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A practical and scalable stereoselective synthesis of the western substituted tetrahydrofuran ring C27-C35 fragment of eribulin was developed by using (2S,3S)-tartaric acid as a cheap starting material that was converted into an intermediate through a stereoselective vinylation and cross-metathesis as the key steps. A regio-and stero-selective intramolecular oxy-Michael cyclization or an iodocyclization reaction finally provided the required western tetrahydrofuran ring fragment and its related isomeric analogues. These key fragments were further utilized in obtaining several types of macrocyclic derivatives for exploration of their biological properties. The simplicity of our present approach has the potential to be considered for large-scale syntheses of key fragments of eribulin and related analogues.

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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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Mild and sweet: The title reaction proceeds under mild conditions with high regio- and diastereoselectivity (see scheme, PG=protecting group, DiPPF=1,1?-bis(diisopropylphosphino)ferrocene). This reaction is suitable for a wide range of glycal-derived gamma-ketone esters and affords C-glycosides with exclusive beta-selectivity. The method was further applied to a concise formal synthesis of aspergillideA. 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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Convergent approach: The total syntheses of (-)-flueggine A and (+)-virosaine B (see scheme) have been accomplished in a concise and convergent manner. Key steps in these approaches were relay ring-closing metathesis reactions for rapid construction of the key intermediates, and 1,3-dipolar cycloaddition reactions for the formation of the natural products. 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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Within recent years, ganglioside patterns have been increasingly analyzed by MS. However, internal standards for calibration are only available for gangliosides GM1, GM2, and GM3. For this reason, we prepared homologous internal standards bearing nonnatural fatty acids of the major mammalian brain gangliosides GM1, GD1a, GD1b, GT1b, and GQ1b, and of the tumor-associated gangliosides GM2 and GD2. The fatty acid moieties were incorporated after selective chemical or enzymatic deacylation of bovine brain gangliosides. For modifi cation of the sphingoid bases, we developed a new synthetic method based on olefi n cross metathesis. This method was used for the preparation of a lyso-GM1 and a lyso-GM2 standard. The total yield of this method was 8.7% for the synthesis of d17:1-lyso-GM1 from d20:1/18:0-GM1 in four steps. The title compounds are currently used as calibration substances for MS quantifi cation and are also suitable for functional studies.

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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 convergent total synthesis of (+)-xestodecalactone A (1) is reported. In addition, a formal synthesis of (+)-sporostatin has been accomplished by means of intercepting a previously reported intermediate en route to 1. The key reaction utilized was a convergent Pd-catalyzed alpha-arylation between a boronic acid and an alpha-bromoester.

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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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In the context of diversity-oriented synthesis, the exploration and optimization of the domino metathesis of decorated norbornenes allowed complex polycyclic architectures to be generated in a highly efficient and atom-economical process. The Royal Society of Chemistry.

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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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Six epothilone D analogues with a bridge between the C4-methyl and the C12-methyl carbons were prepared in an attempt to constrain epothilone D to its proposed tubulin-binding conformation. Ring-closing metathesis (RCM) was employed as the key step to build the C4-C26 bridge. In antiproliferative assays in the human ovarian cancer (A2780) and prostate cancer (PC3) cell lines, and also in tubulin assembly assay, all these compounds proved to be less active than epothilone D.

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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 syntheses (total and formal) of four phenylacetic acid lactone (PAL) natural products have been accomplished by utilizing a unified strategy of an umpolung Pd-catalyzed alpha-arylation of complex alpha-bromo esters and boronic acids under mild reaction conditions. As part of the synthetic approaches to these natural products, it was observed that the mild coupling reaction conditions readily tolerated terminal alkenes, other labile ester functionalities, an alpha,beta-unsaturated ester moiety, and a protected allylic alcohol, while chemoselectively engaging the alpha-bromo ester. The completion of (+)-xestodecalactone A and (-)-curvularin coupled with the formal syntheses of (+)-12-oxocurvularin and (-)-citreofuran highlight the umpolung Pd-catalyzed alpha-arylation strategy as a key convergent tactic in complex natural product synthesis.

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

Extended knowledge of (1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium

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Site-selective introduction of biotin and benzophenone probes onto ginkgolide scaffolds is described. The Royal Society of Chemistry 2007.

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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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An approach to aromatic compounds using combinations of ring-closing olefin metathesis (RCM), dehydration, oxidation, and tautomerization is reported. The RCM reaction of l,7-diene-3,5-diols, which were readily prepared by the allylation of aldol products, gave corresponding cyclized products, 4-cyclohexene-l,3-diols, in high yields. The subsequent dehydration or oxidation of 4-cyclohexene-1,3-diols led to versatile substituted benzenes including phenol and resorcinol derivatives.

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