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Br°nsted ionic liquids: Study of physico-chemical properties and catalytic activity in aldol condensations

A serie of substituted amines based ionic liquids was prepared using an aliphatic linear carboxylic acid (pentanoic acid). The ionic liquids synthesised are 2-hydroxy ethylammonium pentanoate (2-HEAPE), 2-hydroxy diethylammonium pentanoate (2-HDEAPE) and 2-hydroxy triethylammonium pentanoate (2-HTEAPE). FT-IR spectra establishes their ionic salt structure. The influence of structural variations on their thermodynamic properties (density, ultrasonic velocity, ionic conductivity, refractive index, viscosity and surface tension) was investigated, as a function of temperature in the range 278.15-338.15. K. In the compounds studied here, the anion has strong effect on the properties if compared with previous studies of the authors, when shorter chains were used. It was found that the elongation of the alkyl chain causes the pronounced depression of fluidity and ionic conductivity. The observed temperature trend of the studied properties points out the special packing of these ionic liquids, as well as, the strong influence of the steric hindrance among linear aliphatic residues. We also describe the catalytic activity of these type of ionic liquids for a representative serie of aldol condensation processes. Conversions higher than 98% and selectivities higher than 85% were obtained. Moreover the catalysts are easily separated from reaction mixture and re-used, obtaining good conversions for at least three consecutive cycles. As a conclusion, it was found that simple structural modifications into anion length and degree of substitution provide a mechanism to manipulate the catalytic potency of these ionic liquids, as well as, tailor physico-chemical properties for potential end-use 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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Olefination of alpha,alpha?-divinyl ketones through catalytic Meyer-Schuster rearrangement

The direct olefination of 1,4-dien-3-ones remains a synthetic challenge. A two-step protocol, employing acetylide addition followed by catalytic Meyer-Schuster rearrangement has been developed for the olefination of 1,4-pentadien-3-ones to afford [3]dendralenes. Many of the traditional methods for the Meyer-Schuster rearrangement of alkynyl carbinols are not suitable with these highly unsaturated substrates because of their acid sensitivity. Unexpected reactivity during attempted rearrangement, including Nazarov-type electrocyclizations, is presented, along with conditions to promote the Meyer-Schuster rearrangement of ethoxyacetylene adducts using catalytic VO(acac)2.

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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 synthesis method according to sets up qu tan hydrobromide (by machine translation)

The invention discloses a method for synthesizing according to sets up qu tan hydrobromide, which comprises the following steps: in the organic solvent, (R)- 1 – acetyl – 3 – (N – methyl pyrrolidine – 2 – methyl) – 5 – bromo – 1 H – indole with the metal to form the metal complex, metal complex in organic solvent with the boron reagent in the reaction to form the aryl borane or aryl borate, acid catalyzed hydrolysis to obtain the aryl boronic acid, aryl boric acid and 2 – chloro ethyl diphenylol in catalyst, under the action of the alkali hydrolysis into coupling and according to sets up qu tan, or metal complex directly with 2 – chloro ethyl phenyl sulphone coupling and hydrolysis into according to sets up qu tan, according to sets up qu tan in the organic solvent with the hydrobromic into finally obtained according to sets up qu tan hydrobromide salt. The method is simple to operate, safe and stable, low cost and high yield, is suitable for industrial production. (by machine translation)

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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

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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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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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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

The Absolute Best Science Experiment for 1,5-Diphenylpenta-1,4-dien-3-one

However, they have proven to be challenging because of the mutual inactivation of both catalysts. Each step is an elementary reaction. In my other articles, you can also check out more blogs about 538-58-9

The transformation of simple hydrocarbons into more complex and valuable products via catalytic C–H bond functionalisation has revolutionised modern synthetic chemistry. An article , which mentions category: chiral-oxygen-ligands, molecular formula is C17H14O. The compound – 1,5-Diphenylpenta-1,4-dien-3-one played an important role in people’s production and life., category: chiral-oxygen-ligands

A simple, efficient, and green procedure for the 1,4-addition of thiols to conjugated alkenes and alkynes catalyzed by sodium acetate in aqueous medium

A benign and inexpensive salt, sodium acetate, efficiently catalyzes 1,4-addition of thiols to a variety of conjugated alkenes such as ?,?-unsaturated ketones, aldehydes, carboxylic esters, nitriles, nitro compounds, and chalcones in aqueous THF. The reactions are clean, fast, and high yielding. CSIRO 2007.

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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

Extracurricular laboratory:new discovery of C17H14O

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Highly stereoselective, one-pot synthesis of azetidines and 2,4-dioxo-1,3-diazabicyclo[3.2.0] compounds mediated by I2

We report here a convenient method to construct polysubstituted azetidines and 2,4-dioxo-1,3-diazabicyclo[3.2.0] compounds with high stereoselectivities in a one-pot reaction mediated by I2. The tetramethylguanidine (TMG)/I2-mediated formal [2 + 2] cycloaddition reaction of alpha-amidomalonate 1 with enones 2 affords functionalized azetidine derivatives 4 in moderate to good yields with high diastereoselectivity. When the alpha-ureidomalonate 5 is used instead of 1, 2,4-dioxo-1,3-diazabicyclo[3. 2.0]heptanes 8 and 2,4-dioxo-1,3-diazabicyclo[3.2.0]heptenes 9 can be prepared selectively through the control of solvent and temperature. 2,4-Dioxo-1,3- diazabicyclo[3.2.0]heptanes 8 can further undergo ring-opening reactions with different nucleophilic reagents to afford the corresponding polyfunctionalized azetidine derivatives 13-16 with high steroselectivities.

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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

The important role of 1,5-Diphenylpenta-1,4-dien-3-one

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Gold(I)-Catalyzed Desymmetrization of 1,4-Dienes by an Enantioselective Tandem Alkoxylation/Claisen Rearrangement

An enantioselective alkoxylation/Claisen rearrangement reaction was achieved by a strategic desymmetrization of 1,4-dienes under the catalysis of (S)-DTBM-Segphos(AuCl)2/AgBF4. This reaction system was highly selective for the formation of 3,3-rearrangement products, providing cycloheptenes with various substitutions in good yield and good to excellent enantioselectivity. This transformation was further extended to bicyclic ring substrates, providing the opportunity to easily assemble 5,6- and 6,7-fused ring systems.

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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