The scope of this thesis was to develop a method for constructing an atroposelective carbon–nitrogen bond. This challenging problem was approached in various ways, and success was not always achieved. Initially, a dehydrogenative approach using phenothiazines and phenols was attempted but proved unsuccessful due to the radical nature of the reaction and starting material. Departing from this, quinones were employed as activated phenols, enabling coupling with indolines at the NH position. Although this approach did not require catalysts and did not yield positive results, it holds potential for future development in enantioselective coupling of indolines with quinones. Moving away from C–N coupling reactions, benzophenothiazine was utilized in a cross-dehydrogenative coupling with phenols and indoles. The chiral Jacobsen-type Cr(III) complex served as the catalyst for this reaction, resulting in an enantiomeric excess of 13%. Despite preparing several other chiral complexes, no improvement was achieved. Using the aforementioned Cr(III) catalyst, an atroposelective version of the Nenitzescu indole synthesis was developed. This name reaction involves the acid-catalyzed combination of β-amino-crotonic derivatives with quinones to produce 5-hydroxyindoles. By employing Lewis acids, including the chiral Cr(III) Jacobsen-type catalyst, up to 81% enantiomeric excess was achieved. A notable discovery in this context is that the resulting product molecules form diastereomeric dimers with distinct physical properties. Specifically, the solubility changes dramatically, with the enantiopure compound being soluble in most solvents, while the racemic dimers can only be dissolved by boiling in polar solvents. This property enables the separation of the racemate from the product mixture through filtration, leading to the isolation of the enantiopure product with up to 99% ee. In a way, this represents a resolution by filtration. One of the major breakthroughs in this thesis was the development of an atroposelective Chan-Lam amination. This achievement is of significant importance since no such reaction has been published previously, including the Buchwald-Hartwig and Ullmann-Goldberg amination reactions, making it the first of its kind to be published. It is not surprising, considering that the development process for the atroposelective Chan-Lam amination was lengthy and challenging, involving multiple attempts to identify a suitable N-heterocycle with the appropriate substitution. Eventually, it was determined that Fuberidazole (2-(2'-furyl)-benzimidazole) was the most suitable candidate for this reaction. In addition to substrate design, a comprehensive ligand design was crucial, resulting in the optimized ligand V-POX. Another important aspect of reaction optimization was the choice of base, as only hydrocarbonates proved successful. With these tools at hand, yields of up to 90% and enantiomeric excesses of up to 92% could be achieved.