Total Synthesis and Structural Revision of the Antibiotic Tetrapeptide GE81112A

The total synthesis of the naturally occurring antibiotic GE81112A, a densely functionalized tetrapeptide, is reported. Comparison of spectral data with those of the natural product and the lack of biological activity of the synthesized compound led us to revise the published configuration of the 3‐hydroxypipecolic acid moiety. This hypothesis was fully validated by the synthesis of the corresponding epimer.     

Highly Enantioselective Reactions of Configurationally Labile Epimeric Diamine Complexes of Lithiated S‐Benzyl Thiocarbamates

Substitution reactions that employ primary‐carbamoyl‐protected arylmethanethiols are described. The enantiodetermining step was found to occur in the post‐deprotonation step as a dynamic thermodynamic resolution with a chiral bis(oxazoline) ligand. The configurationally labile lithium complexes were trapped with various electrophiles to yield different substitution products in good to excellent yields and enantiomeric excesses. The absolute configurations of the substitution products were determined, and the stereochemical pathway of the substitution reaction was elucidated for different classes of electrophiles. The temperature‐dependent epimerization process was monitored by ¹H and ⁶Li NMR spectroscopy.     

Organic semiconductors for solution-processable field-effect transistors (OFETs)

The cost-effective production of flexible electronic components will profit considerably from the development of solution-processable, organic semiconductor materials. Particular attention is focused on soluble semiconductors for organic field-effect transistors (OFETs). The hitherto differentiation between "small molecules" and polymeric materials no longer plays a role, rather more the ability to process materials from solution to homogeneous semiconducting films with optimal electronic properties (high charge-carrier mobility, low threshold voltage, high on/off ratio) is pivotal. Key classes of materials for this purpose are soluble oligoacenes, soluble oligo- and polythiophenes and their respective copolymers, and oligo- and polytriarylamines. In this context, micro- or nanocrystalline materials have the general advantage of somewhat higher charge-carrier mobilities, which, however, could be offset in the case of amorphous, glassy materials by simpler and more reproducible processing.     

Synthesis of 6H-indolo[2,3-b]quinoxaline-N-glycosides and their cytotoxic activity against human ceratinocytes (HaCaT)

N-glycosides of 6H-indolo[2,3-b]quinoxalines were prepared and structurally characterized. The synthesis relies on the cyclocondensation of isatine-N-glycosides with 1,2-diaminobenzenes. Some products exhibit weak cytotoxic activity against human ceratinocytes (HaCaT).     

Determination of molindone enantiomers in human plasma by high-performance liquid chromatography-tandem mass spectrometry using macrocyclic antibiotic chiral stationary phases

A sensitive and selective bioanalytical assay was developed and validated for the determination of enantiomeric molindone in human plasma using high-performance liquid chromatography-tandem mass spectrometry along with supported liquid extraction procedures. The chiral separation was evaluated and optimized on macrocyclic antibiotic type chiral stationary phases (CSPs) based on teicoplanin aglycone (Chirobiotic TAG) in polar organic, polar ionic, and reversed-phase mode chromatography, respectively. Complete baseline separation was achieved on a Chirobiotic TAG column under isocratic condition in reversed-phase chromatography. The method validation was conducted using a Chirobiotic TAG column (100 mm x 2.1 mm) over the curve range 0.100-100 ng/ml for each molindone enantiomer using 0.0500 ml of plasma sample. The flow rate was 0.8 ml/min and the total run time was 9 min. Supported liquid extraction in a 96-well plate format was used for sample preparation. Parameters including recovery, matrix effect, linearity, sensitivity, specificity, carryover, precision, accuracy, dilution integrity, and stability were evaluated. The intra- and inter-day precision and accuracy of the quality control samples at low, medium, and high concentration levels were RSD 相似文献   

Hydrogen and dihydrogen bonding of transition metal hydrides

Intermolecular interactions between a prototypical transition metal hydride WH(CO)₂NO(PH₃)₂ and a small proton donor H₂O have been studied using DFT methodology. The hydride, nitrosyl and carbonyl ligand have been considered as site of protonation. Further, DFT-D calculations in which empirical corrections for the dispersion energy are included, have been carried out. A variety of pure and hybrid density functionals (BP86, PW91, PBE, BLYP, OLYP, B3LYP, B1PW91, PBE0, X3LYP) have been considered, and our calculations indicate the PBE functional and its hybrid variation are well suited for the calculation of transition metal hydride hydrogen and dihydrogen bonding. Dispersive interactions make up for a sizeable portion of the intermolecular interaction, and amount to 20–30% of the bond energy and to 30–40% of the bond enthalpy. An energy decomposition analysis reveals that the H?H bond of transition metal hydrides contains both covalent and electrostatic contributions.     

C60/corannulene on Cu(110): a surface-supported bistable buckybowl-buckyball host-guest system

Corannulene (COR) buckybowls were proposed as near ideal hosts for fullerene C60, but direct complexation of C60 and COR has remained a challenge in supramolecular chemistry. We report the formation of surface-supported COR-C60 host-guest complexes by deposition of C60 onto a COR lattice on Cu(110). Variable-temperature scanning tunneling microscopy studies reveal two distinctly different states of C60 on the COR host lattice, with different binding energies and bowl-ball separations. The transition from a weakly bound precursor state to a strongly bound host-guest complex is found to be thermally activated. Simple model calculations show that this bistability originates from a subtle interplay between homo- and heteromolecular interactions.     

Investigation of the Catalytic Activity of a 2‐Phenylidenepyridine Palladium(II) Complex Bearing 4,5‐Dicyano‐1,3‐bis(mesityl)imidazol‐2‐ylidene in the Mizoroki‐Heck Reaction

The phenylidenepyridine (ppy) palladacycles [PdCl(ppy)(IMes)] ( 4 ) [IMes = 1,3‐bis(mesityl)imidazol‐2‐ylidene] and [PdCl(ppy){(CN)₂IMes}] ( 6 ) [(CN)₂IMes = 4,5‐dicyano‐1,3‐bis(mesityl)imidazol‐2‐ylidene] were prepared by facile two step syntheses, starting with the reaction of palladium(II) chloride with 2‐phenylpyridine followed by subsequent addition of the NHC ligand to the precatalyst precursor [PdCl(ppy)]₂. Suitable crystals for the X‐ray analysis of the complexes 4 and 6 were obtained. It was shown that 6 has a shorter NHC‐palladium bond than the IMes complex 4 . The difference of the palladium carbene bond lengths based on the higher π‐acceptor strength of (CN)₂IMes in comparison to IMes. Thus, (CN)₂IMes should stabilize the catalytically active central palladium atom better than IMes. As a measure for the π‐acceptor strength of (CN)₂IMes compared to IMes, the selone (CN)₂IMes · Se ( 7 ) was prepared and characterized by ⁷⁷Se‐NMR spectroscopy. The π‐acceptor strength of 7 was illuminated by the shift of its ⁷⁷Se‐NMR signal. The ⁷⁷Se‐NMR signal of 7 was shifted to much higher frequencies than the ⁷⁷Se‐NMR signal of IMes · Se. Catalytic experiments using the Mizoroki‐Heck reaction of aryl chlorides with n‐butyl acrylate showed that 6 is the superior performer in comparison to 4 . Using complex 6 , an extensive substrate screening of 26 different aryl bromides with n‐butyl acrylate was performed. Complex 6 is a suitable precatalyst for para‐substituted aryl bromides. The catalytically active species was identified by mercury poisoning experiments to be palladium nanoparticles.