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(Chemical Equation Presented) The regiospecific [5C+1C] annulation of readily available R-alkenoyl ketene (S,S)-acetals 1 with aryl methyl ketones 2, the less active methylene compounds, has been developed. Upon treatment of 1 with 2 in the presence of t-BuOK inDMFat room temperature, highly substituted 2-cyclohexenones 3 were synthesized in high to excellent diastereoselectivities with high yields. On the basis of this strategy, sterically hindered benzophenones 4 were conveniently prepared via the iodonationaromatization of 2-cyclohexenones 3 with I2 in MeONa/MeOH basic medium. Furthermore, benzophenones 4 were also obtained directly from 1 and 2 following a sequential [5 + 1] annulation-iodonation-aromatization procedure in a one-pot operation.

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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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In the presence of tetrakispyridine cobalt dichromate (CoPy4(HCrO4)2), pyridinium ylides and alpha,beta-unsaturated aldehydes or ketones undergo 1,3-dipolar cycloaddition reactions followed by in situ aromatization to give 1-acyl substituted indolizines in moderate to good 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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Chiral aldehyde catalysis is uniquely suitable for the direct asymmetric alpha-functionalization of N-unprotected amino acids, because aldehydes can reversibly form imines. However, there have been few successful reports of these transformations. In fact, only chiral aldehyde catalyzed aldol reactions of amino acids and alkylation of 2-amino malonates have been reported with good chiral induction. Here, we report a novel type of chiral aldehyde catalyst based on face control of the enolate intermediates. The resulting chiral aldehyde is the first efficient nonpyridoxal-dependent catalyst that can promote the direct asymmetric alpha-functionalization of N-unprotected glycine esters. Possible transition states and the proton transfer process were investigated by density functional theory calculations.

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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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13C NMR, alone or in combination with 1H NMR, allows the assignment of the absolute configuration of chiral alcohols, amines, carboxylic acids, thiols, cyanohydrins, sec,sec-diols and sec,sec-aminoalcohols, derivatized with appropriate chiral auxiliaries. This extends the assignment possibilities of NMR to fully deuterated and to nonproton containing compounds.

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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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Seventeen examples of 2,6-diarylspiro[cyclohexane-1,3′-indoline]-2′,4-diones were efficiently prepared by the Cs2CO3-catalysed chemoselective double Michael additions of indolin-2-one to divinyl ketones. This method has the advantage of high chemoselectivity, mild reaction conditions, high yield and atom- and step-economy.

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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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1- and 2-phenylbicyclo<2.1.1>hex-2-enes-5-d undergo thermal rearrangement to give products, differing only in the location of the deuterium, in ratio of about 9:1, but with identical activation enthalphies.Similarly, opticallly active trans-2-methyl-1-(trans-2-phenylethenyl)cyclopropane is found to rearrange to enantiomeric methylphenylcyclopentenes that are formed in a 5.9:1 ratio but with virtually identicyl activation enthalphies.Barring repeated coincidence, these results do not seem to be explicable within the framework of statistical theories of unimolecular kinetics such as RRKM theory, transition state theory, and variational transition state theory.The possible influence of dynamic effects in these and other unimolecular reactions is discussed.

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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 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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Balanced chemical reaction does not necessarily reveal either the individual elementary reactions by which a reaction occurs or its rate law.Related Products of 19132-06-0. In my other articles, you can also check out more blogs about 19132-06-0

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Chiral crystalline sponges with preinstalled chiral references were synthesized. On the basis of the known configurations of the chiral references, the absolute structures of guest compounds absorbed in the pores of the crystalline sponges can be reliably determined without crystallization or chemical modification.

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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 new strategy was introduced for the catalytic resolution of 1,2-propanediol involving the successive oxidative kinetic resolution and asymmetric hydrogenation by two hydrogen transfer reactions catalyzed by nano SiO2-bonded Ru-TsDPEN [TsDPEN = N-(p-toluenesulfonyl)-1,2-diphenylethylene diamine]-derived catalysts composed of two opposite configurations. The catalysts were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), Brunauer-Emmett-Teller (BET), Fourier-transform infrared spectroscopy (FT-IR), thermogravimetry-derivative thermogravimetry (TG-DTG) analysis, and inductively coupled plasma atomic emission spectrometry (ICP-AES). Results showed that Ru-TsDPEN derived catalysts were successfully grafted on the nano SiO2, affording high catalytic conversions of >99 and 99%, selectivities of 47 and 98% and maximum ee values of >99 and >99% in the two reactions, which were due to the nano SiO2 with Ru-TsDPEN in the reaction system with high dispersion. Additionally, the catalysts exhibited excellent durability and were filtered and reused at least five times without noticeable catalysts deactivations.

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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 Bull-James boronic acid assembly is used simultaneously as a chiral auxiliary for kinetic resolution and as a chiral shift reagent for in situ enantiomeric excess (ee) determination by 1H NMR spectroscopy. Chiral terminal alkyne-containing amines, and their corresponding chiral triazoles formed via CuAAC, were probed in situ. Selectivity factors of up to s = 4 were imparted and measured, accurate to within ±3% when compared to chiral GC.

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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