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ROM-RCM of azabicycloheptene derivatives-Study of products distribution by the substituent on alkyne

ROM-RCM (ring-opening metathesis and ring-closing metathesis) of azabicyclo[2.2.1]heptene-ynes using the second-generation Grubbs catalyst was investigated. When an azabicycloheptene derivative was exposed to a catalytic amount of a ruthenium carbene complex, pyrrolizidine and indolizidine derivatives were obtained in good yields. The distribution of these products depends on the substituents on the alkyne.

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

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Iriomoteolides: Novel chemical tools to study actin dynamics

Despite its promising biological profile, the cellular targets of iriomoteolide-3a, a novel 15-membered macrolide isolated from Amphidinium sp., have remained unknown. A small library of non-natural iriomoteolide-3a analogues is presented here as a result of a novel, highly convergent, catalysis-based scaffold-diversification campaign, which revealed the suitable sites for chemical editing in the original core. We provide compelling experimental evidence for actin as one of iriomoteolides’ primary cellular targets, establishing the ability of these secondary metabolites to inhibit cell migration, induce severe morphological changes in cells and cause a reversible cytoplasmic retraction and reduction of F-actin fibers in a time and dose dependent manner. These results are interpreted in light of the ability of iriomoteolides to stabilize F-actin filaments. Molecular dynamics simulations provide evidence for iriomoteolide-3a binding to the barbed end of G-actin. These results showcase iriomoteolides as novel and easily tunable chemical probes for the in vitro study of actin dynamics in the context of cell motility processes including cell invasion and division.

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

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Potent inhibitors of hepatitis C core dimerization as new leads for anti-hepatitis C agents

New indoline alkaloid-type compounds which inhibit HCV production by infected hepatoma cells have been identified. These compounds, dimeric-type compounds of previously known inhibitors, display double digit nanomolar IC 50 and EC50 values, with cytotoxicity CC50 indexes higher than 36 muM, thus providing ample therapeutic windows for further development of HCV drugs.

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

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Stereoselective synthesis of dienyl phosphonates via extended tethered ring-closing metathesis

Allylphosphonates of allylic alcohols were converted to conjugated dienyl phosphonates in a one-flask reaction, comprising a ring-closing metathesis (RCM), a base-induced ring-opening, and an alkylation. The ring-opening proceeds with very high diastereoselectivity, giving exclusively the (1Z,3E)-configured dienes. Single diastereomers and mixtures of diastereomers can be used as starting materials without noticeable effect on the diastereoselectivity of the sequence.

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

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Total synthesis of the aspercyclides

Two different approaches to the eleven-membered biaryl ether lactones of the aspercyclide family are disclosed. The core regions of these highly strained targets, which are able to interfere with the binding of immunoglobulinE to its high affinity receptor, can either be forged by ring-closing olefin metathesis (RCM) or by a highly diastereoselective chromium-mediated Nozaki-Hiyama-Kishi (NHK) reaction. Whereas the RCM approach turned out to be responsive to minor changes in the substitution pattern of the substrate, the NHK route is more generally applicable. The preparation of the required cyclization precursor 43 hinged on a palladium-catalyzed orthoiodination reaction of 2-methylbenzoic acid, an efficient copper-catalyzed Ullmann coupling, and a Takai-Utimoto olefination as the key steps. Moreover, the esterification of the 2,6-disubstituted benzoic acid 34 with the sterically hindered secondary alcohol 37 was far from trivial. However, this and related transformations were accomplished by recourse to the corresponding acid fluorides, which provided excellent yields in cases in which the more commonly used acid chlorides or mixed anhydrides failed to afford any of the desiredproducts.

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

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Cross-metathesis/isomerization/allylboration sequence for a diastereoselective synthesis of anti-homoallylic alcohols from allylbenzene derivatives and aldehydes

We describe a highly diastereoselective approach to anti-homoallylic alcohols from allylbenzene derivatives and aldehydes. The strategy is based on a cross-metathesis/isomerization/allylboration sequence catalyzed successively by ruthenium and iridium. This methodology provides another way to access this class of compounds, which leads to the preparation of hitherto-unknown homoallylic alcohols without the requirement to control the stereochemistry of the 1-alkenyl boronate intermediates. Our study towards an enantioselective version of this sequential reaction is also reported.

