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CONVENIENT PREPARATION OF BINAP-RUTHENIUM(II) COMPLEXES CATALYZING ASYMMETRIC HYDROGENATION OF FUNCTIONALIZED KETONES

Ligand exchange between 2 or RuCl23 and (R)- or (S)-BINAP produces BINAP-Ru(II) complexes which act as catalysts for the highly enantioselective hydrogenation of functionalized ketones.

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate

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Capturing a ghost. synthesis and structural characterization of Pd(dba)[P(o -Tol)3]2

In an effort to improve upon a literature synthesis of bis[tris(o-tolyl) phosphine]palladium(0) (1) from tris(o-tolyl)phosphine and Pd 2(dba)3, we instead isolated a new compound which proved to have the composition Pd(dba)[P(o-Tol)3]2 (2), upon analysis by X-ray crystallography. While this is not the first known palladium compound containing both dba and phosphine ligands, it is, to our knowledge, the first containing dba and tris(o-tolyl)phosphine. This is significant, because mixtures of Pd2(dba)3 and tris(o-tolyl)phosphine are routinely used in cross-coupling protocols, and palladium complexes containing dba and tris(o-tolyl)phosphine have been cited as intermediates in organometallic and polymerization reactions. The most interesting crystallographic parameter for 2 is an abnormally long Pd-P bond length of 2.388(1) A, which we believe is the cause of this complex’s metastability. We also present an alternative synthesis of 1 that does not require a large excess of phosphine.

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate

New explortion of (S)-Propane-1,2-diol

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A chemical/computational approach to the determination of absolute configuration of flexible and transparent molecules: Aliphatic diols as a case study

(Graph Presented) By reacting flexible and optically transparent in UV-vis molecules such as 1,2-, syn- and anti-1,3-diols, 1,3-sulfanylalcohols of known absolute configuration (AC) with fluorenone dimethyl acetal, the corresponding ketals are obtained. They are conformationally well-defined (only one conformer in most cases) compounds exhibiting medium-high optical rotation (OR) values, which are independent of the solvent, and electronic circular dichroism (ECD) spectra, which show several (up to five) Cotton effects in the 350-200 nm range due to valence shell pi?pi* transitions. These features allow simulation of the chiroptical properties of these compounds at the TDDFT/B3LYP/6-31G* level of theory to obtain, using the known ACs of these compounds, a satisfactory reproduction of the OR values (sign and order of magnitude; quantitatively, the predicted values are twice the experimental ones), and a more than satisfactory reproduction of the ECD spectra (sign, intensity, and position of the lowest-energy four Cotton effects) for all the compounds studied. Therefore, this approach can be used to assign the AC of such flexible molecules, in particular, syn-1,3-diols, which are important substrates in organic synthesis and for which nonempirical methods of AC assignment have not been devised so far. Furthermore, since the fluorene chromophore leads to the presence of several Cotton effects from, say, 350 to 200 nm, their correct simulation of sign, intensity, and position is a guarantee of the correct assignment of AC: in this way, ECD spectroscopy gains the same advantages of VCD spectroscopy, that is, the need of reproducing many ECD bands and then a solid guarantee of a correct AC assignment.

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate

Archives for Chemistry Experiments of 19132-06-0

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Sorption and selective chromatographic properties of isomer-selective composite sorbent based on a eutectic mixture of nematic liquid crystals and perbenzoylated beta-cyclodextrin

Mesomorphic, sorption, and selective properties of a three-component sorbent based on a mixture of nematic (N) liquid crystals of 4-methoxy-4?-ethoxyazoxybenzene (MEAB) and 4,4?-diethoxyazoxybenzene (azoxyphenetol, AOP) of an eutectic composition and heptakis-(2,3,6-tri-O-benzoyl)-beta-cyclodextrin (Bz-beta-CD) are studied. For 30 organic compounds of different classes with linear and cyclic molecular structures, including optical isomers of limonene, pinene, camphene, and butanediol-2,3, thermodynamic functions are determined for their gas-phase sorption using a three-component MEAB-AOP-Bz-beta- CD sorbent (62: 28: 10 wt %). It is found that the investigated sorbent possesses high structural selectivity (alphap/m = 1.128-1.059, 100-130C, N) and moderate enantioselectivity (1.07-1.02) within a broad temperature range (95-170C) including both mesomorphic and isotropic phases of the sorbent. It is shown that the enantioselectivity of the sorbent is apparent under conditions of both increasing retention when a chiral Bz-beta-CD additive is introduced into the MEAB-AOP system (limonenes, pinenes, camphenes) and decreasing retention (butanediols-2,3).

