Open this publication in new window or tab >>2020 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]
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.
Place, publisher, year, edition, pages
Stockholm: Department of Organic Chemistry, Stockholm University, 2020. p. 71
Keywords
fluorination, fluorocyclization, fluorine chemistry, trifluoromethylthiolation, rhodium-catalysis, organocatalysis, asymmetric synthesis, hypervalent iodine, multicomponent reaction, bifunctionalization, diazo compounds
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-180547 (URN)978-91-7911-138-0 (ISBN)978-91-7911-139-7 (ISBN)
Public defence
2020-06-01, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 14:00 (English)
Opponent
Supervisors
Note
At the time of the doctoral defense, the following paper was unpublished and had a status as follows: Paper 1: Manuscript.
2020-05-072020-04-012022-02-26Bibliographically approved