Properties and Exciting Facts About C3H8O2

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Enhanced cooperative activation effect in the hydrolytic kinetic resolution of epoxides on [co(salen)] catalysts confined in nanocages

(Chemical Equation Presented) Being cagey: More than two chiral [Co-(salen)] catalyst molecules can be confined in one nanocage of SBA-16 by reducing the pore entrance size by silylation. The [Co(salen)]/SBA-16 catalysts with more than two [Co(salen)] complexes in each cage show a significantly enhanced cooperative activation effect and exhibit much higher activity than the homogeneous [Co(salen)] catalyst in the hydrolytic kinetic resolution of epoxides (see scheme).

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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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First enantiopure calix[6]aza-cryptand: Synthesis and chiral recognition properties towards neutral molecules

The synthesis of the first enantiopure calix[6]aza-cryptand was achieved in five steps from the known 1,3,5-tris-O-methylated calix[6]arene. A 1H NMR spectroscopic study has shown that the chiral tren cap constrains the calixarene core in a straight cone conformation ideal for host-guest chemistry applications. As a result, the tetra-protonated derivative displays remarkable host properties towards polar neutral molecules and enantioselective recognition processes have been evidenced with chiral guests.

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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

Simple exploration of (S)-Propane-1,2-diol

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The regioselective and stereospecific substitution of unsymmetrical 1,2-diols using the 1,3,2lambda5-dioxaphospholane methodology

Stereo specific tosylate (-OTs) or azide (N3-) substitution at the C-4 stereocenter of a monosubstituted 1,3,2lambda5-dioxaphospholane (the equivalent of the C-2 stereocenter in an unsymmetrical 1,2-diol) is readily achieved by treatment with either P-toluenesulfonic acid (P-TsOH) in tetrahydrofuran solvent or P-TsOH/sodium azide in acetonitrile solvent, respectively.

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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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Bispalladacycle-catalyzed bronsted acid/base-promoted asymmetric tandem azlactone formation-michael addition

Cooperative activation by a soft bimetallic catalyst, a hard Bronsted acid, and a hard Bronsted base has allowed the formation of highly enantioenriched, diastereomerically pure masked alpha-amino acids with adjacent quaternary and tertiary stereocenters in a single reaction starting from racemic N-benzoylated amino acids. The products can, for example, be used to prepare bicyclic dipeptides.

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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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Efficient synthesis of trifluoromethylated cyclopentadienes/fulvenes/ norbornenes from divinyl ketones

The synthetic methods of trifluoromethylated cyclopentadienes/fulvenes/ norbornenes have been developed using 3-CF3-1,4-dien-3-ols as the synthons, which can be easily prepared by the regiospecific 1,2-addition of the Ruppert-Prakash reagent (TMSCF3) to divinyl ketones. All the reactions are carried out under mild, metal-free conditions to afford the corresponding products in high to excellent yields.

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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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NMR determination of the absolute configuration of chiral 1,2- and 1,3-diols

Each of the chiral 1,2- and 1,3-diols examined was derivatized exclusively to a single diastereomeric acetal by the use of a new axially chiral reagent, 2?-methoxy-1,1?-binaphthalene-8-carbaldehyde (MBC). The absolute configuration of the original 1,2- and 1,3-diols was determined by the NOE correlation between the proton signals of the reagent moiety and those of the diol moiety in the acetals.

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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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Effect of Methyl Substitution on Conformation and Molecular Arrangement of BEDT-TTF Derivatives in the Crystalline Environment

Two methylated bis(ethylenedithio)tetrathiafulvalene (ET) derivatives, Me2ET and Me4ET were stereoselectively synthesized to examine the effect of methylation on conformations of dihydrodithiin rings and molecular arrangements in the crystalline state.Since the donating ability of Me2ET and Me4ET are similar to that of ET, the methylated ET derivatives are considered to be appropriate to investigate the “lattice pressure” effect on ET radical salts by changing the volume of donor molecules.The upper limit of an activation energy for the ring inversion of the dimethylated dihydrodithiin in solution was estimated to be 32 kJ mol-1 by 13C NMR spectroscopy.The X-ray structure analyses revealed that orientations of methyl groups are fixed to axial in Me2ET and to equatorial in Me4ET, accompanied by the change of molecular stacking.The “volume of a methyl group” was evaluated by comparing the molecular volumes of Me2ET and Me4ET with that of ET, and the effective volume for the axial methyl group turns out to be 15percent larger than that of the equatorial.The solid state 13C NMR (CP/MAS) spectra of ET and its derivatives showed that the chemical shifts of resonance lines reflect the conformations of dihydrodithiin rings in crystals.

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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 RhCl(PPh3)3/BF3·OEt2 co-promoted direct C-C cross-coupling of alcohols at beta-position with aldehydes

A novel RhCl(PPh3)3/BF3·OEt2 co-promoted direct C-C cross-coupling of primary and secondary alcohols at beta-position with aldehyde was developed. This reaction could provide an efficient synthesis of a series of alpha,beta-unsaturated aldehydes and diarylidene ketones, just from simple and easily available alcohols and aldehydes.

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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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Stereochemistry of hydroxylation during the conversion of alpha-ketoisocaproate to beta-hydroxyisovalerate by 4-hydroxyphenylpyruvate dioxygenase

4-Hydroxyphenylpyruvate dioxygenase catalyzes the oxidative decarboxylation and hydroxylation of alpha-ketoisocaproate 1 to beta-hydroxyisovalerate 2 with retention of configuration during the hydroxylation step.

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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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Nature and characterization of the singlet and triplet excited states of the dibenzylideneacetone and di-3-(N-ethylcarbazoylidene)acetone bridging ligands

The lowest energy singlet state in di-3-(N-ethylcarbazoylidene)acetone (dNECa), a luminescent model compound at room temperature for dibenzylidenecacetone (dba), has been assigned to a charge transfer (CT) state using the medium polarity effect on lambdamax(F) and fluorescence polarized spectra of dNECa at 77 K.The dNECa fluorescence quantum yields (phiF) and lifetimes (tauF) are solvent sensitive where both phiF and tauF tend to increase with polarity.The very weak and moderately structured phosphorescences have been located for the first time for both dba and dNECa in the 550-800 nm range and are also assigned to a CT state.In this case the CT interactions are less pronounced than lambda(0-0)P and taup are much less solvent sensitive.Finally, EHMO type calculations confirm that the CT transition is the lowest energy transition in dba and di-3-(N-methylindoylidene)acetone (a model compound for dNECa), but also suggest that the n?* state must lie near the CT state in dba.

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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