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A ruthenium complex was found to catalyze the hydrogen reduction of esters under mild and neutral conditions. A variety of optically active esters can be reduced to the corresponding alcohols in excellent yield without loss of their optical purity or causing undesirable side reactions. Hydrogen reduction needs such simple operations – reaction, concentration, and purification – that the violent quench step and extraction step, which accompany conventional sodium borohydride or lithium aluminum hydride reduction, can be omitted.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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The double Michael reactions between benzofuran-3-one or 1-indone and symmetric dienones in the presence of catalytic ionic liquids were successfully developed and spiro[benzofuran-2,1?-cyclohexane]-3-one or spiro[cyclohexane-1,2?-indene]-1?,4(3?H)-dione derivatives containing a spiro quaternary stereogenic center, which widely exist in biologically active products and building blocks in organic synthesis, were obtained in excellent yields (up to 99%). This catalytic system was also extended to the double Michael reaction of less reactive 1-indone and the desired products were also obtained in 31%-62% yields. The catalytic system was highly active and efficient for a broad of substrates under mild conditions.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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Twelve new analogues of 19-nor-1alpha,25-dihydroxyvitamin D3 (5-16) were prepared by convergent syntheses, employing the Wittig Horner reaction. The necessary Grundmann type ketones (45-48), possessing fixed configurations of the hydroxyl group at C-25, were obtained by a multistep procedure from commercial vitamin D2 and enantiomers of 1,3-butanediol (23 and 24). We have examined the influence of removal of one of the methyl groups located at C-25 on the biological in vitro and in vivo activity. The in vivo tests showed that the synthesized vitamin D compounds (5-16) exhibit reduced calcemic activity both in bone and in the intestine. However, in vitro potency of 2-methylene and 2alpha-methyl compounds (5-10, 13, and 14) remained similar or enhanced as compared to that of 1alpha,25-(OH)2D3.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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(Diagram presented) The fully functionalized core structure of the macrolactone queenslandon was prepared using a novel strategy consisting of a glycolate aldol reaction and hydroboration of the derived enol ether 17 followed by Suzuki cross-coupling with an iodostyrene. After conversion of the cross-coupling product to the seco acid 22, Mitsunobu macrolactonization and protecting group manipulations led to the queenslandon model 5.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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We have analyzed the effects of mutations inserted during directed evolution of a specialized enzyme, Escherichia coli S-1,2-propanediol oxidoreductase (FucO). The kinetic properties of evolved variants have been determined and the observed differences have been rationalized by modeling the tertiary structures of isolated variants and the wild-type enzyme. The native substrate, S-1,2-propanediol, as well as phenylacetaldehyde and 2S-3-phenylpropane-1,2-diol, which are new substrates accepted by isolated variants, were docked into the active sites. The study provides a comprehensive picture of how acquired catalytic properties have arisen via an intermediate generalist enzyme, which had acquired a single mutation (L259V) in the active site. Further mutagenesis of this generalist resulted in a new specialist catalyst. We have also been able to relate the native enzyme activities to the evolved ones and linked the differences to individual amino acid residues important for activity and selectivity. F254 plays a dual role in the enzyme function. First, mutation of F254 into an isoleucine weakens the interactions with the coenzyme thereby increasing its dissociation rate from the active site and resulting in a four-fold increase in turnover number with S-1,2-propanediol. Second, F254 is directly involved in binding of aryl-substituted substrates via pi-pi interactions. On the other hand, N151 is critical in determining the substrate scope since the side chain amide group stabilizes binding of 1,2-substituted diols and is apparently necessary for enzymatic activity with these substrates. Moreover, the side chain of N151 introduces steric hindrance, which prevents high activity with phenylacetaldehyde. Additionally, the hydroxyl group of T149 is required to maintain the catalytically important hydrogen bonding network. A specialist enzyme, Escherichia coli propanediol oxidoreductase, was subjected to laboratory evolution with the purpose of broadening the substrate scope to include aryl-substituted alcohols and aldehydes. The wild-type enzyme displays very low and undetectable activity with phenylacetaldehyde and 3-phenyl-1,2-propanediol, respectively. Two rounds of directed evolution produced a variant enzyme displaying characteristics of a new specialist and others with traits of generalist enzymes.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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Practical catalytic cross-coupling of secondary alkyl electrophiles with secondary alkyl nucleophiles under Cu catalysis has been realized. The use of TMEDA and LiOMe is critical for the success of the reaction. This cross-coupling reaction occurs via an SN2 mechanism with inversion of configuration and therefore provides a general approach for the stereocontrolled formation of C-C bonds between two tertiary carbons from chiral secondary alcohols.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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Optically active crown ethers 1a-11, 2, 3a,b, 4a,b, 5a,b and the analogue 6 are synthesized.The efficiency of these compounds as phase-transfer catalysts for a series of enantioselective reactions will be tested.This will be described in a following publication. Key Words: Crown ethers, chiral, optically active / Phase transfer catalysts

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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A series of iridium and ruthenium N-heterocyclic carbene based catalysts of general formula [IrI2(AcO)(bis-NHC)] or [Ru(eta6-arene) (NHC)CO3] have been tested in the reduction of several organic carbonyl compounds using glycerol as solvent and hydrogen donor, by the transfer hydrogenation methodology. The Ir(III) complexes with a chelating bis-NHC ligand and sulfonate groups were the most efficient, due to their solubility in the reaction media and to the strong electron-donor properties of the bis-carbene ligands. The same two catalysts were moderately active in the reduction of olefins and alkynes and, more remarkably, show excellent chemoselectivity in the reduction of the alkenic double bond of alpha,beta-unsaturated ketones, a valuable process for which glycerol had never been used before.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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An efficient method for Michael addition of indoles hasbeen developed using bismuthyl perchlorate (BiOClO4·xH2O) as catalyst. The reaction proceeds to give 3-substituted indoles excellently stirring indoles and Michael acceptors in acetonitrile in the presence of the catalyst at room temperature or in much shorter reaction times under sonication at ambient temperature.{A figure is presented}.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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For the role of monomeric metaphosphate and the nature of the transition states in the alcoholysis of phosphoric monoesters to be examined, phenyl <(R)-16O,17O,18O>phosphate and 2,4-dinitrophenyl <(R)-16O,17O,18O>phosphate have been synthesized and the stereochemical course of the methanolysis of phenyl phosphate monoanion and of dinitrophenyl phosphate dianion has been evaluated. <(R)-16O,17O,18O>Phosphocreatine has also been synthesized and the stereochemical course of the methanolysis of this molecule determined.In each case, complete inversion of configuration at phosphorus is observed.It is clear that metaphosphate, if it exists as a true intermediate in these reactions in protic solvent, does not leave the solvent cage in which it is generated.Indeed, product formation occurs more rapidly than rotation of the putative metaphosphate intermediate.These displacements must therefore occur by preassociative mechanisms in which there may be some assistance from the incoming nucleophile.The present results do not allow a distinction to be made between a “preassociative concerted” path (that is, an SN2-like displacement via a very loose transition state) and a “preassociative stepwise” path via a metaphosphate intermediate of very short lifetime.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate