The thesis focuses on the development of organocatalytic methods to efficiently generate novel enantioenriched products. The different projects are united by the utilization of base catalysis, which promotes the isomerization of allylic- and propargylic compounds in a stereospecific manner. The effective chirality transfer processes give access to a variety of functionalized compounds with potential applications in drug discovery. 

The first project of this thesis demonstrates that a simple bicyclic guanidine base, namely 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), enables the stereospecific isomerization of α-chiral allylic amines (Paper I). The resulting enamine–imine tautomeric mixture is directly exploited in a one-pot sequence through diastereoselective reduction with DIBAL-H, enabling the preparation of a wide array of α,-γ-chiral γ-trifluoromethylated aliphatic amines. This method offers a new and efficient entry to functionalized chiral amines. 

The second project presents a different strategy that further highlights the synthetic potential of the abovementioned enamine-imine tautomeric mixture (Paper II). Therein, acyl chlorides were subsequently added in a one-pot fashion to access a new class of γ-chiral trifluoromethylated enamides. A broad library of such compounds was synthesized with different substituents and functional groups. A variety of chemical transformations were performed to obtain novel chiral complex scaffolds.

This thesis also explores TBD as an organocatalyst able to promote central-to-axial chirality transfer through stereospecific isomerization of protected propargylic alcohols into axially chiral siloxyallenes (Paper III). A potential application was demonstrated, and the reaction mechanism has been theoretically investigated by DFT calculations. 

In the last project, multiple chiral base catalysts were evaluated to establish an asymmetric isomerization of allylic compounds via kinetic resolution (Project IV). Thereby, extensive optimization studies were carried out to identify suitable reaction conditions. An efficient design of key control experiments led us to suggest a plausible reaction mechanism.