Novel route to 5-position vinyl derivatives of thiolactomycin: Olefination vs. deformylation

Vinyl and diene derivatives of thiolactomycin have been prepared via Horner-Wadsworth-Emmons olefination from protected 5-formyl-3,5-dimethylthiotetronic acid. Several 4-position protecting groups and a variety of phosphonates were evaluated, with MOM protection and β-ketophosphonates yielding the highest ratio of the desired product to deformylated product.     

The synthesis of 6-trifluoroethyl-l-lysine: a method to introduce functionality at C-6 of l-lysine

Described is a method of introducing trifluoroalkyl groups at C-6 of lysine. This chemistry has the potential to introduce a variety of functionality at C-6 of lysine.     

Dark cure studies of cationic photopolymerizations of epoxides: Characterization of kinetic rate constants at high conversions

The effective propagation rate constant (k_p; averaged over all the propagating active centers) was characterized for solvent‐free cationic photopolymerizations of phenyl glycidyl ether over the entire range of conversions, including the high conversion regime in which mass transfer limitations become important. The profile for the k_p as a function of conversion was found to exhibit a constant plateau value at low to intermediate conversions, followed by a monotonic increase above a threshold value of conversion. To explain this trend, it is proposed that at high conversion the diffusional mobility of the photoinitiator counterion is reduced whereas the mobility of the cationic active center remains high because of reactive diffusion. Therefore, with increasing conversion, the average distance between the active centers and counterions may increase, resulting in an increase in the propagation rate constant. The profiles for the k_p values were investigated as a function of the temperature, photoinitiator anion, and photoinitiator concentration. As the photoinitiator concentration was increased, the plateau value of the effective propagation rate constant decreased whereas the threshold conversion increased. All of the experimental trends are consistent with the proposed increase in ion separation at high conversions. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4409–4416, 2004     

Synthesis and conformational studies of a new host system based on cholic acid

New synthetic hosts have been designed incorporating two molecules of cholic acid linked by a rigid diamine. Proton NMR studies indicate that the compounds exist in a rigid conformation with the steroid hydroxyl groups intramolecularly hydrogen-bonded. Heat or addition of methanol leads to conformational isomerism due to insertion of methanol into the cavity.A preliminary report of this work was presented at the 4th International Symposium on Inclusion Phenomena, July 20–25, 1986, Lancaster, U.K.     

Probing the surface structure of quasicrystals via angle-resolved low-energy ion scattering

Angle-resolved low-energy ion scattering is a valuable technique for examining the topmost surface layers of materials. Using this technique, information about both composition and structure can be obtained. We discuss the physical basis of this technique and present our findings for the fivefold surface of icosahedral (i-) Al–Pd–Mn. Our results clearly show that the exposed surface has a higher Al content than the bulk and can have fivefold periodicity. Information about frequently occurring interatomic distances on the surface can also be obtained by this technique. We discuss the results and compare them to recent scanning tunneling microscopy studies and to bulk structure models.