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This paper describes a concise synthesis of six- to eight-membered alpha,alpha?-substituted cyclic ethers by exploiting diastereoselective ring-closing metathesis (RCM) of 1,4-pentadien-3-yl ether derivatives. The RCM precursors could be efficiently prepared via a vinylation of the corresponding alpha-acetoxy ether derivatives using divinylzinc. Diastereoselective RCM of 1,4-pentadien-3-yl ether derivatives afforded a series of six- to eight-membered alpha,alpha?-substituted cyclic ethers with moderate to good diastereoselectivity. The stereochemical consequence of the diastereoselective RCM appeared to be dependent on the structure of the ring being forged. The diastereoselectivity of six- and seven-membered cyclic ethers appeared to be largely under kinetic control irrespective of the catalyst reactivity, whereas that of an eight-membered cyclic ether could be controlled by the catalyst reactivity. Finally, the diastereoselective RCM chemistry was applied to the synthesis of a biotin-tagged photoactivatable derivative of gambierol.

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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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Tandem bicycle: In the title reaction double bonds created during ring-closing metathesis isomerize to generate reactive iminium intermediates that undergo intramolecular cyclization reactions with tethered heteroatom and carbon nucleophiles. In this way, a series of biologically interesting heterocyclic compounds can be made, including a known precursor for the total synthesis of the antiparasitic natural product harmicine. 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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We describe the covalent post-modification of a hydrogen-bonded assembly with the subsequent formation of a potent transmembrane Na+ ion transporter. Olefin metathesis is used to cross-link all 16 guanosine subunits in a lipophilic G-quadruplex. The resulting unimolecular G-quadruplex folds in the environment of a phospholipid membrane and functions as a Na+ ion transporter as judged by fluorescence and 23Na NMR transport assays. 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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(Chemical Equation Presented) A general strategy for the synthesis of exo-methylidenecycloalkanes, which are salient features of many terpenoid natural products, is presented. Ring-closing alkene metathesis of allylsilanes provides intermediates that can be protodesilylated with alkene transposition to afford the exocyclic alkene; alternatively, the reactivity of the cyclic allylsilane intermediate can be harnessed to introduce allylic functionality. These two modes of reactivity are showcased in short syntheses of the sesquiterpene natural products teucladiol and poitediol, 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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Methyltrioxorhenium impregnated on ZnCl2-modified mesoporous alumina at Al/Zn ratio of 8-12 was revealed as an effective catalyst for self-metathesis of methyloleate at mild reaction conditions. The use of other promoters either in form of metal chlorides or as other zinc halides did not promote the metathesis of methyloleate as zinc chloride. The enhancement of the activity was not only due to the chloride and/or zinc but could be attributed to the interaction of both elements as Zn-Cl or ZnCl2 bonds with the mesoporous alumina. The results of this research suggest that it is possible to design a heterogeneous catalyst for the efficient and selective self-metathesis of functionalized olefins such as methyloleate and edible oils, avoiding the utilization of expensive homogeneous catalysts or use of toxic promoters such as SnR4 with heterogeneous catalysts.

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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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1,2-Diketones were synthesized from styrenes by combining a cross metathesis and a Ru-catalyzed alkene oxidation to an assisted tandem catalytic sequence. The synthesis relies on the use of just one metathesis precatalyst, which was in situ converted to the oxidation catalyst by addition of an alkyl hydroperoxide as a chemical trigger and oxidant. The one-flask sequence can be extended beyond 1,2-diketones to quinoxalines, by condensation of the oxidation products with ortho-phenylenediamine.

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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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(Chemical Equation Presented) General synthetic methods of substituted carbocyclic aromatic compounds are reported. Ring-closing enyne metathesis (RCEM)/dehydration of 1,5-octadien-7-yn-4-ols 6 and RCEM/tautomerization of 1,5-octadien-7-yn-4-ones 7 furnished a wide variety of substituted styrenes 4 and 4-vinylphenols 8, respectively. Acyclic precursors 6 and 7 were readily prepared from beta-halo-alpha,beta-unsaturated aldehydes 9 or 3-halo-2-propene-1-ols 13 by utilizing combinations of the Sonogashira coupling, allylation, and the Dess-Martin oxidation. The RCEM/dehydration for the synthesis of 1,3,5-tris(1-phenylethenyl)benzene derivative 4r and the RCEM/RCM/dehydration for the synthesis of 1,1?-binaphthyl derivative 19a are also presented as applications of this method.