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate

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Enantioselective synthesis of decarestrictine J

An efficient total synthesis of decarestrictine J has been achieved using ring-closing metathesis and Yamaguchi esterification as key steps. The stereogenic centres were generated by means of iterative hydrolytic kinetic resolution (HKR) of racemic epoxides.

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate

Extracurricular laboratory:new discovery of 1,5-Diphenylpenta-1,4-dien-3-one

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Highly enantioselective synthesis of spiro[cyclohexanone-oxindoles] and spiro[cyclohexanone-pyrazolones] by asymmetric cascade [5+1] double Michael reactions

The asymmetric catalytic synthesis of naturally occurring and biologically active spiro compounds is a challenge for modern chemical methodology. Here we report the construction of spiro compounds through cascade [5+1] double Michael reactions between divinyl ketones and N-unprotectedoxindoles or N-phenyl-protected pyrazolones catalyzed by a combination of the easily available 9-amino-9-deoxy-epi-quinine with N-Boc-D-phenylglycine. The desired multistereogenic spiro[cyclohexanone-oxindoles and -pyrazolones] were obtained with high yields (up to 98 %) andstereoselectivities (up to >20:1 dr, 99 % ee). An efficient approach to spiro compounds through cascade [5+1] double Michael reactions between divinyl ketones and oxindoles or N-protected pyrazolones in the presence of 9-amino-9-deoxy-epi-quinine and N-Boc-D-phenylglycine is reported. Multistereogenic spiro[cyclohexanone- oxindoles and -pyrazolones] are obtained with high yields (up to 98 %) and stereoselectivities (up to >20:1 dr, 99 % ee). Copyright

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate

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Highly Regioselective and Stereospecific Functionalization of 1,2-Proanediol with Trimethyl(X)silanes Employing the 1,3,2lambda5-Dioxaphospholane Methodology

The regioselective ring opening of (S)-4-methyl-2,2,2-triphenyl-1,3,2lambda5-dioxaphospholanes (2) was initiated with several trimethylsilyl reagents (Me3SiX: X = PhS, I, Br; Cl, CN, and N3) to afford the regioisomeric (silyloxy)phosphonium salts.A stereospecific extrusion of triphenylphosphine oxide from these oxyphosphonium salts gave predominatly the thermodynamically less stable C-2-X-substituted derivatives with nearly complete inversion of stereochemistry at the C-2 stereogenic center (i.e., X = PhS).

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate

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ARYLBORONIC ACIDS WITH INTRAMOLECULAR B-N INTERACTION: CONVENIENT SYNTHESIS THROUGH ortho-LITHIATION OF SUBSTITUTED BENZYLAMINES

Ortho-lithiation of N,N-dimethylbenzylamine and reaction with trimethylborate gave the corresponding boronic acid in good yields.The reaction was extended to the synthesis of various aromatic boron compounds with nitrogen-containing substituents in the ortho-position, including a chiral boroxin prepared from (S)-N,N-dimethyl-1-phenylethylamine.From N-Methyl-benzylamine a stable boronium salt was obtained under certain conditions.The spectra of the newly synthesized compounds are discussed.Intramolecular B-N interaction is established by 11B NMR spectroscopy.

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate

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OPTIMIZATION OF THE PAPAIN CATALYZED ESTERIFICATION OF AMINO ACIDS BY ALCOHOLS AND DIOLS

Esterification of Boc-Alanine and Boc-Aspartic acids by alcohols CnH2n+1OH and diols HO(CH2)nOH with immobilized papain (XAD-7 or Sepharose) is discussed.Great improvement is obtained for the esterification of Boc-Ala-OH if papain is entrapped in XAD-7.For example no esterification is observed with 1-decanol if free papain is used whereas a 55 percent yield is obtained with papain immobilized on XAD-7.Esterification of Boc-Asp-OH with diols has been achieved with papain immobilized on Sepharose.In the case of ethyleneglycol no condensation could be observed with free papain or papain on XAD-7 whereas a 40 percent yield of esterification was obtained with papain on Sepharose.

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate

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2 Tyrosine kinase mediated signal transduction inhibitors (by machine translation)

[Problem] 2 tyrosine kinase mediated signal transduction inhibitor. (I) a pharmaceutically acceptable salt of the compound of the formula [a] and (In the formula, R1 , R2 , R3 , R4A , R4B , X1 , X2 , X3 , X4 , X5 And the n, as herein defined), pharmaceutical compositions containing the same, as well as preparation and use of the method, are disclosed herein. Figure 1 [drawing] (by machine translation)

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate