Synthesis of 2,2,5,5‐Tetrasubstituted 1,4‐Dioxa‐2,5‐disilacyclohexanes via Organotin(IV)‐Catalyzed Transesterification of (Acetoxymethyl)alkoxysilanes

(Acetoxymethyl)silanes 2 , 7 a – c , and 10 a – c with at least one alkoxy group, of the general formula (AcOCH₂)Si(OR)_3?n(CH₃)_n (R: Me, Et, iPr; n=0, 1, 2), were synthesized from the corresponding (chloromethyl)silanes 1 , 6 a – c , and 9 a – c by treatment with potassium acetate under phase‐transfer‐catalysis conditions. These compounds were found to provide 2,2,5,5‐organo‐substituted 1,4‐dioxa‐2,5‐disilacyclohexanes 3 , 8 a – c , and 11 a – c if treated with organotin(IV) catalysts such as dioctyltin oxide. The reaction proceeds through transesterification of the acetoxy and alkoxy units followed by ring‐closure to form a dimeric six‐membered ring. The corresponding alkyl acetates are formed as the reaction by‐products. With these mild conditions, the method overcomes the drawbacks of previously reported synthetic routes to furnish 2,2,5,5‐tetramethyl‐1,4‐dioxa‐2,5‐disilacyclohexane ( 3 ) and even allows the synthesis of 1,4‐dioxa‐2,5‐disilacyclohexanes bearing hydrolytically labile alkoxy substituents at the silicon atom in good yields and high purity. These new materials were fully characterized by NMR spectroscopy, elemental analysis, mass spectrometry, and X‐ray analysis (trans‐ 8 a ).     

Solvothermal Synthesis and Characterization of the New Iron Thioantimonates(III) [Fe(C6H18N4)]FeSbS4 and [Fe(C4H13N3)2]Fe2Sb4S10 Containing FeII and FeIII and Protein‐Analogous [2FeIII‐2S]2+ Clusters

The two new compounds [Fe(tren)]FeSbS₄ ( 1 ) (tren = tris(2‐aminoethyl)amine) and [Fe(dien)₂]Fe₂Sb₄S₁₀ ( 2 ) (dien = diethylendiamine) were prepared under solvothermal conditions and represent the first thioantimonates(III) with iron cations integrated into the anionic network. In both compounds Fe³⁺ is part of a [2Fe^III‐2S] cluster which is often found in ferredoxines. In addition, Fe²⁺ ions are present which are surrounded by the organic ligands. In ( 1 ) the Fe²⁺ ion is also part of the thioantimonate(III) network whereas in ( 2 ) the Fe²⁺ ion is isolated. In both compounds the primary SbS₃ units are interconnected into one‐dimensional chains. The mixed‐valent character of [Fe(tren)]FeSbS₄ was unambiguously determined with Mössbauer spectroscopy. Both compounds exhibit paramagnetic behaviour and for ( 1 ) a deviation from linearity is observed due to a strong zero‐field splitting. Both compounds decompose in one single step.     

Lower Rim Substituted p-tert-Butyl Calix[4]arenes (V). Synthesis of New 5,11,17,22-tetrakis-p-tert-Butyl-25,27-bis(methoxy)- 26,28-bis(dialkoxyphosphorylmethoxy)calix[4]arenes and Cation Complexation Studies in Ion-Selective Membrane Electrodes

The synthesis and characterization of the lower rim bis-phosphorylatedtetrakis-p-tert-butyl-25,27-bis(methoxy)calix[4]arenas(compounds 2–4) is presented. The studied compounds were examined as ionophores in ion-selective membrane electrodes, showing selectivity for rubidium, potassium, and for the large and flat guanidinium cations (G⁺). The correlation wasstudied between the stereochemical structure of the ligands andpotentiometrically determined ion-selectivity. Complex formationconstants in the PVC/BEHS (bis(ethyl)hexyl sebacate) membranes weredetermined. The crystal and molecular structures of compound 4 have been determined by single crystal X-ray diffraction study.     

Identification and relative quantification of specific glycation sites in human serum albumin

Glycation (or non-enzymatic glycosylation) is a common non-enzymatic covalent modification of human proteins. Glucose, the highest concentrated monosaccharide in blood, can reversibly react with amino groups of proteins to form Schiff bases that can rearrange to form relatively stable Amadori products. These can be further oxidized to advanced glycation end products (AGEs). Here, we analyzed the glycation patterns of human serum albumin (HSA) in plasma samples obtained from five patients with type 2 diabetes mellitus. Therefore, glycated peptides from a tryptic digest of plasma were enriched with m-aminophenylboronic acid (mAPBA) affinity chromatography. The glycated peptides were then further separated in the second dimension by RP-HPLC coupled on-line to an electrospray ionization (ESI) tandem mass spectrometer (MS/MS). Altogether, 18 Amadori peptides, encompassing 40% of the HSA sequence, were identified. The majority of the peptides were detected and relatively quantified in all five samples with a high reproducibility among the replicas. Eleven Lys-residues were glycated at similar quantities in all samples, with glycation site Lys₅₄₉ (K_Am(Glc)QTALVELVK) being the most abundant. In conclusion, the established mAPBA/nanoRP-HPLC-ESI-MS/MS approach could reproducibly identify and quantify glycation sites in plasma samples, potentially useful in diagnosis and therapeutic control.     

Multireference spin-adapted variant of density functional theory

A new Kohn-Sham formalism is developed for studying the lowest molecular electronic states of given space and spin symmetry whose densities are represented by weighted sums of several reference configurations. Unlike standard spin-density functional theory, the new formalism uses total spin conserving spin-density operators and spin-invariant density matrices so that the method is fully spin-adapted and solves the so-called spin-symmetry dilemma. The formalism permits the use of an arbitrary set of reference (noninteracting) configurations with any number of open shells. It is shown that the requirement of degeneracy of the total noninteracting energies of the reference configurations (or configuration state functions) is equivalent to the stationary condition of the exact energy relative to the weights of the configurations (or configuration state functions). Consequently, at any molecular geometry, the weights can be determined by minimization of the energy, and, for given reference weights, the Kohn-Sham orbitals can be determined. From this viewpoint, the developed theory can be interpreted as an analog of the multiconfiguration self-consistent field approach within density functional theory.     

The first and second cinchona rearrangement. Two fundamental transformations of alkaloid chemistry

Stereochemistry, products, and driving forces of the "first and second Cinchona rearrangement" have been investigated and a unified theory is presented. The first cage expansion affords [3.2.2]azabicyclic alpha-amino ether and is formulated via a configurationally stable bridgehead iminium ion and quasiequatorial nucleophilic attack. The second cage expansion affords beta-functionalized [3.2.2]azabicycles. In this case a nonclassical nitrogen-bridged cation is postulated to account for retention of configuration and potential reversibility of the cage expansion. The second rearrangement is favored for the so-called cinch bases (6'-R = H) in trifluoroethanol. Stereoelectronic factors, electron demand at C9, ground state conformation, and solvent type are crucial in all cases. A two-step protocol for preparing 9-epi-configured Cinchona alkaloids from 9-nat precursors is described.     

Orientability of the Minor Director of Homeotropically Aligned Smectic‐A Elastomers in External Mechanical Fields

We present studies on bulk smectic‐A copolymer networks with end‐on attached homeotropically oriented mesogens that show spontaneous optical biaxiality at room temperature. Orthoscopic and conoscopic investigations under uniaxial extension in the layer planes give first evidence of the orientability of the minor director in mechanical fields yielding biaxial monodomains with 3‐d orientational long‐range order of all three principle axes. This is an important step towards the synthesis of permanently oriented biaxial monodomain elastomers for which highly interesting mechanical and optical properties are expected.     

SYNTHESES,STRUCTURES AND REACTIONS OF NEW AND NOVEL FOUR-, FIVEAND SIX-MEMBERED UNSATURATED N,P-HETEROCYCLE COMPLEXES

Metal-assisted heterocyclic ligand syntheses are reported using 2-H-azaphosphirene complex 1 or 7-phosphanorbornadiene complex 7 as starting material. Thermal decomposition of complex 1 led to 1,2dihydro-1,2,3-azadiphosphete complex 2, which was transformed into 2,6-dihydro-1,3,2,6-diazadiphosphinines 5a, b via ring expansion with carbonitriles 3a, b. Insertion of tert-butyl isonitrile into the P─ P bond of 2 at ambient temperature furnished the first Δ ¹ -1,3,5-azadi-phospholene complex 6─P bond of 2 using 7 failed. The 1,2,3,4-azatriphospholene complexes 9a, b were obtained by thermolysis of complex 2 in the presence of functionalized carbonitriles 8a, b.