D‐Glucosamine in iron‐catalysed cross‐coupling reactions of Grignards with allylic and vinylic bromides: application to the synthesis of a key sitagliptin precursor

A sustainable D ‐glucosamine ligand is successfully introduced into iron‐catalysed C ? C cross‐coupling reactions for the first time. The Fe(acac)₂/D ‐glucosamine·HCl/Et₃N catalytic system was effective at 5 mol% loading in coupling reactions of Grignard reagents with organic bromides. Moderate to high efficiency was achieved with preserved stereochemistry when allyl (Csp³) or alkenyl (Csp²) bromides were coupled with phenylmagnesium (Csp²) or benzylmagnesium (Csp³) bromides. The catalytic system developed was also successfully applied for the novel and economic preparation of a Michael‐acceptor‐like starting material used in an alternative synthesis of the drug sitagliptin, a known blockbuster for the treatment of type II diabetes mellitus. Copyright © 2015 John Wiley & Sons, Ltd.     

Ethylenediamine diacetate-catalyzed three-component reaction for the synthesis of 2,3-dihydroquinazolin-4(1H)-ones and their spirooxindole derivatives

Ethylenediamine diacetate (EDDA)-catalyzed one-pot syntheses of biologically interesting 2,3-dihydroquinazolin-4(1H)-ones and their spirooxindole derivatives from isatoic anhydride, amines, and benzaldehydes or isatins via a three-component condensation in aqueous media have been described. This method is of great value because of high yields and ease of handling.     

Propagation‐based phase‐contrast X‐ray microtomography of a cerebral protection device retrieved after carotid artery stenting

Phase‐contrast synchrotron X‐ray microtomography (pcSyncX) based on the highly coherent X‐ray beam has previously been used to visualize the microstructures of biologic specimens, but it has never been used to evaluate embolic debris adherent on a cerebral protection device (CPD). The purpose of this study was to demonstrate the feasibility of pcSyncX for evaluating embolic debris during carotid artery stenting (CAS). Five patients (four males, age range 67–77 years) with severe carotid artery stenosis underwent CAS. The retrieved CPD was exposed to synchrotron radiation and 1000 pcSyncX projection images were obtained by rotating the CPD through 180°. An X‐ray shadow of a CPD was converted into a visual image by the scintillator. After microtomographic reconstruction, the three‐dimensionally reconstructed images were further segmented into the embolic debris and CPD. The total volume of emboli was calculated by summing the volume at each scanning level. The number of membrane pores covered by emboli as seen from the outer surface was counted and the percentage of covered area was calculated. Embolic debris was clearly demonstrated not only on the inner surface and within pores but also on the outer surface of the CPD. The mean total volume of embolic debris was 0.538 × 10^–6 mm³ (range 0.225–0.965 × 10^–6 mm³). Most (61.5%) of the debris was located at the apical one‐third of the CPD and 20.8% of the pore area was covered by debris.     

Entanglement switching via the Kondo effect in triple quantum dots

We consider a triple quantum dot system in a triangular geometry with one of the dots connected to metallic leads. Using Wilson’s numerical renormalization group method, we investigate quantum entanglement and its relation to the thermodynamic and transport properties in the regime where each of the dots is singly occupied on average, but with non-negligible charge fluctuations. It is shown that even in the regime of significant charge fluctuations the formation of the Kondo singlets induces switching between separable and perfectly entangled states. The quantum phase transition between unentangled and entangled states is analyzed quantitatively and the corresponding phase diagram is explained by exactly solvable spin model. In the framework of an effective model we also explain smearing of the entanglement transition for cases when the symmetry of the triple quantum dot system is relaxed.     

Rhodium(II)‐Catalyzed Reaction of Iodonium Ylides with Electron‐Deficient and Conjugated Alkynes: Efficient Synthesis of Substituted Furans

The rhodium(II)‐catalyzed reactions of iodonium ylides with electron‐deficient and conjugated alkynes have been examined. These reactions provide a rapid route to the preparation of furan derivatives with a variety of substituents on the furan ring.     

Development of a new contactless dielectrophoresis system for active particle manipulation using movable liquid electrodes

This study presents a new DEP manipulation technique using a movable liquid electrode, which allows manipulation of particles by actively controlling the locations of electrodes and applying on–off electric input signals. This DEP system consists of mercury as a movable liquid electrode, indium tin oxide (ITO)‐coated glass, SU‐8‐based microchannels for electrode passages, and a PDMS medium chamber. A simple squeezing method was introduced to build a thin PDMS layer at the bottom of the medium chamber to create a contactless DEP system. To determine the operating conditions, the DEP force and the friction force were analytically compared for a single cell. In addition, an appropriate frequency range for effective DEP manipulation was chosen based on an estimation of the Clausius–Mossotti factor and the effective complex permittivity of the yeast cell using the concentric shell model. With this system, we demonstrated the active manipulation of yeast cells, and measured the collection efficiency and the dielectrophoretic velocity of cells for different AC electric field strengths and applied frequencies. The experimental results showed that the maximum collection efficiency reached was approximately 90%, and the dielectrophoretic velocity increased with increasing frequency and attained the maximum value of 10.85 ± 0.95 μm/s at 100 kHz, above which it decreased.     

Ribosomal protein mutations in Korean patients with Diamond-Blackfan anemia

Diamond-Blackfan anemia (DBA) is a congenital bone marrow failure syndrome characterized by hypoproliferative anemia, associated physical malformations and a predisposition to cancer. DBA has been associated with mutations and deletions in the large and small ribosomal protein genes, and genetic aberrations have been detected in ∼50–60% of patients. In this study, nine Korean DBA patients were screened for mutations in eight known DBA genes (RPS19, RPS24, RPS17, RPS10, RPS26, RPL35A, RPL5 and RPL11) using the direct sequencing method. Mutations in RPS19, RPS26 and RPS17 were detected in four, two and one patient, respectively. Among the mutations detected in RPS19, two mutations were novel (c.26T>A, c.357-2A>G). For the mutation-negative cases, array-CGH analysis was performed to identify copy-number variations, and no deletions involving the known DBA gene regions were identified. The relative mRNA expression of RPS19 estimated using real-time quantitative PCR analysis revealed two- to fourfold reductions in RPS19 mRNA expression in three patients with RPS19 mutations, and p53 protein expression analysis by immunohistochemistry showed variable but significant nuclear staining in the DBA patients. In conclusion, heterozygous mutations in the known DBA genes RPS19, RPS26 and RPS17 were detected in seven out of nine Korean DBA patients. Among these patients, RPS19 was the most frequently mutated gene. In addition, decreased RPS19 mRNA expression and p53 overexpression were observed in the Korean DBA patients, which supports the hypothesis that haploinsufficiency and p53 hyperactivation represent a central pathway underlying the pathogenesis of DBA.     

Novel Reductive Cleavage Reaction of Thiobenzoates with Samarium Diiodide: Convenient Synthesis of Disulfides

The reductive cleavage of thiobenzoates promoted by samarium diiodide afforded various kinds of disulfides in good yields under mild and neutral conditions.     

Preparation of99mTc complexes with diastereomeric dimercaptosuccinic acids

Four stereoisomeric^99mTc complexes from meso and racemic 2,3-dimercaptosuccinic acids /DMSA/ were prepared controlling the pH and the molar ratio of ligand to tin/II/ chloride. The complexes showed different thermal stability and lipophilicity.