10.1016/j.jfluchem.2009.11.013
Anke Schwarzer et al. investigate the impact of fluorine substitution on the crystalline packing structures of tricyclic Diels–Alder adducts. The study synthesizes and analyzes a series of fluorinated molecules (1–18) derived from diarylfulvenes and N-arylimides, including a non-fluorinated parent compound. The researchers used X-ray crystallography to determine the crystal structures and found that fluorine substitution significantly influences the packing arrangements, with a balanced interplay of C–H…O, C–H…F, and C–H…p contacts being typical. The study also explores the effects of bromine substitution and identifies trends in the observed interaction modes, concluding that while fluorine substitution affects the crystal packing, the interactions are complex and not strictly systematic. The findings provide insights into the role of fluorine in crystal engineering and its competition with other weak intermolecular interactions.
10.1016/j.tet.2005.07.022
The study focuses on the carbometallation reactions of fluorine-containing internal acetylenes with various organocopper reagents derived from organolithium, Grignard, and organozinc reagents. The main objective was to investigate the regio- and stereo-selectivity of these reactions, which are crucial for the synthesis of fluoroalkylated molecules, particularly alkenes with fluoroalkyl groups that are found in biologically active compounds. The reactions proceeded smoothly, yielding vinylcopper intermediates that could then react with electrophiles to form trisubstituted alkenes in high to excellent yields. The study also successfully applied these reactions in the total synthesis of the anti-estrogen drug, panomifene, demonstrating the synthetic utility of the developed methods. Chemicals used in the study included fluoroalkylated internal alkynes, organocopper reagents, and various electrophiles for cross-coupling reactions, serving the purpose of exploring novel synthetic approaches for the preparation of fluoroalkylated molecules with potential pharmaceutical applications.