Development of a new and practical route to chiral 3,4-disubstituted cyclopentanones: asymmetric alkylation and intramolecular cyclopropanation as key C-C bond-forming steps

An efficient and practical asymmetric synthesis of (+)-trans-3-hydroxymethyl-4-(3-fluorophenyl)cyclopentanone (1) is described. An asymmetric Mo-catalyzed alkylation reaction was used to establish the first stereocenter and a Cu-catalyzed intramolecular diastereoselective cyclopropanation reaction was used to set the second stereocenter. The last step involved a one-pot ring-opening/deprotection/hydrolysis/decarboxylation sequence that furnished the desired product in good yield.     

Synthesis development of an aminomethylcycline antibiotic via an electronically tuned acyliminium Friedel-Crafts reaction

With the goal of improving the synthetic efficiency, the development of a convergent synthesis of a minocycline derivative PTK0796 via an intermolecular acyliminium Friedel-Crafts reaction (Tscherniac-Einhorn reaction) is described. The entire C9 neopentylaminomethyl side chain was installed in one step using an electronically optimized chloromethylacyliminium precursor in 83% yield. Deprotection and re-equilibration to the C4 α-epimer in the presence of CaCl₂ and ethanolamine or NaOH afforded the target aminomethylcycline antibiotic. The corresponding crystalline tosylate salt was found to exhibit improved solid state stability.     

Synthesis and antitrypanosomal activity of 2-aminomethyl-1-(2-oxyphenyl)naphthalenes

A broad variety of enantiopure axially chiral 2-aminomethyl-1-(2-oxyphenyl)naphthalenes were prepared via short and efficient synthetic pathways by using the ‘lactone method’ for the regio- and stereoselective construction of the biaryl axis. Their in vitro activity against Trypanosoma cruzi, the causative agent of Chagas' disease, was evaluated. In particular, the M-configured atropisomers, with the 2-oxy function equipped with an O-triflate group, were found to exhibit good antitrypanosomal activities (down to IC₅₀=1.6 μg/mL), combined with low levels of cytotoxicity.     

SrBi2Ta2O9 ferroelectric thin film capacitors: degradation in a hydrogen ambient

The effects of annealing in forming gas 5% hydrogen, 95% nitrogen; FGA) are studied on spin-coated SrBi₂Ta₂O₉ (SBT) thin films. SBT films on a platinum bottom electrode are characterized with and without a platinum top electrode. Films are characterized by residual stress measurements, scanning electron microscopy (SEM), Auger electron spectroscopy (AES), high-temperature X-ray diffraction (HT-XRD) and secondary ion mass spectrometry (SIMS). To determine the degree of strain, lattice constants of Pt are measured by X-ray diffraction (XRD). HT-XRD of blanket SBT/Pt/Ti films in forming gas revealed that the bismuth-layered perovskite structure of SBT is stable up to approximately 500 °C. After formation of an intermediate phase between 550 °C and 700 °C, SBT changes its structure to an amorphous phase. SIMS analysis of Pt/SBT/Pt samples annealed in deuterated forming gas (5% D₂, 95% N₂) showed that hydrogen accumulates in the SBT layer and at the platinum interfaces next to the SBT. After FGA of blanket SBT films, tall platinum–bismuth whiskers are seen on the SBT surface. It is confirmed that these whiskers originate from the platinum bottom electrode and grow through the SBT layer. FGA of the entire Pt/SBT/Pt/Ti stack shows two different results. For the samples with a high-temperature annealing (HTA) step in oxygen after top electrode patterning, peeling of the top electrode is observed after FGA. For the samples without a HTA step, no peeling is observed after FGA. The residual stress at room temperature is measured for blanket platinum wafers deposited at different temperatures. It is found that an increase in tensile stress caused by the HTA step in oxygen is followed by a decrease in stress caused by the hydrogen in the forming gas. Without HTA, however, an increase of stress is observed after FGA. PACS 77.84.-s; 81.40.-z; 77.55.+f