The dissertation work that is summarized in this thesis describes novel syntheses of organofluorine compounds with a broad coverage of different fluorine-containing motifs.

Chapter 2.1 covers works on the exploration of new trifluoromethylthiolating reactions of diazocarbonyl compounds. A rhodium-catalyzed oxy-trifluoromethylthiolation reaction enabled the synthesis of densely functionalized carbonyl compounds. Different oxygen nucleophiles, for instance alcohols, ethers and acetals underwent this transformation.

A zinc triflimide mediated three-component reaction established an arylation-trifluoromethylthiolation of diazocarbonyl compounds. In situ generation of triarylboranes was rendered most effective for the arylation event. Both procedures made use of the high reactivity of a recently developed electrophilic trifluoromethylthiolating reagent.

The second chapter (2.2) is dedicated to the late-stage construction of trifluoromethyl motifs. By means of halide exchange, nucleophilic fluoride from a copper(I)-complex could be used to exchange bromide with fluoride in the α-position to carbonyl groups as well as in benzylic positions.

The third chapter (2.3) covers the development of an enantioselective fluorocyclization reaction. In situ generated aryliodine(III)-fluoride species were used as organocatalysts. Through this oxidative olefin difunctionalization reaction, quaternary C-F stereogenic centers could be constructed with high enantiomeric excesses. DFT calculations enabled deeper understanding of the mechanism and the origin of stereoselectivity.