Bifunctionalization of Small Organic Molecules Based on Fluorine Incorporation

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of the mechanism and the origin of stereoselectivity.At the time of the doctoral defense, the following paper was unpublished and had a status as follows: Paper 1: Manuscript.