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Migrastatin and isomigrastatin analogues have been synthesised in order to contribute to structure-activity studies on tumour cell migration inhibitors. These include macrocycles varying in ring size, functionality and alkene stereochemistry, as well as glucuronides. The synthesis work included application of the Saegusa-Ito reaction for regio- and stereoselective unsaturated macroketone formation, diastereoselective Brown allylation to generate 9-methylmigrastatin analogues and chelation-induced anomerisation to vary glucuronide configuration. Compounds were tested in vitro against both breast and pancreatic cancer cell lines and inhibition of tumour cell migration was observed in both wound-healing (scratch) and Boyden chamber assays. One unsaturated macroketone showed low affinity for a range of secondary drug targets, indicating it is at low risk of displaying adverse side effects.

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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 invention provides a silicon-containing diphenol and a preparation method thereof, wherein a structure of the silicon-containing diphenol is represented as the formula (I). The preparation method includes following steps: (A) with di-substituted divinyl silane as a raw material, performing a catalytic olefin double-decomposition reaction with vinylphenol to obtain an intermediate, di-substituted bis(hydroxylstyryl)silane; (B) performing catalytic hydrogenation and catalytic transfer hydrogenation to obtain di-substituted bis(hydroxylphenethyl)silane, which is the silicon-containing diphenol in the invention. The silicon-containing diphenol represented in the formula (I) is excellent in toughness, flame resistance and heat resistance. The preparation method is simple in operation, is mild in conditions, is high in product yield, is low in cost, is green and environment-friendly, and is high in industrialization value.

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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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Highly substituted polycyclic aromatic and heteroaromatic compounds are produced via a two-stage tandem benzannulation/cyclization strategy. The initial benzannulation step proceeds via a pericyclic cascade mechanism triggered by thermal or photochemical Wolff rearrangement of a diazo ketone. The photochemical process can be performed using a continuous flow reactor which facilitates carrying out reactions on a large scale and minimizes the time required for photolysis. Carbomethoxy ynamides as well as more ketenophilic bis-silyl ynamines and N-sulfonyl and N-phosphoryl ynamides serve as the reaction partner in the benzannulation step. In the second stage of the strategy, RCM generates benzofused nitrogen heterocycles, and various heterocyclization processes furnish highly substituted and polycyclic indoles of types that were not available by using the previous cyclobutenone-based version of the tandem strategy.

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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, flexible, and high yielding entry into the family of amphidinolide T macrolides, a series of cytotoxic natural products of marine origin, has been developed. All individual members, except amphidinolide T3 (3), derive from compound 39 as a common synthetic intermediate which is formed from three building blocks of similar size and complexity. The fragment coupling steps involve a highly diastereoselective SnCl4 mediated reaction of the furanosyl sulfone derivative 11 with the silyl enol ether 18 and a palladium-catalyzed Negishi type coupling reaction between the polyfunctional organozinc reagent derived from iodide 32a and the enantiopure acid chloride 24b. The 19-membered macrocyclic ring is then formed by a high yielding ring closing metathesis (RCM) reaction of diene 33 catalyzed by the “second generation” ruthenium carbene complex 34. The efficiency of the RCM transformation stems, to a large extent, from the conformational bias introduced by the syn-syn-configured stereotriad at C12-C14 of the substrate which constitutes a key design element of the synthesis plan. The use of Nysted’s reagent 38 in combination with TiCl4 was required for the olefination of the sterically hindered ketone group in 36, whereas more conventional alkene formations were unsuccessful for this elaboration. Finally, it is shown that the inversion of a single and seemingly remote stereocenter (C12) in one of the building blocks not only affects the efficiency and stereochemical outcome of the RCM step but also exerts a significant influence on the course of the acyl-Negishi reaction, allowing a radical manifold to compete with productive cross coupling.