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

A new application about (1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium

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At room temperature, NMR spectroscopy indicates that the ruthenium benzylidene complex (Cl)2(PCy3)2Ru=CHPh reacts with 1-pyrroline to yield (Cl)2(PCy3)(1-pyrroline)Ru=CHPh. Heating a solution of (Cl)2(PCy3)2Ru=CHPh with excess 1-pyrroline to 90C results in ring-opening oligomerization of the cyclic imine. The combination of ruthenium carbene complexes (Cl)2(PCy3)2Ru=CHPh and (Cl)2(PCy3)(H2IMes)Ru=CHPh (H2IMes = 1,3-dimesityl-4,5-dihydroimidazolylidene) with acyclic imines of the type (R)N=CH(R?) results in metathesis reactions when the imine possesses a C-H bond alpha to the imine carbon. Imines that lack C-H bonds alpha to the imine carbon do not react with (Cl)2(PCy3)2Ru=CHPh. The primary products from the reactions of (Cl)2(PCy3)2Ru=CHPh and (Cl)2(PCy3)(H2IMes)Ru=CHPh with acyclic imines are olefins and new Fischer carbene complexes of the type (Cl)2(L)(L?)Ru=CH{N(H)R} (L = L? = PCy3; L = PCy3 L? = H2IMes). The ruthenium complex (Cl)2(PCy3)2Ru=CH{N(H)Pr} has been isolated from the reaction of (Cl)2(PCy3)2 Ru=CHPh with (Pr)N=CH(i-Pr) and has been fully characterized. A possible pathway for the reactions of (Cl)2(PCy3)2Ru=CHPh and (Cl)2(PCy3)(H2IMes)Ru=CHPh with acyclic imines that involves imine to enamine tautomerism followed by C=C bond metathesis reactions is discussed. The failure of the ruthenium benzylidene complexes (Cl)2(PCy3)2Ru=CHPh and (Cl)2- (PCy3)(H2IMes)Ru=CHPh to react with the C=N bonds of a cyclic imines in combination with observed reactivity between Ru(Cl)2(PPh3)3 and 1-pyrroline indicates that the oligomerization of 1-pyrroline with (Cl)2(PCy3)2Ru=CHPh likely proceeds via a Lewis acid catalyzed mechanism.

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

A new application about (1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium

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The dictyostatins are a promising class of potential anti-cancer drugs because they are powerful microtubule-stabilizing agents, but the complexity of their chemical structures is a severe impediment to their further development. On the basis of both synthetic and medicinal chemistry analyses, 16-desmethyl-25,26-dihydrodictyostatin and its C6 epimer were chosen as potentially potent yet accessible dictyostatin analogues, and three new syntheses were developed. A relatively classical synthesis involving vinyllithium addition and macrocyclization gave way to a newer and more practical approach based on esterification and ring-closing metathesis reaction. Finally, aspects of these two approaches were combined to provide a third new synthesis based on esterification and Nozaki-Hiyama-Kishi reaction. This was used to prepare the target dihydro analogues and the natural product. All of the syntheses are streamlined because of their high convergency. The work provided several new analogues of dictyostatin, including a truncated macrolactone and a C10 E-alkene, which were 400- and 50-fold less active than (-)-dictyostatin, respectively. In contrast, the targeted 16-desmethyl-25,26-dihydrodictyostatin analogues retained almost complete activity in preliminary biological assays.

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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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This invention relates generally to olefin metathesis, more particularly, to tri- or tetra-substituted imidazoliniupsilonm salts which are precursors to N-heterocyclic carbene (NHC) ligands with tri- or tetra-substituted irnidazolinium rings, organometallic ruthenium complexes comprising gem di-substituted imidazoiinium NHC ligands, organometallic ruthenium complexes comprising tri- or tetra-substituted imidazoiinium NHC ligands, and to olefin metathesis methods using them. The catalysts and methods of the invention have utility in the fields of catalysis, organic synthesis, and industrial chemistry.

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