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The vibrational circular dichroism (VCD) spectrum (800 to 1500 cm-1) is reported for 2-methylthietane (2MT).Fixed partial charge (FPC), atomic polar tensor (APT), and charge flow (CF) methods are used to compute the VCD spectra for both stable conformers (CH3 in the axial or equatorial orientation) for the complete range of fundamental vibrations, based on 3-21G and 6-31G* harmonic force fields.The experimental and computed absorption and VCD spectra of R-(+)-2MT are compared to the previously reported spectra of R-(-)-2-methyloxetane.The success of the APT and CFmodels for reproducing the dominant ring stretching IR and VCD features of that compound is rationalized by a comparison of APT and FPC intensity expressions.Further comparison of the APT and FPC calculated electric dipole moment derivatives are interpreted to suggest values for the diagonal CS and CH stretching charge flow terms for 2MT.These investigations then provide a rationale for previously reported successes of the FPC model, and permit identification of specific vibrational modes of 2MT that are amenable to FPC-VCD modeling.The previously established conformational mixture of ca. 30percent axial and 70percent equatorial is shown to be in accord with FPC-VCD predictions for the most appropriate (beta-CH2 wagging) mode. Key words: vibrational circular dichroism, 2-methylthietane, fixed partial charge, atomic polar tensor, charge flow.

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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 process is described for preparing optically active alpha-arylalkanoic acids consisting of rearranging an optically active ketal of formula STR1 in which the substituents have the meaning given in the description of the invention.

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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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This article describes the palladium-catalysed three-component coupling of 1,3-dicarbonyl compounds with nucleophiles and propargylic electrophiles for the generation of quaternary all-carbon centres in a single step, which necessitates the simultaneous control of regio-, chemo- and enantioselectivity. The use of propargyl enol carbonates, the source of two of the components, was found to be essential in maintaining high levels of regiocontrol and chemoselectivity, whereas a careful analysis of p K a trends of O-, C- and N-nucleophiles as the other coupling partner indicates that the highest levels of selectivity are likely to be obtained with relatively acidic species, such as phenols, 1,3-dicarbonyl compounds and aromatic N-heterocycles. Finally, studies towards the development of the catalytic enantioselective construction of quaternary all-carbon centres by means of alkenylation and allylic alkylation are disclosed.

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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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Compositions comprising stereocomplexes of enantiomeric polymer chains having individual repeat units formed from the reaction of an epoxide and cyclic anhydride. The compositions can be made by mixing two types of enantiomeric polymer chains having opposite absolute stereochemistry. The compositions can be used in applications such as biomedical applications and drug delivery applications.

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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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Reaction of 2-ethoxy-2-methyl-1,3-dioxolan (1c) with 1-methoxy-1-trimethylsilyloxyethene (4a) in dichloromethane in the presence of titanium tetrachloride gave 62percent of methyl 2-(2′-methyl-1′,3′-dioxolan-2′-yl)acetate (5a).Similarly, reaction of (1c) with 1-methoxy-1-trimethylsilyloxyprop-1-ene (4b) afforded 73percent of methyl 2-(2′-methyl-1′,3′-dioxolan-2′-yl)propanoate (5b).

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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, highly enantioselective methodology for the synthesis of alpha-phosphanyl ketones 7 and 2-phosphanyl alcohols 12 and 13, important hemilable ligands for enantioselective homogeneous catalysis and chiral building blocks in general, has been developed. The key step of this first enantioselective synthesis of alpha-phosphanyl ketones is the diastereoselective phosphanylation of SAMP hydrazones 2 to produce alpha-phosphanyl hydrazones, isolated as the more stable borane adducts 6. Subsequent ozonolysis afforded alpha-phosphanyl ketones 7. The enantioselective synthesis of 2-phosphanyl alcohols 12 and 13 has been accomplished by two fundamentally different procedures: the phosphanylation of unsubstituted chiral aldehyde hydrazones 9 and the alkylation of alpha-diphenylphopshanyl acetaldehyde SAMP hydrazone 10. After separation of the minor diastereomer, the borane-protected alpha-phosphanyl aldehyde hydrazones 11 were converted to unprotected 2-phosphanyl alcohols 13 by ozonolysis, reduction and removal of the borane group. The absolute configuration of the functionalized phosphanes was determined by X-ray analysis, NOE experiments or polarimetry. VCH Verlagsgesellschaft mbH, 1997.

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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 palladium catalyst supported on fibrous silica nanospheres (KCC-1) has been developed for the hydrogenation of alkenes and alpha,beta-unsaturated carbonyl compounds, providing excellent yields of the corresponding products with remarkable chemoselectivity. Comparison (high-resolution TEM, chemisorption) with analogous mesoporous (MCM-41, SBA-15) silica-supported Pd nanocatalysts prepared under identical conditions, demonstrates the advantage of employing the fibrous KCC-1 morphology versus traditional supports because it ensures superior accessibility of the catalytically active cores along with excellent Pd dispersion at high metal loading. This morphology ultimately leads to higher catalytic activity for the KCC-1-supported nanoparticles. The protocol developed for hydrogenation is advantageous and environmentally benign owing to the use of HCOOH as a source of hydrogen, water as a solvent, and because of efficient catalyst recyclability and durability. The recycled catalyst has been analyzed by XPS spectroscopy and TEM showing only minor changes in the oxidation state of Pd and in the morphology after the reaction, thus confirming the robustness of the catalyst.

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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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Ruthenium complexes of phosphinoferrocenylaminophosphine ligands (BoPhoz ligands) have been prepared by combining the ligands with tris(triphenylphosphine)ruthenium dichloride and precipitating the complexes. The optimal species exhibit high enantioselectivities for the asymmetric hydrogenation of functionalized ketones, particularly beta-ketoesters.

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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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Compounds structurally related to 2-cyclohexen-1-one 1,4-di-O-benzyl-L-threitol ketal were prepared and subjected to the Simmons-Smith cyclopropanation.From these experiments a mechanistic model for diastereoselective cyclopropanation of common ring systems (five-, six-, and seven-membered) has been formulated.Diastereoselectivity is thought to result from preferential chelation of the Simmons-Smith reagent at the least sterically hindered lone pair of electrons on the dioxolane oxygen proximal to the alkene.It is found that the presence of oxygen atoms in the dioxolane appendages provide sites for competitive chelation of the reagent, which can antagonize the diastereoselection due to chelation at dioxolane oxygen.That chelation by dioxolane oxygen does occur and is responsible for diastereoselectivity is inferred from studies with a hydrocarbon model system.Surprisingly, both dioxolane appendages are shown to be necessary for optimum diastereoselection since, under the conditions of the Simmons-Smith cyclopropanation, 2-cycloalken-1-one ethylene ketals are reversibly ring opened to zwitterionic intermediates.

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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 possibilities and limitations of 13C NMR spectroscopy for the determination of the basicity of carbonyl-containing compounds are examined.It is shown that the protonation of polycyclic aromatic ketones in deutero acids increases the contribition of the C+-OD form relative to that of the C=+OD form, whereas in the case of aliphatic ketones and of monosubstituted acetophenones and benzaldehydes the C=+OD form is predominant.

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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