Interactions of nitrated aromatics with electron rich species: Chiral and achiral

Binding interactions between nitrated aromatics and electron rich aromatic groups are at the core of the chiral recognition process for many classes of organic compounds. The majority of the work described in the thesis is concerned with problems encountered in chiral chromatography. A method predicting elution order of a class of racemic compounds using a commercially available chiral stationary phase is described in Chapter 2. The method uses a new thermodynamic approach.;Chapters 3, 4, and 5 are devoted to the design of various chiral stationary phases. The emphasis of all projects is on preparative aspects of chiral chromatography. One of the developed chiral stationary phases (Chapter 4) is capable of preparative resolution of enantiomers of two commercially important compounds in polar organic mobile phases with very large enantioseparation factors.;The work described in Chapter 6 is of a mechanistic nature. Identification of the formation of Meisenheimer complexes under conditions of phase transfer catalysis helped to rationalize the enantioselectivity observed in these systems. Quaternary ammonium cations are identified as stabilizing factors for the negatively charged Meisenheimer complexes in non-polar organic solvents. The gained mechanistic insight allowed the development of the first enantioselective nucleophilic aromatic substitution reactions.