Enantioselective Rhodium-Catalyzed Pauson–Khand Reactions of 1,6-Chloroenynes with 1,1-Disubstituted Olefins

An enantioselective rhodium(I)-catalyzed Pauson–Khand reaction (PKR) using 1,6-chloroenynes that contain challenging 1,1-disubstituted olefins is described. In contrast to the previous studies with these types of substrates, which are only suitable for a single type of tether and alkyne substituent, the new approach results in a more expansive substrate scope, including carbon and heteroatom tethers with polar and non-polar substituents on the alkene. DFT calculations provide critical insight into the role of the halide, which pre-polarizes the alkyne to lower the barrier for metallacycle formation and provides the proper steric profile to promote a favorable enantiodetermining interaction between substrate and chiral diphosphine ligand. Hence, the chloroalkyne enables the efficient and enantioselective PKR with 1,6-enynes that contain challenging 1,1-disubstituted olefins, thereby representing a new paradigm for enantioselective reactions involving 1,6-enynes.     

Four-Component Borocarbonylation of Vinylarenes Enabled by Cooperative Cu/Pd Catalysis: Access to β-Boryl Ketones and β-Boryl Vinyl Esters

We report here a general four-component synthetic procedure for the preparation of β-boryl ketones and β-boryl vinyl esters. Joint catalyzed by palladium and copper catalysts, borocarbonylative reaction between vinylarenes, aryl halides/triflates, B₂Pin₂, and carbon monoxide proceed successfully. A variety of synthetically useful β-boryl ketones were synthesized in good to high yields by using aryl iodides as the substrates. It is noteworthy that when aryl triflates were applied as the starting materials, β-boryl vinyl esters were synthesized in a similar manner and with broad functional group tolerance. A rational mechanism for this reaction was also proposed.     

Enantioselective Hydrosilylation of β,β-Disubstituted Enamides to Construct α-Aminosilanes with Vicinal Stereocenters

Despite the advances in the area of catalytic alkene hydrosilylation, the enantioselective hydrosilylation of alkenes bearing a heteroatom substituent is scarce. Here we report a rhodium-catalyzed hydrosilylation of β,β-disubstituted enamides to directly afford valuable α-aminosilanes in a highly regio-, diastereo-, and enantioselective manner. Stereodivergent synthesis could be achieved by regulating substrate geometry and ligand configuration to generate all the possible stereoisomers in high enantio-purity.     

Selective Modification of β-Cyclodextrin on the Secondary Side 4:Preparation of Arylated β-Cyclodextrins with a Flexible Chain

Cyclodextrins(CDs,includinga-,o-,a-CD,etc.)havegainedprominenceinrecentyearsbecauseoftheirtorus-shapedcavity,whichishydrophilicoutsideandhydrophobicinside,caPableofprovidingidealprototypestoconstructefficientartificialenzymes,molecuIarrecognitionsensorsandotherfunctionalmodels.l-3Forbuildingmoreefficientartificialenzymesandmolecularrecognitionsensors,wehavepreparedaseriesof6-CDderivativesbearingchromophores'-'andfoundthat3"-'anarylmoietycouldactasaspectrometryprobeaswellasafunctionalgroup.F…     

Tackling N-Alkyl Imines with 3d Metal Catalysis: Highly Enantioselective Iron-Catalyzed Synthesis of α-Chiral Amines

A readily activated iron alkyl precatalyst effectively catalyzes the highly enantioselective hydroboration of N-alkyl imines. Employing a chiral bis(oxazolinylmethylidene)isoindoline pincer ligand, the asymmetric reduction of various acyclic N-alkyl imines provided the corresponding α-chiral amines in excellent yields and with up to >99 % ee. The applicability of this base metal catalytic system was further demonstrated with the synthesis of the pharmaceuticals Fendiline and Tecalcet.     

Diastereoselective elaboration of the carbon skeleton of β-hydroxyesters from yeast reductions Preparation of (2S)-2-Hydroxy-cyclohexane Carboxylic Acids with Three Contiguous Stereogenic Centers

The dioxanone-type acetal 2 from (1R, 2S)-2-hydroxy-cyclo-hexane carboxylic acid (1) and pivalaldehyde is dehydrogenated to a derivative 3 of 6-hydroxy-cyclohexene carboxylic acid. Highly selective Michael additions and trapping of the resulting enolates with electrophiles give single diastereomers 4 and 5 which can be hydrolized to 6-substituted 2-hydroxy-cyclohexane carboxylic acids of type C and D.     

