General strategy for a short and efficient synthesis of 3-hydroxy-4-methylprolines (HMP)

The non-proteinogenic amino acid 3-hydroxy-4-methylproline (HMP) is an active constituent of some potent antimicrobials including echinocandins, nostopeptins, pneumocandins, sporiofungin and mulundocandins. A synthesis has been achieved in 10 steps with 29% overall yield; the Evans’ aldol reaction using Crimmins’ modified method was pivotal to the success of the strategy.     

Amphoteric trap modeling of multidielectric scaled SONOS nonvolatile memory structures

We have characterized multidielectric scaled SONOS nonvolatile memory structures with the quasi-static linear voltage ramp (LVR) technique and dynamic pulse measurements. We have formulated physically-based ERASE/WRITE and retention methods with deep level amphoteric traps which capture and emit carriers to the bands in the silicon nitride film. Amphoteric trap parameters are extracted by the LVR technique. ERASE/WRITE and retention amphoteric trap model simulations agree well with the experimental dynamic pulse measurements. Experimental scaled SONOS structures have been fabricated with tunnel oxide X_OT=20 Å, nitride X_N=30 Å and blocking oxide X_OB=55 Å and demonstrated a static flatband shift of 3.6 V with ±5 V programming voltages. These structures may be used as the nonvolatile memory element in high density VLSI circuits.     

Aeroelastic flutter of a disk rotating in an unbounded acoustic medium

The linear aeroelastic stability of an unbaffled flexible disk rotating in an unbounded fluid is investigated by modeling the disk-fluid system as a rotating Kirchhoff plate coupled to the irrotational motions of a compressible inviscid fluid. A perturbed eigenvalue formulation is used to compute systematically the coupled system eigenvalues. Both a semi-analytical and a numerical method are employed to solve the fluid boundary value problem. The semi-analytical approach involves a perturbation series solution of the dual integral equations arising from the fluid boundary value problem. The numerical approach is a boundary element method based on the Hadamard finite part. Unlike previous works, it is found that a disk with zero material damping destabilizes immediately beyond its lowest critical speed. Upon the inclusion of small disk material damping, the flutter speeds become supercritical and increase with decreasing fluid density. The competing effects of radiation damping into the surrounding fluid and disk material damping control the onset of flutter at supercritical speed. The results are expected to be relevant for the design of rotating disk systems in data storage, turbomachinery and manufacturing applications.     

Tevatron: Recent results and prospects at the upgrade

In this article, we review some of the recent results from CDF and DØ experiments at the Tevatron and their prospects at the upgrade. Among the topics discussed are top quark physics, electroweak physics, qcd physics and new physics beyond standard model.     

Use of a chiral surfactant for enantioselective reduction of a ketone

The influence of a chiral surfactant and a polymer-supported chiral additive on reduction of ketones using sodium borohydride will be described. Initial preparations involved methylation of (S)-leucinol to give (2S)-N , N-dimethyl-2-amino-4-methyl-1-pentanol (1) (67%). The chiral surfactant (2) was synthesized by reacting (1) with bromohexadecane (71%). The functionalized styrene for the polymer-supported chiral additive (5) was synthesized by reacting (1) with 4-vinylbenzyl chloride. Polymerization was carried out with 10% of the functionalized monomer (4), 5% cross-linking agent divinylbenzene, and 85% styrene with AIBN as the initiator. The activity of the chiral surfactant and polymeric additive were examined by using them as additives in a standard reduction of 2-pentanone with sodium borohydride to yield (R)- and (S)-2-pentanol (3) (20%). The resulting alcohol was analyzed by polarimetry (ee 9.5%) and also esterified with (2S)-methylbutyric acid prior to characterization by NMR. 13C NMR indicated an enantiomeric excess of 5.2% when the chiral surfactant was used, and 7% when the polymeric additive was used.     

Mapping the Geometry of Metal Three‐Coordination Using Crystal Structure Data: Reaction Pathway for Ligand Addition to Linear HgII Species

Symmetry‐modified principal‐component analysis has been used to visualise the geometrical distortions of three‐coordinate metal centres observed in crystal structures retrieved from the Cambridge Structural Database. It is shown that compounds of Cu, Ag, Hg, Zn, and Au dominate the dataset, and exhibit distortions away from the trigonal planar archetype towards a) T‐shaped and b) Y‐shaped geometries. A small number of compounds, principally of Cu and Ag, also show distortions towards trigonal pyramidal geometries. The interconversions from Y‐shaped geometries, through the trigonal planar form to T‐shaped geometries are clearly mapped by the PC analysis. For Hg^II complexes, it is possible to interpret the transition from T‐shaped geometries to the trigonal planar form in terms of a reaction pathway for ligand addition to linear L₁? Hg^II? L₂ species.     

Synthesis of cyclopentane building blocks via an intramolecular CH insertion reaction of a chiral pool derived α-diazo-γ-hydroxy-β-ketosulfone

A highly functionalized cyclopentanone building block 13 was prepared by a facile Rh-catalyzed intramolecular CH insertion reaction of an enantiopure α-diazo-γ-hydroxy-β-ketosulfone 12, in turn derived from an α-hydroxy acid 2. A cyclic γ-hydroxy vinyl sulfone 16 was also prepared from 13.     

Carbene-catalyzed enantioselective annulation of dinucleophilic hydrazones and bromoenals for access to aryl-dihydropyridazinones and related drugs

4,5-Dihydropyridazinones bearing an aryl substituent at the C6-position are important motifs in drug molecules. Herein, we developed an efficient protocol to access aryl-dihydropyridazinone molecules via carbene-catalyzed asymmetric annulation between dinucleophilic arylidene hydrazones and bromoenals. Key steps in this reaction include polarity-inversion of aryl aldehyde-derived hydrazones followed by chemo-selective reaction with enal-derived α,β-unsaturated acyl azolium intermediates. The aryl-dihydropyridazinone products accessed by our protocol can be readily transformed into drugs and bioactive molecules.

Polarity inversion of arylidene hydrazones to react with bromoenals via carbene organic catalysis is disclosed. The reaction enantioselectively affords 6-aryl-4,5-dihydropyridazinones and related drugs with proven commercial applications.     

Polyhydroxy pregnanes from Dregea volubilis

Three new polyhydroxy pregnanes named dregealol (1), volubilogenone (2) and volubilol (3) were isolated from the flowers of Dregea volubilis, and their structures elucidated from extensive 2D NMR analysis. The structure of volubilol (3) was confirmed by X-ray crystallographic studies. The known pregnane derivatives drevogenin D, iso-drevogenin P and 17α-marsdenin were also isolated.     

Extending Coggia–Couvreur attack on Loidreau’s rank-metric cryptosystem

Designs, Codes and Cryptography - A recent paper by Coggia and Couvreur presents a polynomial time key-recovery attack on Loidreau’s encryption scheme, based on rank-metric codes, for some...