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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 reactions of terminal olefins with acrylic esters catalyzed by a Ru-carbene complex ((H2IMes)(PCy3)Cl 2RuCHPh, H2IMes = N,N-bis(mesityl)-4,5-dihydroimidazol-2- ylidene) were applied to the end-capping of [2]pseudorotaxanes composed of dibenzo[24]crown-8 (DB24C8) and ferrocenylmethylammonium derivatives as the macrocyclic and axle components. A [3]rotaxane consisting of two DB24C8s and an axle molecule having ferrocenyl groups at both ends was obtained from the cross-metathesis reaction of two [2]pseudorotaxanes with Fe(C5H 4CH2OCOCHCH2)2. Cyclic voltammograms of the ferrocene-containing rotaxanes show reversible redox reactions whose potentials vary depending on the presence or absence of cationic dialkylammonium groups in the vicinity of the ferrocene units. The Royal Society of Chemistry.

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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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Aiming at improving catalyst activity, ten ruthenium promoters have been investigated in carbenoid transfer from ethyl diazoacetate to styrene as a model substrate. Optimal selectivity in cyclopropanation has been attained with the new NHC-Ru complex 10, as well as with the Fischer carbene 7. The surprising non-metathetical behavior of the Grubbs’ first-generation catalyst in this multifaceted process is highlighted. 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 comparative density functional theory study of tungsten-based Fischer carbenes, tungsten- and molybdenum-based Schrock carbenes, and ruthenium- and osmium-based Grubbs-type olefin metathesis catalysts reveals that the last group of catalysts should not be taken to be intermediate between the two established categories of carbenes. Rather, the Grubbs catalysts have characteristic properties similar to those of the Schrock family of carbenes and can be viewed as an extension of the latter class. Whereas an appreciable fraction of the electrons involved in the carbene bond of Fischer carbenes are unshared, and these compounds may be classified as “ionic” or “donor- acceptor” carbenes, a distinct covalent character is observed for both Schrock carbenes and Grubbs catalysts, which thus together fall into a larger category that may be termed “covalent” or “electron-sharing” carbenes. For these compounds, the energies of the atomic valence d orbitals determine the polarization of the and pi components of the carbene bond. Whereas the early metals (as reflected in valence d orbitals of relatively high energies) W and Mo render Schrock carbenes weakly nucleophilic, the later metals Ru and Os form weakly to moderately electrophilic carbenes. Schrock carbenes may thus, more accurately, be classified as “nucleophilic covalent” or “nucleophilic electron-sharing” carbenes, while Grubbs catalysts could be termed “electrophilic covalent” or “electrophilic electron-sharing” carbenes.

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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 convergent synthesis of the macrolactone core of amphidinolactone A has been achieved, in a 10 step linear sequence with 32% overall yield, through a ring-closing metathesis reaction as the macrolactonization step. The RCM precursor was obtained by the union of acid and alcohol fragments derived from (R)-epichlorohydrin and (R)-2,3-O-isopropylidene glyceraldehyde, respectively.

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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 describe a flexible and divergent route to the pyrrolo-/pyrido[1,2-j]quinoline frameworks of tricyclic marine alkaloids via a common intermediate formed by the ester-enolate Claisen rearrangement of a cyclic amino acid allylic ester. We have synthesized the proposed structure of polyci-torols and demonstrated that the structure of these alkaloids requires revision. In addition to asymmetric formal syntheses, stereoselective and concise total syntheses of (-)-lepadi-formine and (-)-fasicularin were also accomplished from simple, commercially available starting materials in a completely substrate-controlled manner. The key step in these total syntheses was the reagent-dependent stereoselective reductive amination of the common intermediate to yield either indolizidines 55 a or 55 b. Aziridinium-mediated carbon homologation of the hindered C-10 group to the homoallylic group facilitated the synthesis.

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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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“Cinnamylation-flavored” synthesis: Cross-metathesis (CM) reactions between an allylsilane andvinylarenes enable the rapidgeneration of various cinnamylsilanes, which may be usedin situ for the highly enantioselective, and diastereodivergent, cinnamylation of imines (see example in scheme). Under this new, simple, and efficient protocol, the potential of imine cinnamylation to produce stereochemically andfunctionally complex products has been more fully realized. Ar = thienyl, Ar? = 2-hydroxyphenyl. (Chemical Equation Presented).

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