Mesoporous micelle templated silica with incorporated C<Subscript>8</Subscript> and C<Subscript>18</Subscript> phase

Mesoporous silica material of MCM-41 type was synthesized by co-condensation of highly concentrated octyltriethoxysilane (OTEOS), octadecyltriethoxysilane (ODTEOS) and tetraethoxysilane (TEOS). The obtained hybrid materials were characterized using XRD, TG-DSC and low temperature adsorption/desorption of nitrogen. It was shown that the applied method of synthesis allows to obtain silica of MCM-41 type with a high degree of hydrocarbon saturation.     

Facile synthesis of acyclic azanucleosides from N-pivaloyloxymethyl amides and sulfonamides: synthesis of aza-analogues of Ganciclovir

N-Pivaloyloxymethyl amides and sulfonamides, readily available from N-alkylation of both amides and sulfonamides with commercial chloromethyl pivaloate, were converted into acyclic azanucleosides via a one-pot base silylation/nucleoside coupling procedure.     

Expanding the Scope of Arylsulfonylacetylenes as Alkynylating Reagents and Mechanistic Insights in the Formation of Csp2?Csp and Csp3?Csp Bonds from Organolithiums

We describe the unexpected behavior of the arylsulfonylacetylenes, which suffer an “anti‐Michael” addition of organolithiums producing their alkynylation under very mild conditions. The broad scope, excellent yields, and simplicity of the experimental procedure are the main features of this methodology. A rational explanation of all these results can be achieved by theoretical calculations, which suggest that the association of the organolithiums to the electrophile is a previous step of their intramolecular attack and is responsible for the unexpected “anti‐Michael” reactions observed for substituted sulfonylacetylenes.     

Highly Diastereoselective [3+2] Cycloadditions Between Non-Racemic p-Tolylsulfinimines and Iminoesters: An Efficient Entry to Enantiopure Imidazolidines and Vicinal Diaminoalcohols

Abstract

Readily available p-tolylsulfinimines undergo highly stereoselective [3 + 2] cycloadditions with azomethine ylides generated from α -iminoesters and LDA to produce N-sulfinylimidazolidines. In the presence of Lewis acids, p-tolylsulfinimines react with glycine iminoester enolates to produce N-sulfinylimidazolidines, after cyclization of open chain intermediates. These mechanistically diverse processes take place with excellent regio-, stereo-, and facial selectivities, and the latter is opposite to most known reactions involving sulfinimines. Some of the resulting imidazolidines have been transformed into examples of a novel class of nonsymmetrical vicinal diamines using reductive and/or hydrolytic protocols.     

Convenient synthesis of epimeric indolizidines by the intramolecular 1,3-dipolar cycloaddition of a sugar derived N-(3-alkenyl)nitrone

The stereoselective synthesis of two epimeric penta-hydroxylated indolizidines was accomplished from 2,3:5,6-di-O-isopropylidene-α-d-mannofuranose and N-(2-methylpent-4-en-2-yl)hydroxylamine. The transformation of these substrates into the corresponding 7-oxa-1-azabicyclo[2.2.1]heptane by the intramolecular 1,3-dipolar cycloaddition was the key step of the synthesis. The adduct was transformed into the tricyclic ammonium salt by intramolecular N-alkylation. The tricyclic ammonium salt was converted to the target compounds by: (route 1) the catalytic hydrogenation; or (route 2) the reaction with sodium azide, followed by the enantioselective reduction of the resulting indolizidinone.     

Studies of conversion progress of calcium aluminate cement hydrates by thermal analysis method

This article presents the investigations of the progress of conversion process of calcium aluminate hydrates formed during hydration of calcium aluminate cement at various temperature conditions occurring over time by thermal analysis method. Moreover, the differences of microstructure were also confirmed by SEM/EDS studies and X-ray diffraction analysis. On the basis of the obtained results, it is concluded that thermal analysis method is a very attractive and useful way to identify the structure of hydrated calcium aluminate cement matrix and allows estimating the degree of the conversion at different times of various process conditions. The conversion process of metastable calcium aluminate hydrates into stable hydrogarnet and gibbsite is strictly temperature dependent and could be completed at different times. Acceleration of the conversion is caused not only by the increasing external temperature of storage, but also the temperature inside the sample is very important. The self-heating, which could be strong in large sample, and occurring during first few hours of hydration of calcium aluminate cement, initiates the transformation.     

Regio- and stereoselective reduction of trans-4-phenylbut-3-en-2-one using carrot,celeriac, and beetroot enzyme systems in an organic solvent

(S)-trans-4-Phenylbut-3-en-2-ol has been obtained in excellent yields and with high enantiomeric excess in the reduction of trans-4-phenylbut-3-en-2-one using the comminuted roots of carrot (Daucus carota L.), celeriac (Apium graveolens L. var. rapaceum), and beetroot (Beta vulgaris L. subsp. Vulgaris) in isooctane. This is the first Letter of this bioreduction with plant tissue in an organic solvent.     

Sulfinyl-mediated chirality transfer in diastereoselective Claisen rearrangements

[reaction: see text] The highly selective Claisen rearrangements of substrates bearing a sulfinyl moiety at C-5 allow for creation of up to two asymmetric centers and preserve a useful vinyl sulfoxide.     

New Molecular Receptors with Cyclophosphazene Subunits: Synthesis, Reactivity, and Structure-Property Relationships

A series of hydrophopic ( 2 and 3) and new hydrophilic ( 4– 7) molecular receptors of the PNP-lariat ether with tetra-substituted cyclotriphosphazene subunits have been prepared by the complete nucleophilic substitution of chlorine atoms in the reactive PNP-crown precursor 1 with the respective sodium cation-paired oxyanions (phenoxy 2, -naphthoxy 3, and methoxytrioxyethylenoxy 4) and aliphatic amines (n-propylamine 5 aziridine 6, and pyrrolidine 7). Their structures were established by MS and ³¹P NMR spectroscopy and their metal ion complexing properties tested by a TLC method. Comparison of the complexation behaviour for ligands 1– 7 shows that the affinity for particular cations is strongly substituent-dependent and, in general, is significantly enhanced by cooperation of the side arm donor atoms (O or N) with the parent PNP-crown structure in the binding process. The remarkable affinity of some ligands for selected cations, in particular lithium, cesium, and silver ions, is interpreted in terms of structure-property relationships.     

Application of chemiluminescence for the detection of peroxy compounds in high-performance liquid chromatography

The possibility of applying post-column reaction and chemiluminescence to determine organic peroxy compounds by RP-HPLC was investigated. Conditions of qualitative and quantitative analyses have been established. The applicability of the method has been demonstrated for a series of compounds representative of the most important groups of peroxy-type compounds, that is, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxyesters, and peroxyacids.