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The Arbuzov reaction of (2S,4S)-methyl-2-phenyl-1,3,2-dioxaphosphorinane with various alkyl halides gave the diastereomerically pure phosphinates with regioselective cleavage of the primary carbon-oxygen bond.These phosphinates reacted with Grignard reagents to give optically active phosphine oxides in high optical yields.

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate

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Stereoselective beta-C-glycosylation by a palladium-catalyzed decarboxylative allylation: Formal synthesis of aspergillide A

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£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate

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Palladium-diphosphite catalysts for the asymmetric allylic substitution reactions

(Chemical Equation Presented) We have designed a series of diphosphite ligands to study the effect of the backbone, the size of the chelate ring, and the substituents of the biphenyl moieties and to determine the scope of this type of ligand in the Pd-catalyzed asymmetric substitution reactions of different types of substrates. Good-to-excellent activities and enantioselectivities have been obtained for disubstituted linear substrate 11 (TOF’s up to >2000 mol ¡Á (mol ¡Á h)-1, ee values up to 99%) and cyclic substrate 14 (TOF up to 285 mol ¡Á (mol ¡Á h) -1, ee values up to 92%). However, these ligands are inadequate for the Pd-catalyzed allylic alkylation of monosubstituted linear substrates because they provide low enantioselectivities.

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate

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Asymmetric intramolecular hydrosilylation of hydroxyketones

A procedure for the catalytic asymmetric intramolecular hydrosilylation of alpha- and beta-hydroxyketones has been developed. A cationic rhodium (I) catalyst bearing the new chiral diphosphine (R,R)-i-Pr-DuPHOS affords the product diols in up to 93% ee.

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate

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HETEROCYST GLYCOLIPIDS OF THE CYANOBACTERIUM CYANOSPIRA RIPPKAE

The heterocyst glycolipids of the cyanobacterium Cyanospira rippkae have been isolated and their structures established to be 1-(O-alpha-D-glucopyranosyl)-3R,27R-octacosanediol and 1-(O-alpha-D-glucopyranosyl)-27-keto-3R-octacosanol by spectroscopic and chemical means.The absolute configuration at the two stereogenic centres in the aglycone moiety of the former compound has been established in a single step by Mosher’s method on the triol derivative.The akinetes of C. rippkae contain the same glycolipids. Key words: Cyanospira rippkae; Cyanobacteria; heterocyst glyclipids; akinetes; stereochemistry.

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate

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Diastereoselective route to (2R,5S)- and (2S,5S)-2-methyl-1,6-dioxaspiro[4.5]decane, a pheromone component of the wasp Paravespula vulgaris

A diastereoselective approach to (2R,5S)- and (2S,5S)-2-methyl-1,6-dioxaspiro[4.5]decane 1 and 1a is described. The route starts with an alkylation reaction among the cyclopentanone N,N-dimethylhydrazone 6 and the chiral iodides (R)-3 or (S)-3, derived from the enantiomers of ethyl beta-hydroxybutyrate, controlling the estereocenter at C-2 of the molecules. The alkylated products 7 and 7a were easily transformed into the 1,8-O-TBS-1,8-dihydroxy-5-nonanones 9 and 9a in four steps, and a subsequent stereoselective spiroketalization, in acidic media, afforded a Z:E mixture (1:2) of compounds 1 and 1a.

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate

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Absolute stereochemistry of amphidinolide C.

[structure in text] The absolute configurations at 12 chiral centers in amphidinolide C (1), a potent cytotoxic 25-membered macrolide isolated from a marine dinoflagellate Amphidinium sp., were determined to be 3S, 4R, 6R, 7R, 8R, 12R, 13S, 16S, 20R, 23R, 24R, and 29S by combination of NMR analyses, degradation experiments, and synthesis of the C-1-C-7 segment.

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate

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Pd(II)-mediated alkynediol spiroketalization: First total synthesis of (-)-cephalosporolide E and (+)-cephalosporolide F

Herein we describe a concise assembly of the central 1,6-dioxaspiro[4.4] nonane core of cephalosporolides E/F by employing a Pd-mediated alkynediol cycloisomerization and their total synthesis. On the basis of spectroscopic data and optical rotation values, the absolute configurations of cephalosporolides E/F were proposed.

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate

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A general synthesis of homochiral beta-hydroxy N-acetylcysteamine thioesters

A convenient and efficient route for the enantioselective synthesis of functionalised beta-hydroxy N-acetylcysteamine thioesters is described. The route allows the facile incorporation of vicinal 13C labelling to produce intermediates required for biosynthetic studies on a wide range of polyketide metabolites, e.g. 6-MSA, monocerin, colletodiol and strobilurins.

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate

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8-METHYL-1-PHENYL-IMIDAZOL[1,5-A]PYRAZ1NE COMPOUNDS

The present invention provides 8- methyl-1-phenyl-imidazo[1,5-a]pyrazine derivatives according to formula I or pharmaceutically acceptable salts thereof. The compounds of the current invention show inhibitory activity against Lck and can be used for the treatment of Lck-mediated diseases or Lck-mediated conditions such as inflammatory disorders.

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate