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Ruthenium Olefin Metathesis Catalysts Systematically Modified in Chelating Benzylidene Ether Fragment: Experiment and Computations

Five Hoveyda?Grubbs-type complexes bearing cyclopropyl to cycloheptyl ether moieties in the chelating benzylidene ligand have been synthesized and investigated by spectroscopic and crystallographic methods. Their experimentally measured catalytic activity in model ring-closing metathesis (RCM) reactions was studied at catalyst loading down to 10 ppm and compared with DFT calculations. The latter can be used as a reliable and accurate guidance in the fast and inexpensive design of new metathesis catalysts, as we were able to find a good correlation between the initiation rate and free-energy barrier of the reaction.

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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 and Evaluation of Ruthenium 2-Alkyl-6-mercaptophenolate Catalysts for Olefin Metathesis

A series of ruthenium carbene catalysts containing 2-sulfidophenolate bidentate ligand with an ortho-substituent next to the oxygen atom were synthesized. The molecular structure of ruthenium carbene complex containing 2-isopropyl-6-sulfidophenolate ligand was confirmed through single crystal X-ray diffraction. An oxygen atom can be found in the opposite position of the N-heterocyclic carbene (NHC) based on the steric hindrance and strong trans-effects of the NHC ligand. The ruthenium carbene catalyst can catalyze ring-opening metathesis polymerization (ROMP) reaction of norbornene with high activity and Z-selectivity and cross metathesis (CM) reactions of terminal alkenes with (Z)-but-2-ene-1,4-diol to give Z-olefin products (Z/E ratios, 70:30?89:11) in low yields (13%?38%). When AlCl3 was added into the CM reactions, yields (51%?88%) were considerably improved and process becomes highly selective for E-olefin products (E/Z ratios, 79:21?96:4). Similar to other ruthenium carbene catalysts, these new complexes can tolerate different functional groups.

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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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In an article, published in an article, once mentioned the application of 301224-40-8, Name is (1,3-Dimesitylimidazolidin-2-ylidene)(2-isopropoxybenzylidene)ruthenium(VI) chloride,molecular formula is C31H38Cl2N2ORu, is a conventional compound. this article was the specific content is as follows.Formula: C31H38Cl2N2ORu

Ruthenium catalysed cross metathesis with fluorinated olefins

The E-selective cross metathesis (CM) of fluorinated olefins with various functionalised alkenes in good to excellent yields is reported.

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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 spirocyclic thiazolidinediones using ring-closing metathesis and one-pot sequential ring-closing/cross metathesis

A novel synthetic route to spirocyclic thiazolidinediones is reported by utilizing ring-closing metathesis (RCM). A selective cross metathesis (CM) of N-allyl azaspiro derivatives with different olefins has been demonstrated to prepare substituted azaspiro-[4.4]nonenediones. The X-ray crystal structure of a spirocyclic thiazolidinedione dimer is described, which has been prepared in two steps from thiazolidinedione using a one-pot sequential ring-closing and self metathesis. Cross metathesis proceeds smoothly with both electron rich and poor olefins. The symmetrical bis-thiazolidinedione spirocyclic system can be used as CM coupling partner with olefins. One-pot sequential RCM-CM has been developed for the synthesis of substituted spirocyclic compounds. The methodology allows a quick access to thia-azaspiro-[4.4]nonene and -[4.5]decene-dione ring systems from readily available starting materials which are not otherwise accessible.

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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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Stereoselective synthesis of macrocyclic peptides via a dual olefin metathesis and ethenolysis approach

Macrocyclic compounds occupy an important chemical space between small molecules and biologics and are prevalent in many natural products and pharmaceuticals. The growing interest in macrocycles has been fueled, in part, by the design of novel synthetic methods to these compounds. One appealing strategy is ring-closing metathesis (RCM) that seeks to construct macrocycles from acyclic diene precursors using defined transition-metal alkylidene catalysts. Despite its broad utility, RCM generally gives rise to a mixture of E- and Z-olefin isomers that can hinder efforts for the large-scale production and isolation of such complex molecules. To address this issue, we aimed to develop methods that can selectively enrich macrocycles in E- or Z-olefin isomers using an RCM/ethenolysis strategy. The utility of this methodology was demonstrated in the stereoselective formation of macrocyclic peptides, a class of compounds that have gained prominence as therapeutics in drug discovery. Herein, we report an assessment of various factors that promote catalyst-directed RCM and ethenolysis on a variety of peptide substrates by varying the olefin type, peptide sequence, and placement of the olefin in macrocycle formation. These methods allow for control over olefin geometry in peptides, facilitating their isolation and characterization. The studies outlined in this report seek to expand the scope of stereoselective olefin metathesis in general RCM.

