A novel regiodivergent resolution reaction mediated by a homochiral lithium amide base

The reaction of a racemic perhydroisoquinolene derivative 9 with the homochiral lithium amide basse 3 in the presence of Me₃SiCl in an regiodivergent fashion to give the two non-racemic regioisomeric enol silanes 10 and 11. Conversion of 10 into enone 15, an intermediate useful in the synthesis of the alkaloid (+)-yohimbine, was also possible.     

Plasma polymerization. V. A systematic investigation of the inductively coupled RF plasma polymerization of the isomeric tetrafluorobenzenes

A systematic investigation has been made of the composition, gross structural features, and rates of deposition of plasma polymer films produced from the excitation of inductively coupled RF plasmas in the isomeric tetrafluorobenzenes. ESCA data reveal that the dominant reaction involves rearrangement such that under a wide variety of experimental conditions the composition of the crosslinked products remains essentially the same as that of the starting material. Small differences in rates of deposition are observed for the different isomers, and theoretical SCF MO studies at the MNDO level provides a basis for discussion of the experimental data.     

A theoretical investigation of molecular core binding and relaxation energies in a series of oxygen-containing organic molecules of interest in the study of surface oxidation of polymers

Nonempirical LCAO MO SCF computations (in the ΔSCF formalism) have been carried out of binding energies and relaxation energies for an extensive series of oxygen-containing organic systems encompassing most of the common functionalities. The molecules for which experimental data are available for comparison demonstrate the adequacy of the treatment for describing the relative binding energies for both the C_ls and O_ls core levels. A sound basis is therefore provided for the discussion of relative core binding energies (C_ls and O_ls) for functionalities for which experimental data are not available, that is, hydroperoxides, peroxides, peroxyacids, and peroxyesters, a knowledge of which is essential for investigations of the surface oxidation of polymers by means of ESCA. C_ls shifts are discussed in terms of primary and secondary substituent effects of oxygen, which greatly simplify the analysis of complex unresolved spectra, whereas for the O_ls levels a similar but less straightforward situation exists. The relaxation energies associated with both C_ls and O_ls core ionization follow a dependence on the binding energy for a given structural type.