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Total synthesis and structural elucidation of azaspiracid-1. Final assignment and total synthesis of the correct structure of azaspiracid-1

The molecular structure of azaspiracid-1, a neurotoxin isolated from mussels, has been elucidated by total synthesis which also enriched its supplies. The degradatively derived fragments of this marine biotoxin, compounds 5 (EFGHI), 6 (FGHI), and 40 (ABCD), were matched with synthetic materials, thus confirming their structural identities. Based on this detective work, a new structure of azaspiracid-1 (i.e., 1) was proposed and constructed by total synthesis. The final strategy for the total synthesis of azaspiracid-1 featured a dithiane anion (C21-C27 fragment) reacting with a pentafluorophenol ester (C1-C20 fragment) followed by a Stille-type union of an advanced allylic acetate substrate (C1-C 27 fragment) with a vinyl stannane as the main coupling processes to assemble the carbon skeleton of the molecule. In addition to the total synthesis of azaspiracid-1 (1), the syntheses of its C1-C20 epimer (2) and of several truncated analogues for biological investigations are described.

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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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Related Products of 246047-72-3, Catalysts are substances that increase the reaction rate of a chemical reaction without being consumed in the process. 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

Synthesis of Various Heterocycles Having a Dienamide Moiety by Ring-Closing Metathesis of Ene-ynamides

Ring-closing metathesis (RCM) of ynamides, having alkene substituents of various lengths on the side chain, was demonstrated using the second-generation Grubbs catalyst. When the reaction of ene-ynamides was carried out in the presence of 5 mol% of the catalyst, RCM proceeded smoothly to give quinoline or isoquinoline derivatives having a dienamide unit in good yields. Furthermore, RCM of ene-ynamides, having one more carbon on the side chain, proceeded smoothly to provide seven-membered heterocycles having a dienamide component. Similarly, eight-membered heterocycles, diazocine and benzodiazocine, were also synthesized by RCM of ene-ynamides in good yields.

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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.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, name: (1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium

Synthesis, Structure, and Local Molecular Dynamics for Crystalline Rotors Based on Hecogenin/Botogenin Steroidal Frameworks

The synthesis and solid-state characterization of a series of cyclic/acyclic molecular rotors derived from naturally occurring steroidal 12-oxosapogenins are described. The bridged molecular rotors with rigid steroidal frameworks were obtained by employing ring-closing metathesis (RCM) as a key step. The X-ray diffraction technique was employed for determination and refinement of the crystal and molecular structure of selected models giving good quality single crystals. In the case of the bridged hecogenin molecular rotor 11E for which poor quality crystals were obtained, an NMR crystallography approach was used for fine refinement of the structure. Solid state NMR spectroscopic techniques were applied for the study of local molecular dynamics of the featured acyclic/cyclic molecular rotors. Analysis of 13C principal components of chemical shift tensors and chemical shift anisotropy (CSA) as well as heteronuclear 1H-13C dipolar couplings (DC) unambiguously proved that aromatic rings located in the space within the rigid steroidal framework both for cyclic and acyclic rotors are under kHz exchange regime. Experimental results were confirmed by theoretical calculations of rotation barrier on the density functional theory level. Small distinctions in the values of CSA and DC for the rotors under investigation are explained on the basis of differences in their molecular structures.

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

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Asymmetric Allylation/RCM-Mediated Synthesis of Fluorinated Benzo-Fused Bicyclic Homoallylic Amines As Dihydronaphthalene Derivatives

Enantiomerically enriched fluorinated benzo-fused bicyclic homoallylic amines have been synthesized through an asymmetric allylation/ring closing metathesis (RCM) sequence. This sequence has been carried out using alpha-trifluoromethylstyrene derivatives as key intermediates, synthesized by microwave radiation. The great deactivating effect exerted by such substituents has been brought to light by a comparative study.

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

Hexacoordinated ruthenium or osmium metal carbene metathesis catalysts

The present invention relates to novel hexacoordinated metathesis catalysts and to methods for making and using the same. The inventive catalysts are of the formula wherein:M is ruthenium or osmium;X and X1 are the same or different and are each independently an anionic ligand;L, L1? and L2 are the same or different and are each independently a neutral electron donor ligand, wherein at least one L, L1? and L2 is an N-heterocyclic carbene ligand; and,R and R1 are each independently hydrogen or a substituent selected from the group consisting of C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, aryl, C1-C20 carboxylate, C1-C20 alkoxy, C2-C20 alkenyloxy, C2-C20 alkynyloxy, aryloxy, C2-C20 alkoxycarbonyl, C1-C20 alkylthio, C1-C20 alkylsulfonyl and C1-C20 alkylsulfinyl. Optionally, each of the R or R1 substituent group may be substituted with one or more moieties selected from the group consisting of C1-C10 alkyl, C1-C10 alkoxy, and aryl which in turn may each be further substituted with one or more groups selected from a halogen, a C1-C5 alkyl, C1-C5 alkoxy, and phenyl. Moreover, any of the catalyst ligands may further include one or more functional groups. Examples of suitable functional groups include but are not limited to: hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate, and halogen.

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

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246047-72-3, Name is (1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium, molecular formula is C46H65Cl2N2PRu, belongs to ruthenium-catalysts compound, is a common compound. In a patnet, once mentioned the new application about 246047-72-3, Formula: C46H65Cl2N2PRu

INTERLOCKED MOLECULES AND RELATED COMPONENTS, COMPOSITIONS, MATERIALS, METHODS AND SYSTEMS

[c2] daisy chain macromers, dimers and polymers and related compositions, materials, methods and systems are described.

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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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Ring-closing metathesis and nanoparticle formation based on diallyldithiocarbamate complexes of gold(I): Synthetic, structural, and computational studies

The gold(I) complexes [Au{S2CN(CH2CHi – =CH2)2}(L)] [L = PPh3, PCy3, PMe3, CNtBu, IDip] are prepared from KS 2CN(CH2CHi – =CH2)2 and [(L)AuCl]. The compounds [L2(AuCl)2] (L2 = dppa, dppf) yield [(L2){AuS2CN(CH2CHi – =CH2)2}2], while the cyclic complex [(dppm){Au2S2CN(CH2CHi – =CH 2)2}]OTf is obtained from [dppm(AuCl)2] and AgOTf followed by KS2CN(CH2CHi – =CH 2)2. The compound [Au2{S2CN(CH 2CHi – =CH2)2}2] is prepared from [(tht)AuCl] (tht = tetrahydrothiophene) and the diallyldithiocarbamate ligand. This product ring-closes with [Ru(i – =CHPh)Cl2(SIMes) (PCy3)] to yield [Au2(S2CNC4H 6)2], whereas ring-closing of [Au{S2CN(CH 2CHi – =CH2)2}(PR3)] fails. Warming [Au2{S2CN(CH2CHi – =CH 2)2}2] results in formation of gold nanoparticles with diallydithiocarbamate surface units, while heating [Au 2(S2CNC4H6)2] with NaBH4 results in nanoparticles with 3-pyrroline dithiocarbamate surface units. Larger nanoparticles with the same surface units are prepared by citrate reduction of HAuCl4 followed by addition of the dithiocarbamate. The diallydithiocarbamate-functionalized nanoparticles undergo ring-closing metathesis using [Ru(i – =CHC6H4O iPr-2)Cl2(SIMes)]. The interaction between the dithiocarbamate units and the gold surface is explored using computational methods to reveal no need for a countercation. Preliminary calculations indicate that the Au-S interactions are substantially different from those established in theoretical and experimental studies on thiolate-coated nanoparticles. Structural studies are reported for [Au{S2CN(CH2CHi – CH2)2}(PPh3)] and [Au2{S 2CN(CH2CHi – CH2)2} 2]. In the latter, exceptionally short intermolecular aurophilic interactions are observed.

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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 convenient system for improving the efficiency of first-generation ruthenium olefin metathesis catalysts

The performance of certain olefin metathesis reactions catalyzed by Grubbs catalysts has been enhanced by the simple addition of phenol. Addition of phenol to self-metathesis reactions catalyzed by 1 produced very small quantities of unwanted byproducts and allowed for room-temperature metathesis at high substrate:catalyst loadings. The efficiency of cross-metathesis reactions between methyl acrylate and 1-decene catalyzed by 2 was also significantly increased by addition of p-cresol to the reaction mixture. Mechanistic studies, including NMR spectroscopy and DFT calculations, established that phenol is playing a number of positive roles in the active metathesis cycle, including altering the relative rates of phosphine loss and rebinding, activating the carbene carbon for reaction with olefinic substrate, and hemilabile stabilization of the key 14-electron intermediate species.

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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 Synthesis of 5-Amino-dihydrobenzo[b]oxepines and 5-Amino-dihydrobenzo[b]azepines via Ichikawa Rearrangement and Ring-Closing Metathesis

The combination of Ichikawa’s rearrangement and a ring-closing metathesis reaction of allyl carbamates is presented as a method for the preparation of 5-amino-substituted 2,5-dihydro-benzo[b]oxepines, 2,5-dihydro-benzo[b]azepines, and 2,5-dihydro-benzo[b]thiepins. It was demonstrated that the use of nonracemic allyl carbamates enables the synthesis of enantioenriched benzo-fused seven-membered heterocycles. Finally, it was shown that further functionalization of the obtained structures allows access to pharmacologically active 5-amino-substituted 2,3,4,5-tetrahydro-1-benzo[b]oxepine scaffolds.

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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 (-)-cleistenolide

An efficient and short total synthesis of (-)-cleistenolide (1) from D-mannitol with an overall yield of 23.6% is described. The chiron approach for the synthesis of (-)-cleistenolide involves a one-C-atom Wittig olefination, a selective allylic triethylsilyl protection, and a Grubbs-catalyzed ring-closure-metathesis (RCM) reaction as the key steps. Copyright

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