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Reactivity and selectivity differences between catecholate and catechothiolate ru complexes. Implications regarding design of stereoselective olefin metathesis catalysts

The origins of the unexpected finding that Ru catechothiolate complexes, in contrast to catecholate derivatives, promote exceptional Z-selective olefin metathesis reactions are elucidated. We show that species containing a catechothiolate ligand, unlike catecholates, preserve their structural integrity under commonly used reaction conditions. DFT calculations indicate that, whereas alkene coordination is the stereochemistry-determining step with catecholate complexes, it is through the metallacyclobutane formation that the identity of the major isomer is determined with catechothiolate systems. The present findings suggest that previous models for Z selectivity, largely based on steric differences, should be altered to incorporate electronic factors as well.

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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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An ionic liquid-tagged second generation Hoveyda-Grubbs ruthenium carbene complex as highly reactive and recyclable catalyst for ring-closing metathesis of di-, tri- and tetrasubstituted dienes

A second generation Hoveyda-Grubbs ruthenium carbene complex bearing an ionic liquid tag was prepared and shown to be a highly reactive catalyst for the ring-closing metathesis of di-, tri- and tetrasubstituted diene and enyne substrates in minimally ionic solvent systems ([Bmim]PF6/CH 2Cl2, 1:9-1:1 v/v). Both the catalyst and the ionic liquid can be conveniently recycled and repeatedly reused (up to 17 cycles) with only a very slight loss of activity. The ionic liquid tag is crucial to the high level of recyclability of the catalyst since the original second generation Grubbs and Hoveyda-Grubbs catalysts rapidly lose their activity when recycled in the ionic liquid layer.

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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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The reaction rate of a catalyzed reaction is faster than the reaction rate of the uncatalyzed reaction at the same temperature.301224-40-8, Name is (1,3-Dimesitylimidazolidin-2-ylidene)(2-isopropoxybenzylidene)ruthenium(VI) chloride, molecular formula is C31H38Cl2N2ORu. In a Article£¬once mentioned of 301224-40-8, Application In Synthesis of (1,3-Dimesitylimidazolidin-2-ylidene)(2-isopropoxybenzylidene)ruthenium(VI) chloride

ADMET reactions in miniemulsion

This work investigates acyclic diene metathesis (ADMET) polymerization reactions in aqueous miniemulsion. Different types of ruthenium-based catalysts and different surfactants (anionic, cationic, and nonionic) were evaluated. A Ru-indenylidene catalyst (Umicore M2) showed higher activity in water if compared to the Ru-benzylidene catalysts (Hoveyda Grubbs second generation and Grubbs first generation). Moreover, the catalyst activity was affected by the type of the surfactant. In summary, the Umicore M2 catalyst and the nonionic poly(ethylene oxide) based surfactant Lutensol AT80 were found to be the most suitable combination for ADMET reactions in miniemulsion allowing the preparation of polymers with number average molecular weight (Mn) of up to 15 kDa.

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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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The reaction rate of a catalyzed reaction is faster than the reaction rate of the uncatalyzed reaction at the same temperature.301224-40-8, Name is (1,3-Dimesitylimidazolidin-2-ylidene)(2-isopropoxybenzylidene)ruthenium(VI) chloride, molecular formula is C31H38Cl2N2ORu. In a Article£¬once mentioned of 301224-40-8, HPLC of Formula: C31H38Cl2N2ORu

Enantioselective total synthesis of pinnaic acid and halichlorine

The enantioselective total synthesis of the bioactive marine natural products pinnaic acid and halichlorine is reported in detail. Our total synthesis features the construction of the five-membered ring and C9 and C13 stereogenic centers through a palladium-catalyzed trimethylenemethane [3+2] cyclization; the installation of the nitrogen atom through a regioselective Beckmann rearrangement of a poorly reactive ketone; the stereoselective cyclization of the spiro ring through a four-step, one-pot hydrogenation- cyclization; and efficient connection of the sterically hindered lower chain through a reduced-pressure cross olefin metathesis reaction. 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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Total synthesis of (-)-dactylolide

Figure Presented Multiple metals in action: Relying on the prowess of various metal-catalyzed C-O and C-C bond-forming reactions, a concise asymmetric total synthesis of (-)dactylolide has been achieved (see scheme). The formation of a Z-trisubstituted vinylboronate through an Alder-ene reaction and subsequent rhenium-mediated regioselective transposition of an allylic alcohol are the key features of this convergent synthesis.

