 (SIMes, Et), 7 (IPr, Me), 8 (SIPr, Me), and 9 (SIPr, Et) with N-chelating benzylidene ligands in yields of 50-75 %. Compared to their respective, conventional, O-Grubbs-Hoveyda complexes, the new complexes are characterized by fast catalyst activation, which translates into fast and efficient ring-closing metathesis (RCM) reactivity. Catalyst loadings of 15-150 ppm (0.0015-0.015 mol %) are sufficient for the conversion of a wide range of diolefinic substrates into the respective RCM products after 15 min at 50 C in toluene; compounds 8 and 9 are the most catalytically active complexes. The use of complex 8 in RCM reactions enables the formation of N-protected 2,5-dihydropyrroles with turnover numbers (TONs) of up to 58 000 and turnover frequencies (TOFs) of up to 232 000 h-1; the use of the N-protected 1,2,3,6-tetrahydropyridines proceeds with TONs of up to 37 000 and TOFs of up to 147 000 h-1; and the use of the N-protected 2,3,6,7-tetrahydroazepines proceeds with TONs of up to 19 000 and TOFs of up to 76 000 h-1, with yields for these reactions ranging from 83-92 %. The tortoise and the hare: The use of diphenylalkylamino-based instead of phenyldialkylamino-based styrenes (see figure) leads to rapidly initiating precatalysts that enable very fast ring-closing metathesis reactions with turnover numbers of up to 58 000 and turnover frequencies of up to 232 000 h-1. 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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The metathesis catalyst 1 allows the first living cyclopolymerization of 1,6-heptadiynes. With the chiral 4-(ethoxycarbonyl)-4-(1S,2R,5S)-(+)-menthoxycarbonyl-1,6-heptadiyne highly tactic polymers with an alternating cis-trans structure and a stereoregularity of greater than 95% are obtained. Fixation of 1 on poly(2-oxazo-line) block copolymers provides access to poly(acetylene) s under aqueous conditions by micellar catalysis.

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