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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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Evolution of a total synthesis of (-)-kendomycin exploiting a Petasis-Ferrier rearrangement/ring-closing olefin metathesis strategy

A convergent stereocontrolled total synthesis of (-)-kendomycin (1) has been achieved. The synthesis proceeds with a longest linear sequence of 21 steps, beginning with commercially available 2,4-dimethoxy-3-methylbenzaldehyde (12). Highlights of the synthesis include an effective Petasis-Ferrier union/rearrangement tactic to construct the sterically encumbered tetrahydropyran ring, a ring-closing metathesis to generate the C(4a-13-20a) macrocycle, an effective epoxidation/deoxygenation sequence to isomerize the C(13,14) olefin, and a biomimetic quinone-methide-lactol assembly to complete the 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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A new model for the presentation of tumor-associated antigens and the quest for an anticancer vaccine: A solution to the synthesis challenge via ring-closing metathesis

Fully synthetic, carbohydrate-based antitumor vaccine candidates have been synthesized in highly clustered modes. Multiple copies of tumor-associated carbohydrate antigens, Tn and STn, were assembled on a single cyclic peptide scaffold in a highly convergent manner. Ring-closing metathesis-mediated incorporation of an internal cross-linker was also demonstrated. In particular, this rigidified cross-linked construct would enhance a cluster-recognizing antibody response by retaining an appropriate distance between glycans attached to the peptide platform. Details of the design and synthesis of highly clustered antigens are described herein.

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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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Comprehensive study on olefin metathesis in PEG as an alternative solvent under microwave irradiation

Polyethylene glycols (PEGs) are non-toxic, biodegradable and sustainable organic solvents, which find a large application in the chemical and pharmaceutical industry. In this study, we present the ring-closing metathesis reaction (RCM) in PEG under microwave irradiation. Several benchmark substrates, yielding 5- to 6-membered rings featuring di- or tri-substituted olefins, were evaluated. This study demonstrated that PEGs are suitable solvent for olefin metathesis. However, depending on the substrate/catalyst couple, isomerization may occur.

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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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Chemodiscrimination of Olefin Bonds Through Cross-Metathesis Reactions ? Synthesis of Functionalized beta-Lactam and beta-Amino Acid Derivatives

Chemodifferentiation of C=C bonds of various diolefinated beta-lactams or beta-amino esters has been investigated through cross-metathesis reactions. The transformations involved substrate-dependent cross-metathesis of dialkenylated azetidinones, derived from the ring opening of constrained unsaturated bicyclic beta-lactam isomers. Cross-metathesis reactions have been carried out under various conditions and catalysts in view of chemodiscrimination affording functionalized beta-lactams or beta-amino acid derivatives.

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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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Enol ethers as substrates for efficient Z-and enantioselective ring-opening/cross-metathesis reactions promoted by stereogenic-at-Mo complexes: Utility in chemical synthesis and mechanistic attributes

The first examples of catalytic enantioselective ring-opening/cross- metathesis (EROCM) reactions that involve enol ethers are reported. Specifically, we demonstrate that catalytic EROCM of several oxa-and azabicycles, cyclobutenes and a cyclopropene with an alkyl-or aryl-substituted enol ether proceed readily in the presence of a stereogenic-at-Mo monopyrrolide-monoaryloxide. In some instances, as little as 0.15 mol % of the catalytically active alkylidene is sufficient to promote complete conversion within 10 min. The desired products are formed in up to 90% yield and >99:1 enantiomeric ratio (er) with the disubstituted enol ether generated in >90% Z selectivity. The enol ether of the enantiomerically enriched products can be easily differentiated from the terminal alkene through a number of functionalization procedures that lead to the formation of useful intermediates for chemical synthesis (e.g., efficient acid hydrolysis to afford the enantiomerically enriched carboxaldehyde). In certain cases, enantioselectivity is strongly dependent on enol ether concentration: larger equivalents of the cross partner leads to the formation of products of high enantiomeric purity (versus near racemic products with one equivalent). The length of reaction time can be critical to product enantiomeric purity; high enantioselectivity in reactions that proceed to >98% conversion in as brief a reaction time as 30 s can be nearly entirely eroded within 30 min. Mechanistic rationale that accounts for the above characteristics of the catalytic process is provided.

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