Facile allylboration of ketones with β-benzyloxy-γ,γ-difluoroallylboronate: Preparation of gem-difluorinated homoallylic tert-alcohols

The reaction of β-benzyloxy-γ,γ-difluoroallylboronate, at room temperature and in the absence of catalysts, with a variety of aromatic and aliphatic ketones of varying sterics and electronic requirements furnishes fluorinated homoallylic tert-alcohols in 62-82% yields. Representatives of these alcohols were converted to their corresponding α,α-difluoro-β-hydroxy ketones in 73-85% yields.     

Enantioselective HPLC combined with spectroscopic methods: A valid strategy to determine the absolute configuration of potential β-secretase inhibitors

A direct HPLC enantioseparation of three representative compounds of a new family of potential non-peptide β-secretase inhibitors was performed on the immobilized Chiralpak IA chiral stationary phase. Semipreparative amounts of enantiopure forms were collected and submitted to stereochemical characterization. The absolute configuration was assigned by a multi-step methodology based on the combination of Mosher's method with circular dichroism (CD) spectroscopy. The results from the NMR/CD study fully correlated the configurational assignment obtained by a second approach involving single crystal X-ray diffraction.     

Inclusion complexes of phosphorylated daidzein derivatives with β-cyclodextrin: Preparation and inclusion behavior study

In the present work the feasibility of β-cyclodextrin in complexation was explored, as a tool for improving the solubility and biological ability of daidzein derivatives. A series of phosphorylated daidzein derivatives featuring different chain lengths were synthesized through a modified Atherton-Todd reaction and their inclusion complexes with βCD were prepared by coprecipitation method. The inclusion complexation behavior was studied by fluorescence, UV, FT-IR, MS and (1)H NMR. The results showed that only phosphorylated daidzein derivative carrying small substituent group ((C(2)H(5)O)(2)PO) entered the cavity of βCD and formed 1:1 inclusion complex. The formation constant was 175(mol/L)(-1).     

Syntheses with sulfones L: Preparation of β-hydroxysulfones through the combined oxidative desulfonylation/condensation reaction of sulfonyl anions. Application to terpene synthesis.

The oxidative desulfonylation of primary sulfonyl anions with the molybdenum perone reagent, MoO₅.Py.HMPA, leads directly to β-hydroxysulfones through condensation of the starting α-sulfonyl anion with the aldehyde formed in situ. Symmetrical polyenes such as (Z)-12-dehydrosqualene (Z)-16-phytoene have been obtained in three steps in > 87% stereoselectivity from the corresponding β-hydroxysulfones.     

A Facile Aldoxime Preparation Via the Reduction of α, β-Unsaturated Nitroalkenes Using Tin (II) Chloride

α, β-Unsaturated nitroalkenes are readily reduced by SnCl₂ 2H₂ O in ethyl acetate to the aldoximes in high yield at room temperature.     

Using PVP/SDS Complex as a Probe to Study the Inclusion Complex of β-cyclodextrin with SDS in Aqueous Solution

PVP/SDS complex was applied as a probe to study the interaction between β-cyclodextrin （β-CD） and sodium dodecyl sulfate （SDS） in aqueous solution. It has been found that a critical concentration, namely cs, exists in the relative viscosity of solution containing PVP/SDS complex versus β-CD concentration plot. As the β-CD concentration is less than cs, the relative viscosity of solution decreases sharply by adding β-CD into solution successively. On the other hand, as the β-CD concentration is greater than cs, the relative viscosity of solution increases gradually by adding β-CD into solution. The decrease of the relative viscosity of solution containing PVP/SDS in the presence of β-CD is just due to the inclusion complex of β-CD with the guest molecule SDS. And, this inclusion interaction takes down SDS from the PVP chains in solution. The ratio of the host molecule β-CD to the guest molecule SDS can be calculated from Cs. In our experiment the inclusion ratio of β-CD to SDS is 1/1. The further experimental results indicate that cs is associated with SDS but free from PVP in PVP/SDS complex. However, the inclusion ratio of β-CD to SDS has proved to be independent of either SDS or PVP in PVP/SDS complex.     

Silica-Supported Perchloric Acid (HClO4-SiO2): An Efficient Catalyst for the Preparation of β-Amido Carbonyl Compounds Using Multicomponent Reactions

A new, one-pot, efficient, three-component condensation of benzaldehyde derivatives, enolizable ketones, acetyl chloride, and acetonitrile or benzonitrile in the presence of silica-supported perchloric acid as an effective catalyst for the synthesis of β-amido carbonyl compounds is described. The present methodology offers several advantages, such as good yields, short reaction times, and simple workup procedure.     

