Stereoselective enolizations mediated by magnesium and calcium bisamides: contrasting aggregation behavior in solution and in the solid state

The reactions of magnesium and calcium bis(hexamethyldisilazide) with propiophenone have been studied with a view to determine the utility of these bases in the stereoselective enolization of ketones and to uncover the nature of the metal enolate intermediates produced. Both base systems are highly Z-selective when the reactions are conducted in the presence of polar solvents. However, in situ monitoring of the magnesium system in arene solution revealed a preference for E-enolate formation, which was confirmed by silyl enol ether trapping studies. Solution NMR studies of the magnesium system in toluene-d8 show the presence of a monomer-dimer equilibrium for the intermediate amidomagnesium enolates. This assignment is supported by the characterization of a disolvated amidomagnesium enolate dimer by crystallographic analysis. Comparative studies of the calcium system show distinctly different behavior. This is exemplified by the characterization of a novel solvent-separated ion pair complex and a monomeric amidocalcium enolate in the solid state. Solution NMR studies of the calcium system in pyridine-d5 reveal the co-existence of the heteroleptic amidocalcium enolate, the bisamide, the bisenolate and the ion pair complex.     

A long-wavelength biolabeling reagent based on the oxonol fluorophore

A red fluorescent dye of the oxonol class, bis-[1-(carboxymethyl)barbituric acid-(5)]-pentamethinoxonol, has been synthesized and, in the form of the succinimidyl active ester, has been applied to antibody labeling for application to flow cytometry and to imaging of tissue sections. The new dye, named CMOX (for carboxymethyloxonol), shows maximum excitation at 583 nm and emission at 611 nm, with a quantum yield of 0.2 in aqueous buffer and methanol. Antibodies labeled with the new dye show favorable brightness, photostability, and low levels of nonspecific binding.     

Two to one images and PFA

We prove that all maps onN ^* that are exactly two to one are trivial if PFA is assumed. This article was considerably improved by the careful referee's reports. Supported by NSF grant DMS-0103985.     

Growth of active Nd-doped YAP thin-film waveguides by laser ablation

3 (YAP) thin films as a promising material for application in a planar waveguide laser has been studied. The films have been grown on sapphire(0001) and YAP(001) substrates by laser ablation. The influence of the substrate temperature and ambient oxygen pressure on the crystalline structure, concentration of Nd incorporated into films, and consequent luminescence spectra were investigated. The waveguiding properties were observed and refractive index of the films was evaluated. Received: 8 February 1998/Accepted: 9 February 1998