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A new one-step strategy for the stereochemical assignment of acyclic 2- and 3-sulfanyl-1-alkanols using the CD exciton chirality method

A new one-step strategy is described for the stereochemical assignment of acyclic 2- and 3-sulfanyl-1-alkanols using the CD exciton chirality method. Using the 9-anthroate chromophore for the derivatization of both functional groups, the resulting bisignate CD curves unequivocally allow the determination of the stereochemistry from a single CD measurement. The usefulness of the new method is demonstrated using synthesized optically pure 3-sulfanyl-1-hexanols and 2-sulfanyl-1-hexanols as model compounds. The developed microscale method is also useful for the stereochemical assignment of 1,2- and 1,3-diols. To our knowledge this is the first application of the CD exciton chirality method to acyclic 2- and 3-sulfanyl-1-alkanols.

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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

Can You Really Do Chemisty Experiments About (S)-Propane-1,2-diol

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The Influence of Intramolecular Dynamics on Branching Ratios in Thermal Rearrangements

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£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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METHOD FOR PRODUCING ALCOHOL BY HYDROGENATING LACTONE AND CARBOXYLIC ACID ESTER IN LIQUID PHASE

Disclosed is a method for producing an alcohol from a lactone or a carboxylic acid ester, which enables to produce an alcohol from a lactone or a carboxylic acid ester under relatively mild conditions with high yield and high catalytic efficiency. This method also enables to produce an optically active alcohol from an optically active lactone or an optically active carboxylic acid ester. Specifically disclosed is a method for producing an alcohol by hydrogen reducing a lactone or a carboxylic acid ester in the presence of a catalyst containing ruthenium and a phosphine compound represented by the following general formula (1): wherein R1 represents a spacer; R2, R3, R4, R5, R6 and R7 independently represent a hydrogen atom, an alkyl group having 1-12 carbon atoms, an aryl group or a heterocyclic group; and R8, R9, R10, R11, R12 and R13 independently represent an alkyl group having 1-12 carbon atoms, an aryl group or a heterocyclic group.

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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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Iridium-Catalyzed Synthesis of Substituted Indanones from Aromatic Carboxylates and Unsaturated Ketones

A catalytic annulation is presented that provides straightforward, modular synthetic access to 3-substituted indanones from benzoic acids and alpha,beta-unsaturated ketones. It is catalyzed by a bimetallic Ir/In system and proceeds via hydroarylation followed by Claisen condensation and optional retro-Claisen deacylation. The annulation may be combined into a one-pot procedure with the synthesis of the unsaturated ketone substrates from aldehydes and acetone. Two complementary reaction protocols are provided that are applicable to diversely functionalized electron-rich and electron-poor substrates.

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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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Synthesis and Absolute Configuration of Natural 2-Pyrones

2-Pyrones are frequently produced by microorganisms and often exhibit interesting bioactivities. Therefore, a short and easy synthetic access to these natural products is desirable. Synthetic routes to nectriapyrone, gibepyrone A, racemic gulypyrone A, (+)-germicidin C, (ent)-desoxygermicidin C and (ent)-prolipyrone A via a modular approach are presented, allowing the assignment of the absolute configurations of the latter three chiral compounds. The method failed for the synthesis of (ent)-phomapyrone B that was thus synthesized via a different route, resulting in an assignment of the absolute configuration of natural phomapyrone B.

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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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A novel transition metal-free conjugate reduction of alpha,beta-unsaturated ketones with tosylhydrazine as a hydrogen source

A novel and efficient method has been developed for the chemoselective conjugate reduction of alpha,beta-unsaturated ketones with tosylhydrazine as a hydrogen source to the corresponding saturated ketones in moderate to good yields. The present protocol does not require the use of transition metal, and is efficient being applicable to a wide range of substrates (25 examples).

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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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Rate and mechanism of the reaction of (E)-PhCH=CH-CH(Ph)-OAc with palladium(0) complexes in allylic substitutions

The reaction of (E)-1,3-diphenyl-3-acetoxyprop-1-ene, PhCH=CH-CH(Ph)-OAc, with palladium(0) complexes Pd0L2, generated from Pd 0(PPh3)4 or Pd0(dba)2 + 2L (L = PPh3 or L2 = dppb), gives cationic [(eta3-PhCH-CH-CHPh)PdL2]+ complexes with AcO- as the counteranion in DMF. It is established that this reaction proceeds through two successive equilibria via neutral intermediate complexes (eta2-PhCH=CH-CH(Ph)-OAc)Pd0L2, characterized from the kinetics and by UV and 31P NMR spectroscopy. The rate constants and equilibrium constants of the successive steps have been determined in DMF. They depend on the ligand and the Pd0 precursor. In all cases, for the concentration range investigated here, the complexation is considerably faster than the ionization, which is the rate-determining step of the overall process. Under similar experimental conditions, the formation of the cationic complex [(eta3-PhCH-CH-CHPh)Pd(dppb)]+ is considerably slower than the formation of the complex [(eta3- CH2-CH-CH2)Pd(dppb)]+ in DMF.

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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 (S)-Propane-1,2-diol

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SYNPHOS: A new atropisomeric diphosphine ligand. From laboratory-scale synthesis to scale-up development

A new optically active diphosphine ligand, [(5,6),(5?,6?)-bis(ethylenedioxy)biphenyl.2,2?-diyl]bis (diphenylphosphine) (SYNPHOS) has been synthesized. Laboratory-scale synthesis and scale-up development of this ligand are described herein. This new atropisomeric diphosphine was also used in ruthenium-catalyzed asymmetric hydrogenation.

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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

Final Thoughts on Chemistry for (S)-Propane-1,2-diol

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Chemoselective Benzoylations of 1,2-Diols. Reactivity Comparisons of Reagents. Triphenylphosphine-Benzoyl Peroxide and Triphenylphosphine-Diethyl Azodicarboxylate-Benzoic Acid

The triphenylphosphine-benzoyl peroxide (TPP-BPO) reagent initiates stereospecific benzoylation of secondary carbinol stereocenters with essentially complete inversion of stereochemistry.Monobenzoylations of 1,2-propanediol and styrene glycol with TPP-BPO and triphenylphosphine-diethyl azodicarboxylate-benzoic acid reagents afford a predominance of the more sterically encumbered C-2 benzoate with complete inversion of stereochemistry.Formation of a quintessential 1,3,2lambda5-dioxaphospholane intermediate, followed by proton-assisted and highly stereoselective ring opening of the phospholanes to isomeric oxyphosphonium ions, allows for Arbusov displacement of triphenylphosphine oxide by benzoate anion.This rationale adequately accounts for both the high chemoselectivity and the stereochemistry of the reactions.

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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

Simple exploration of 1,5-Diphenylpenta-1,4-dien-3-one

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A powerful synergistic effect for highly efficient diastereo- and enantioselective phase-transfer catalyzed conjugate additions

An efficient, catalytic, diastereo- and enantioselective conjugate addition of N-(diphenylmethylene)glycine tert-butyl ester to beta-aryl substituted enones was realized in the presence of 1 mol% of newly desired dinuclear N-spiro-ammonium salts, affording functionalized alpha-amino acid derivatives in 57-98% yields with high diastereoselectivity (up to 99:1 dr) and enantioselectivity (up to 96.5:3.5 er).

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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