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Tandem catalysis: Generating multiple contiguous carbon-carbon bonds through a ruthenium-catalyzed ring-closing metathesis/Kharasch addition

Tandem catalysis can offer unique and powerful strategies for converting simple starting materials into more complex products in a single reaction vessel while generating less waste and minimizing handling. In this regard, Grubbs’ ruthenium alkylidene (Cy3P)2Cl2Ru=CHPh is shown to catalyze two mechanistically distinct transformations to offer a unique protocol that effects multiple bond changes in a single operation. A tandem ruthenium-catalyzed olefin ring-closing metathesis (RCM)/Kharasch addition allows for the facile preparation of bicyclic [3.3.0], [4.3.0], and [5.3.0] ring systems in one step from the appropriately functionalized acyclic precursors. For substrates where the intramolecular Kharasch addition fails, an intermolecular Kharasch addition is possible. By combining the intra- and intermolecular Kharasch additions with RCM, three new contiguous carbon-carbon bonds with multiple stereocenters can be generated by the ruthenium catalyst in a controlled fashion in one operation through two mechanistically distinct pathways.

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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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Assemblies of supramolecular porphyrin dimers in pentagonal and hexagonal arrays exhibiting light-harvesting antenna function

Porphyrin-based supramolecular macrocyclic arrays were synthesized as mimics of photosynthetic light-harvesting (LH) antennae. Pentameric and hexameric macrocyclic porphyrin arrays EP5 and EP6 were constructed by complementary coordination of m-bis(ethynylene)phenylene-linked zinc-imidazolylporphyrin Zn-EP-Zn. The proton NMR spectra of noncovalently linked N-EP5 and N-EP6 indicate fast rotation of the porphyrin moieties along the ethyne axis. These macrocycles were covalently linked and identified as C-EP5 (6832 Da) and C-EP6 (8199 Da) by mass spectrometry. Fluorescence quantum yields of C-EP2 (10.0%), C-EP5 (10.1%), and C-EP6 (11.0%), even larger than that of the unit coordination dimer C-EP1 (9.3%), were significantly increased from those of the series without the ethynylene linkage. The order of increasing fluorescence quantum yields was parallel to that of decreasing fluorescence lifetimes (C-EP1 (1.65 ns), C-EP2 (1.45 ns), C-EP5 (1.42 ns), and C-EP6 (1.38 ns)), indicating that the radiative decay rate kF increased relative to the other decay rates with an increase in the number of ring components. Based on the exciton-exciton annihilation and anisotropy depolarization times, the excitation energy hopping (EEH) times in these macrocyclic systems were obtained as 21 ps for C-EP5 and 12.8 ps for C-EP6. EEH times depend strongly on the orientation factor of the component transition dipoles in the macrocyclic arrays. The hexagonal macrocyclic array with an orientation of better transition dipole coupling resulted in faster EEH time compared to the pentagonal one.

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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 [6,n] cis-fused ring compounds via Cr-mediated dearomatisation-ring-closing metathesis

cis-Fused [6,8], [6,7], [6,6] and [6,5] ring systems containing a cyclohexadiene ring unit, a cycloenone ring and a quaternary carbon at the ring junction were obtained in only two steps from [Cr(CO)3(eta 6-p-methoxyphenyl oxazoline)]. The sequence proceeds via diastereoselective addition of three C-substituents across an arene double bond, followed by allylation and ring closing metathesis (RCM). RAMP-hydrazone and (R)-isopropyloxazoline were used as chiral auxiliaries to provide, after removal of the auxiliaries, the enantiomerically highly enriched [6,7] cis-fused system. The Royal Society of Chemistry 2006.

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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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Coordination assembled rings of ferrocene-bridged trisporphyrin with flexible hinge-like motion: Selective dimer ring formation, its transformation to larger rings, and vice versa

