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The complex [(IMesH2)(PPh2Cy)Cl2Ru{double bond, long}CHPh] was synthesised and shown to be an active catalyst in ring-closing metathesis of a diallylmalonate. Its phosphine exchange was investigated in C6D6 using magnetisation transfer 31P NMR spectroscopy and it was found to operate via a dissociative mechanism with k353 = 4.1 ± 0.9 s-1, DeltaH? = 84 ± 10 kJ mol-1 and DeltaS? = 4 ± 28 J mol-1 K-1.

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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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Ring-closing alkene metatheses of trans,trans-(C6F 5)(Ph2P-Z-CHCH2)2Pt(CC) 4Pt(Ph2P-Z-CHCH2)2(C 6F5) (Z = (CH2)9, (CH 2)4O(CH2)2), followed by hydrogenation, give the title compounds; the former exhibits an exceptionally twisted conformation, and the latter establishes that functional groups can be incorporated into the flexible sp3 chain. The Royal Society of Chemistry 2006.

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

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Tandem enyne metathesis between 1-alkynes and 1,5-cyclooctadiene or all-cis-1,4-polybutadiene resulted in a direct, one-step ring synthesis of cyclohexadienes by methylene-free metathesis. The use of methylene-free metathesis conditions provided apparent Z-selectivity in the intermolecular enyne metathesis step. 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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An asymmetric total synthesis of (-)-incarvillateine, a natural product having potent analgesic properties, has been achieved in 11 steps and 15.4% overall yield. The key step is a rhodium-catalyzed intramolecular alkylation of an olefinic C-H bond to set two stereocenters. Additionally, this transformation produces an exocyclic, tetrasubstituted alkene through which the bicyclic piperidine moiety can readily be accessed. 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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The design of small molecules that mimic the BH3 domain and bind to Bcl-2 proteins has emerged as a promising approach to discovering novel anti-cancer therapeutics. We reveal the design and synthesis of conformationally constrained benzoylurea scaffolds as conformational probes. Central to helix mimicry, the intramolecular hydrogen bond in the benzoylurea plays a key role in the pre-organisation of the acyclic substrates for cyclisation via ring closing metathesis, providing efficient access to the constrained mimetics. The Royal Society of Chemistry 2012.

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

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The invention relates to new (pre)catalysts of ruthenium complexes of formula (I), wherein L1, X, X’, R1, R2, R3 and n are defined herein. The novel ruthenium complexes of formula 1 are convenient (pre)catalysts for metathesis reactions and can be applied i.e. for ring-closing metathesis, cross metathesis or ene-ine metathesis reactions. Another aspect of the invention are the novel intermediates of formula (II).

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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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New carbamato-kappaN-benzylidene ruthenium chelates were synthesized from the first [RuCl2(PCy3)2(=CHPh)] and second [RuCl2(SIMes)(PCy3)(=CHPh)] generation Grubbs catalysts by metathetic exchange of benzylidene ligand for tert-butyl (2-vinylphenyl)carbamates bearing benzylidene ligand substituted in the position para to carbamato functionality with methyl or trifluoromethyl group. In all metathetical transformations tested, i.e. in ROMP of cycloocta-1,5-diene, RCM of diethyl diallylmalonate and diethyl 2-allyl-2-(2-methylallyl)malonate and cross-metathesis of allylbenzene with Z-1,4-diacetoxybut-2-ene, the complexes behave like latent catalysts. Complexes remain completely inactive until they are activated by the addition of ethereal solution of HCl. The presence of the electron-withdrawing group results in a slight increase in the catalytic activity of the activated form of the catalyst relative to a similar form of the unsubstituted complex or the least active complex carrying the electron donating group.

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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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The use of a mixed phosphite/N-heterocyclic carbene bearing ruthenium precursor permits the synthesis and characterisation of unprecedented four-coordinate Ru(ii) and Ru(iii) cationic complexes adopting an unusual sawhorse structure. The cationic Ru(ii) complex performs very effectively on challenging substrates at high temperature in very short reaction times and low catalyst loadings. The Royal Society of Chemistry 2012.

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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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Isolated from Hypericum species H. Chinese L. var. salicifolium, biyouyanagin A was assigned structure 1a or 1b on the basis of NMR spectroscopic analysis. This novel natural product exhibited significant anti-HIV properties and inhibition of lipopolysaccharide-induced cytokine production. Described herein are the total syntheses of biyouyanagin A and several analogues (3-11), structural revision of biyouyanagin A to 2b, and the biological properties of all synthesized compounds. The total synthesis proceeded through cascade sequences that efficiently produced enantiomerically pure key building blocks 15b (ent-zingiberene) and 18 (hyperolactone C) and featured a novel [2 + 2] photoinduced cycloaddition reaction which occurred with complete regioand stereoselectivity. Biological investigations with the synthesized biyouyangagins A (2-11) and hyperolactones C (12-16) revealed that the activity of biyouyanagin A most likely resides in its hyperolactone C structural domain.

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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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The selective synthesis of substituted 4-vinylindoles by the ring-closing enyne metathesis (RCEM)/dehydration sequence is reported. In contrast with many known methods in which a pyrrole ring is constructed onto a functionalized benzene precursor, this method enables the construction of a benzene ring onto a pyrrole precursor. The RCEM/tautomerization sequence for the synthesis of 7-hydroxy-4-vinylindole is also presented as an application of this method.

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