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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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301224-40-8, Name is (1,3-Dimesitylimidazolidin-2-ylidene)(2-isopropoxybenzylidene)ruthenium(VI) chloride, molecular formula is C31H38Cl2N2ORu, belongs to ruthenium-catalysts compound, is a common compound. In a patnet, once mentioned the new application about 301224-40-8, name: (1,3-Dimesitylimidazolidin-2-ylidene)(2-isopropoxybenzylidene)ruthenium(VI) chloride

Fast olefin metathesis: Synthesis of 2-aryloxy-substituted Hoveyda-type complexes and application in ring-closing metathesis

Four 1-(4-R-phenoxy)-2-ethenylbenzenes (R=NMe2, H, Cl, NO 2) 4a, 4b, 4c and 4d were reacted with the ruthenium complexes [RuCl2(NHC)(3-phenylindenylidene)(py)] in the presence of a protic resin to result in the formation of the respective Hoveyda-type complexes 5a-d {NHC=SIMes [1,3-bis(2,4,6-trimethylphenylimidazolin)-2-ylidene]} and 6a-d {NHC=SIPr [1,3-bis(2,6-diisopropylphenylimidazolin)-2-ylidene]} in 66-84% yield. The lower steric bulk and the decreased donation of the diaryl ether oxygen atoms in complexes 5 and 6 led to rapidly initiating precatalysts. The Ru(II/III) redox potentials of complexes 6 were determined (6a-d: DeltaE=0.89-1.08 V). In the crystal structure of 5b two independent molecules were observed in the unit cell, displaying Ru-O distances of 226.6(4) and 230.5(3) pm. The catalytic performance of complexes 5 and 6 in various ring-closing metathesis (RCM) reactions was studied. Catalyst loadings of between 15-200 ppm are sufficient for the formation of >90% yield of the respective cyclic products. Complex 6b catalyzes the formation of N-protected 2,5-dihydropyrroles with up to TON 64,000 and TOF 256,000 h-1, of the N-protected 1,2,3,6- tetrahydropyridines with up to TON 18,200 and TOF 73,000 h-1 and of the N-protected 2,3,6,7-tetrahydroazepines with up to TON 8,100 and TOF 32,000 h-1 with yields ranging between 77 and 96%.

Balanced chemical reaction does not necessarily reveal either the individual elementary reactions by which a reaction occurs or its rate law.name: (1,3-Dimesitylimidazolidin-2-ylidene)(2-isopropoxybenzylidene)ruthenium(VI) chloride. In my other articles, you can also check out more blogs about 301224-40-8

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

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A catalyst don’t appear in the overall stoichiometry of the reaction it catalyzes, but it must appear in at least one of the elementary reactions in the mechanism for the catalyzed reaction. 301224-40-8, Name is (1,3-Dimesitylimidazolidin-2-ylidene)(2-isopropoxybenzylidene)ruthenium(VI) chloride, molecular formula is C31H38Cl2N2ORu. In a Article£¬once mentioned of 301224-40-8, Recommanded Product: 301224-40-8

A highly efficient ruthenium catalyst for metathesis reactions

A simple three-step synthesis leads to the formation of the active complex 1, which operates under very mild conditions (even at 0 C!) and can be successfully applied in various types of olefin metathesis (ring-closing metathesis, cross metathesis, enyne metathesis), for example, in the cyclization of 2 to form 3.

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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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Modular Synthesis of Diverse Natural Product-Like Macrocycles: Discovery of Hits with Antimycobacterial Activity

A modular synthetic approach was developed in which variation of the triplets of building blocks used enabled systematic variation of the macrocyclic scaffolds prepared. The approach was demonstrated in the synthesis of 17 diverse natural product-like macrocyclic scaffolds of varied (12?20-membered) ring size. The biological relevance of the chemical space explored was demonstrated through the discovery of a series of macrocycles with significant antimycobacterial activity.

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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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Template-directed one-step synthesis of cyclic trimers by ADMET

A trifurcated template, containing three secondary dialkylammonium ion recognition sites for encirclement by a dibenzo [24]crown-8-containing acyclic diene, is used to promote acyclic diene metatheses (ADMET) catalyzed by ruthenium-alkylidene complexes, affording a cyclic trimer in 55% yield. Following this one-step, threefold ADMET reaction, the resulting cyclic trimer was isolated by preparative HPLC and characterized by NMR spectroscopy and mass spectrometry. 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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Reactivity Studies of Alkoxy-Substituted [2.2]Paracyclophane-1,9-dienes and Specific Coordination of the Monomer Repeating Unit during ROMP

The polymerization of alkoxy-substituted [2.2]paracyclophane-1,9-dienes via ring-opening metathesis polymerization (ROMP) to obtain soluble poly(p-phenylenevinylene)s is a versatile method due to its living nature which enables the possibility of block copolymerization and end group modification. However, detailed studies on the reactivity behavior and the polymerization process of alkoxy-substituted [2.2]paracyclophane-1,9-dienes have not been reported so far. Herein we present a detailed study on the varying tendencies of the four isomers of dimethoxy-(2-ethylhexyloxy)-[2.2]paracyclophane-1,9-diene to undergo ROMP. Therefore, we carried out polymerization combining all individual isomers with five different metathesis catalysts and collected initiation and propagation kinetics for various combinations. Furthermore, we revealed a specific coordination of the monomer repeating unit to the catalyst during the polymerization process and succeeded to polymerize not only the pseudogeminal isomers but also one of the pseudo-ortho isomers.

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