Enantioselective ring opening of epoxides with trimethylsilyl azide (TMSN3) in the presence of β-cyclodextrin: an efficient route to 1,2-azido alcohols

The ring opening of epoxides with nucleophiles such as TMSN₃ and isopropylamine takes place enantioselectively in the presence of β-cyclodextrin under extremely mild conditions and the azido alcohols and amino alcohols are formed as (S)-isomers.     

High-pressure mediated Diels-Alder reaction of di-l-menthyl acetoxy-methylenemalonate with furan: Enantioselective synthesis of β-D-ribofuranosylmalonate,a prospective synthon for C-nucleoside

β-D-Ribofuranosylmalonate [D]-4 has been synthesized through high-pressure Diels-Alder reaction of furan with di-l-menthyl acetoxymethylenemalonate (1b), followed by reductive retrograde aldol CC bond fission. A mechanism accounting for the observed diastereoselectivity in the Diels-Alder reaction is proposed.     

Quantification of Four Isoflavones in Forages with UPLC®-MS/MS,Using the Box–Behnken Experimental Design to Optimize Sample Preparation

A performant method for the simultaneous quantification of daidzein, genistein, formononetin, and biochanin A in forages using an UPLC^®-MS/MS was developed and fully validated. The ultrasound-assisted extraction and enzymatic hydrolysis used in the sample preparation step were optimized using the Box–Behnken experimental design. The optimal extraction conditions used for a representative mix of forage plants were 80 °C, 10 min, and 55 % methanol, and for hydrolysis, they were 20 °C, 18 h, and pH = 6. The chromatographic separation was achieved using an Acquity UPLC^® HSS T3 column, with a water/methanol linear gradient containing 0.01 % of formic acid at a 0.55 mL min⁻¹ flow rate. The four isoflavones were detected by ESI mass spectrometry in positive ion MRM mode. The method allows high throughput analyses of samples and showed an adequate linear regression model for all isoflavones over a range from 5 to 125 ng mL⁻¹. There were good intra- and inter-day precisions (≤8.2 and ≤7.6 %) and accuracy (≤11.4 and ≤7.1 %). The recovery rates were in an acceptable range of 70–120 %, except for biochanin A, where the rate was about 50 %. Good method repeatability was also observed, and there was no matrix effect or carryover problem. The sample extracts were stable for at least 6 days of storage at -21 and 6 °C. The method proved to be sensitive, precise, and accurate for discriminating a wide variety of forages likely to be grazed by ruminants according to their isoflavone contents and to observe the impact of storage process on isoflavone content in forages.

     

Formic acid oxidation on Pd/RuO2: does the RuO2 support enhance the electrocatalytic activity of Pd nanoparticles?

Journal of Solid State Electrochemistry - The aim of this work was to study the effect of a RuO2 support on the activity of Pd nanoparticles for formic acid oxidation, comparing the results with...     

Enantioselective synthesis of β-amino acids. Part 9: Preparation of enantiopure α,α-disubstituted β-amino acids from 1-benzoyl-2(S)-tert-butyl-3-methylperhydropyrimidin-4-one,

Double alkylation of enantiopure N,N-acetal pyrimidinone (S)-1, a masked chiral derivative of β-alanine prepared from (S)-asparagine, proceeds with high stereoselectivity to give C(5) disubstituted adducts (2S,5R)-6, (2S,5S)-6, (2S,5R)-7, and (2S,5S)-7. Acid hydrolysis of these derivatives affords enantiopure α,α-dialkylated β-amino acids (R)-8, (S)-8, (R)-9, and (S)-9 in very good yields.     

Time Programmed Feed of Semi-Batch Reactors with Non-Linear Radical Copolymerizations: An Experimental Study of the System Styrene + Divinylbenzene Using SEC/MALLS

Summary: The radical crosslinking copolymerization of mono and divinyl monomers was experimentally studied with a 2.5 dm³ semi-batch reactor using styrene + divinylbenzene as a model system. The analysis of products was carried out by SEC with a MALLS detector. The influence of the feed policy of divinylbenzene on the time evolution of the copolymer molecular weights and z-average mean square radius of gyration was assessed. A detailed kinetic model, in the absence of intramolecular reactions but taking into account the presence of the two isomers m- and p- in the commercial divinylbenzene and the different reactivities of the various radicals and double bonds was developed; most parameters have been collected from previous kinetic studies, and only two have been regressed using our measured molecular weights. These results can be used to improve the production of branched/crosslinked polymers with controlled molecular architecture.