Ferrocene-bridged trisporphyrin (2) was synthesized by two-steps condensation of corresponding aldehydes and dipyrromethanes, and its self-assembling behavior based on the complementary coordination motif of imidazolylporphyrinatozinc(II) was investigated in conjunction with hinge-like flexibility given by freely rotating cyclopentadienyl rings of ferrocene connector. Ferrocene-bridged trisporphyrin (2) spontaneously and exclusively generated the dimeric ring (7) upon simple zinc(II) insertion, indicating that the freely rotating hinge connector favored the smallest ring formation. Taking advantage of the unique hinge-like flexibility of ferrocene, we attempted to transform the dimer ring into a mixture of porphyrin macrocycles by reorganizing the structure cleaved once by pyridine. A series of porphyrin macrocycles from trimer to decamer can be separated into its components by preparative gel permeation chromatograms. Macrocycles obtained are kept stable in the absence of coordinating solvents. On the other hand, they were easily transformed to the dimer ring in the presence of coordinating solvents such as methanol, showing that the transformation is completely reversible and can be controlled by the choice of the solvent system. A series of porphyrin macrocycles was confirmed via covalent linking of each complementary coordination dimer pair by metathesis reaction in the presence of Grubbs’s catalyst. The coordination behavior of the bidentate ligands with different spacer lengths toward the dimer ring revealed that only the bidentate ligand (15) with a spacer length that matched the facing central porphyrins was selectively accommodated inside the ring. Coordination assembled flexible rings with tunable cavities and multiple coordination sites will be used as versatile hosts for a wide variety of guest molecules.

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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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PHOSPHONIUM SALTS DERIVATIVES AND THEIR USE AS SOLUBILITY CONTROLLING AUXILIARIES

The present invention relates to the use of compounds of formula (IA) or (IIA): insert formula (IA) and (IIA) from page 15 of the disclosure wherein A represents various substituted or unsubstituted groups such as furyl, phenyl, pyridyl, naphthyl, or thiophenyl; X- represents an anion; and L1 represents a linker, as solubility controlling auxiliaries. These compounds can also be used as solubility controlling fragments of a molecule. The invention also relates to various methods of controlling the solubility of a molecule or a substrate. Moreover, the invention also relates to various phosphonium supported reagents or various phosphonium salts 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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HCV NS3 PROTEASE INHIBITORS

The present invention relates to macrocyclic compounds of formula (I) that are useful as inhibitors of the hepatitis C virus (HCV) NS3 protease, their synthesis, and their use for treating or preventing HCV infections.

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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 fast organometallic route from p-xylene, mesitylene, and p-diisopropylbenzene to organoiron and polycyclic aromatic cyclophanes, capsules and polymers

New organic and organoiron polycyclic paracyclophane cages (see picture) and polymers are rapidly formed using two different, extremely efficient C-C bond coupling reactions from p-xylene, mesitylene and p-diisopropylbenzene: the eta5C5H5-Fe+-induced perallylation- or peralkenylation reaction followed by Rucatalyzed ring-closing and cross-coupling metathesis by using the commercially available Grubbs catalysts.

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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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172222-30-9, Name is Benzylidenebis(tricyclohexylphosphine)dichlororuthenium, molecular formula is C43H72Cl2P2Ru, belongs to ruthenium-catalysts compound, is a common compound. In a patnet, once mentioned the new application about 172222-30-9, name: Benzylidenebis(tricyclohexylphosphine)dichlororuthenium

Application of tandem Ugi multi-component reaction/ring closing metathesis to the synthesis of a conformationally restricted cyclic pentapeptide

A conformationally restricted cyclic pentapeptide, containing an unsaturated 9-membered lactam as a semi-rigid scaffold, was prepared in a very convergent manner, through tandem Ugi reaction/ring closing metathesis.

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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 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. 172222-30-9, Name is Benzylidenebis(tricyclohexylphosphine)dichlororuthenium, molecular formula is C43H72Cl2P2Ru. In a Patent£¬once mentioned of 172222-30-9, HPLC of Formula: C43H72Cl2P2Ru

PROCESS FOR THE PREPARATION OF 1-OCTENE

Process in two steps for the preparation of 1-octene starting from butadiene which comprises: a first step (a) in which the bis-hydrodimerization of butadiene to 1,7-octadiene is effected in the presence of a catalyst based on a palladium complex containing one or more tri-substituted monodentate phosphines, in an aprotic polar solvent optionally containing an organic base; a second step (b) in which the partial catalytic hydrogenation of 1,7-octadiene to 1-octene is effected, the above process being characterized in that: (i) in the first step the aprotic polar solvent is selected from disubstituted cyclic ureas; (ii) in the second step the catalyst is selected from non? supported ruthenium complexes having general formula (I I): RuXmLn (I I).

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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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Extension of ring closing metathesis methodology to the synthesis of carbocyclic methyl and silyl enol ethers

Carbocyclic methyland silylenol ethers (TBDMS is optimum) can be synthesised regiospecifically by ring closing metathesis using the ‘second generation’ Grubbs ruthenium carbene catalyst incombination with molecular sieves.

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