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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. 246047-72-3, Name is (1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium, molecular formula is C46H65Cl2N2PRu. In a Erratum£¬once mentioned of 246047-72-3, Application In Synthesis of (1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium

Correction: Exploiting and understanding the selectivity of Ru-N-heterocyclic carbene metathesis catalysts for the ethenolysis of cyclic olefins to alpha,omega-Dienes (Journal of the American Chemical Society (2017) 139:37 (13117-13125) DOI: 10.1021/jacs.7b06947)

The isotropic chemical shielding (iso) was mislabeled as the isotropic chemical shift (iso) in Table S40, Figures 2, 4, S153 and in the respective discussion of these figures in the text. The corrected figures are shown below; the SI graphics are provided in the corrected SI file. In the conclusion section, “cyclic olefins” was incorrectly written as “cyclic dienes” to be the essential structural feature for the selective ethenolysis toward w-dienes. The ROMP activity of Ru-20 is not detectable in the “presence of ethylene”; this was incorrectly written as the “absence of ethylene”. Equations 5 and 7, pages S47 and S135 respectively, had errors that have been fixed in the corrected SI file. None of the above affects any conclusions of the article. (Figure Presented).

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

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Divergent total synthesis of the antimitotic agent leiodermatolide

Subtle but distinctive: The stereostructure of the biologically highly promising antimitotic agent leiodermatolide was uncertain. A short, efficient, and flexible total synthesis based on ring-closing alkyne metathesis as the key step has now solved the puzzle. Subtle differences in the 1H NMR spectra of the structure shown and the conceivable isomer proved invaluable for the assignment. Copyright

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

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Synthesis and biological evaluation of nucleoside dicarboxylates as potential mimics of nucleoside diphosphates

A series of nucleotide analogues wherein the diphosphate moiety has been replaced by a dicarboxylate were synthesized and tested for inhibitory activity against nucleoside diphosphate (NDP) kinase as well as several pathogenic bacterial strains. This journal is The Royal Society of Chemistry.

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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. 246047-72-3, Name is (1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium, molecular formula is C46H65Cl2N2PRu. In a Article£¬once mentioned of 246047-72-3, HPLC of Formula: C46H65Cl2N2PRu

Ring-closing metathesis reactions of terminal alkene-derived cyclic phosphazenes

The first examples of ring-closing metathesis (RCM) reactions of a series of terminal alkene-derived cyclic phosphazenes have been carried out. The tetrakis-, hexakis-, and octakis(allyloxy)cyclophosphazenes (NPPh 2)(NP(OCH2CH = CH2)2)2 (1), N3P3(OCH2CH = CH2)6 (2), and N4P4(OCH2CH = CH2) 8 (3) and the tetrakis(allyloxy)-S-phenylthionylphosphazene (NS(O)Ph)[NP(OCH2CH = CH2)2]2 (4) were prepared by the reactions of CH2 = CHCH2ONa with the cyclophosphazenes (NPPh2)(NPCl2)2, N 3P3Cl6, and N4P4Cl 8 and the S-phenylthionylphosphazene (NS(O)Ph)(NPCl2) 2. The reactions of 1-4 with Grubbs first-generation olefin metathesis catalyst Cl2Ru = CHPh(PCy3)2 resulted in the selective formation of seven-membered di-, tri-, and tetraspirocyclic phosphazene compounds (NPPh2)[NP(OCH2CH = CHCH2O)]2 (5), N3P3(OCH 2CH = CHCH2O)3 (6), and N4P 4(OCH2CH = CHCH2O)4 (7) and the dispirocyclic S-phenylthionylphosphazene compound (NS(O)Ph)[NP(OCH2CH = CHCH2O)]2 (8). X-ray structural studies of 5-8 indicated that the double bond of the spiro-substituted cycloalkene units is in the cis orientation in these compounds. In contrast to the reactions of 1-4, RCM reactions of the homoallyloxy-derived cyclophosphazene and thionylphosphazene (NPPh2)[NP(OCH2CH2CH = CH2) 2]2 (9) and (NS(O)Ph)[NP(OCH2CH2CH = CH2)2]2 (10) with the same catalyst resulted in the formation of 11-membered diansa compounds NPPh2[NP(OCH 2CH2CH = CHCH2CH2O)]2 (11) and (NS(O)Ph)[NP(OCH2CH2CH = CHCH2CH 2O)]2 (13) and the intermolecular doubly bridged ansa-dibino-ansa compounds 12 and 14. The X-ray structural studies of compounds 11 and 13 indicated that the double bonds of the ansa-substituted cycloalkene units are in the trans orientation in these compounds. The geminal bis(homoallyloxy)tetraphenylcyclotriphosphazene [NPPh2] 2[NP(OCH2CH2CH = CH2)2] (15) upon RCM with Grubbs first- and second-generation catalysts gave the spirocyclic product [NPPh2]2[NP(OCH2CH 2CH = CHCH2CH2O)] (16) along with the geminal dibino-substituted dimeric compound [NPPh2]2[NP(OCH 2CH2CH = CHCH2CH2O) 2PN][NPPh2]2 (17) as the major product. The dibino compound 17, upon reaction with the Grubbs second-generation catalyst, was found to undergo a unique ring-opening metathesis reaction, opening up the bino bridges and partially converting to the spirocyclic compound 16.

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