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Synthesis and activity of ruthenium olefin metathesis catalysts coordinated with thiazol-2-ylidene ligands

A new family of ruthenium-based olefin metathesis catalysts bearing a series of thiazole-2-ylidene ligands has been prepared. These complexes are readily accessible in one step from commercially available (PCy 3)2Cl2Ru=CHPh or (PCy3)Cl 2Ru=CH(o-iPrO-Ph) and have been fully characterized. The X-ray crystal structures of four of these complexes are disclosed. In the solid state, the aryl substituents of the thiazole-2-ylidene ligands are located above the empty coordination site of the ruthenium center. Despite the decreased steric bulk of their ligands, all of the complexes reported herein efficiently promote benchmark olefin metathesis reactions such as the ring-closing of diethyldiallyl and diethylallylmethallyl malonate and the ring-opening metathesis polymerization of 1,5-cyclooctadiene and norbornene, as well as the cross metathesis of allyl benzene with cis-1,4-diacetoxy-2-butene and the macrocyclic ring-closing of a 14-membered lactone. The phosphine-free catalysts of this family are more stable than their phosphine-containing counterparts, exhibiting pseudo-first-order kinetics in the ring-closing of diethyldiallyl malonate. Upon removing the steric bulk from the ortho positions of the N-aryl group of the thiazole-2-ylidene ligands, the phosphine-free catalysts lose stability, but when the substituents become too bulky the resulting catalysts show prolonged induction periods. Among five thiazole-2-ylidene ligands examined, 3-(2,4,6-trimethylphenyl)-and 3-(2,6-diethylphenyl)-4,5-dimethylthiazol-2- ylidene afforded the most efficient and stable catalysts. In the cross metathesis reaction of allyl benzene with cis-1,4-diacetoxy-2-butene increasing the steric bulk at the ortho positions of the N-aryl substituents results in catalysts that are more Z-selective.

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

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Ruthenium nitronate complexes as tunable catalysts for olefin metathesis and other transformations

Novel ruthenium(ii) complexes were obtained as a result of a stoichiometric reaction of Grubbs’ benzylidene second generation catalysts with 3-nitropropene. These stable complexes, formally ruthenaisoxazole N-oxide derivatives, display activity in both metathesis and non-metathetic processes such as cycloisomerisation, isomerisation and transfer hydrogenation.

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

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Highly efficient nitrogen chelated ruthenium carbene metathesis catalysts

A series of nitrogen chelated ruthenium carbene metathesis catalysts containing an N-heterocyclic carbene (NHC) and a carbonyl group have been developed and their catalytic activities for olefin metathesis reactions were investigated. The X-ray structure of the [(H2IMes)(Cl)2Ru]C(H)CH2[p-F(C6H3)NC(CF3)(C(O)OCH2CH3)] complex shows that the carbonyl oxygen of the ester and the imine nitrogen are both coordinated to the Ru metal to give an octahedral structure. The catalytic activity of these ruthenium carbene complexes for olefin metathesis reactions was tested. Some of the complexes bearing electron withdrawing groups had high initiation rates. These complexes exhibited excellent performance for both ring-closing metathesis and cross 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 Article£¬once mentioned of 172222-30-9, name: Benzylidenebis(tricyclohexylphosphine)dichlororuthenium

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

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A short convergent synthesis of the [3.2.1]dioxabicyclooctane subunit of sorangicin A via regioselective epoxide opening

In this paper, we disclose the synthesis of the dioxabicyclo[3.2.1]octane subunit of the potent antibiotic sorangicin A. The synthesis was achieved in a convergent manner in 8 steps. Regio- and stereoselective intermolecular epoxide opening, ring-closing metathesis and iodo-etherification are key steps. cis-2-Butene diol has been employed as a common staring material.

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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 stereochemistry of decarestrictines H and J

The first synthesis of (7S,9R)-decarestrictine H and (7R,9R)-decarestrictine H as well as the improved synthesis of decarestrictine J were achieved. The overall yields of (7S,9R)-decarestrictines H and J were 20.9% each in nine to ten steps from (R)-Roche ester using a unified synthetic route via esterification with 3,3-ethylenedioxyhex-5-enoic acid and ring-closing metathesis, which were the key steps. The relative stereochemistry of decarestrictine H was determined to be 7,9-syn by comparing the spectral data of the natural product and synthetic epimers of decarestrictines H.

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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 concise formal stereoselective total synthesis of (-)-swainsonine

A short formal stereoselective synthesis of (-)-swainsonine (1) is described. Our synthesis started with the versatile building block (R)-3-benzyloxyglutarimide 5. Through controlled regioselective reduction, Ley’s-sulfone chemistry (N-alpha-sulfonylation and ZnCl2-catalyzed N-alpha-amidovinylation), an RCM reaction, and an amide reduction, the synthesis of unsaturated indolizidine (8R,8aS)-3 has been achieved in five steps. The indolizidine (8R,8aS)-3 is an advanced intermediate toward the synthesis of (-)-swainsonine (1).

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

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Efficient total syntheses of (-)-colombiasin A and (-)-elisapterosin B: Application of the Cr-catalyzed asymmetric quinone Diels-Alder reaction

(Chemical Equation Presented) A made-to-order asymmetric catalytic reaction was applied in the key quinone Diels-Alder step of the total syntheses of the title compounds (see scheme for the synthesis of colombiasin A). The reaction was highly regio- and diastereoselective.

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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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Enantioselective total synthesis of FD-891

The enantioselective synthesis of FD-891 has been achieved with a longest linear sequence of 21 steps. The synthetic strategy involves the use of aldol additions of a chlorotitanium enolate of N-acylthiazolidinethiones as the key reaction to establish 6 of the 10 stereogenic centers. A key cross-metathesis and a late-stage Julia olefination serve to assemble three key subunits. Copyright

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