Organofluorine Chemistry

1. Fundamentals in organic fluorine chemistry.

1.1 Some physical properties of organic fluorine compounds.

1.2 Electronic effect.

1.2.1 Electronic effects of the fluorine atom – insight from Hammett substituent.

constants.

1.2.2 Electronic effects on acidity, bond length, and bond energy of fluoroorganic.

molecules.

1.2.3 Halogen bonding.

1.2.4 Electronic effect to the destabilization of carbonyl and imono groups.

1.2.5 p-p Stacking of fluoroaromatics.

1.2.6 Increased p-character (Bent’s rule) and low-lying LUMO in carbon-fluorine.

bonding orbitals.

1.2.7 Negative hyperconjugation.

1.2.8 Electron-donating effect (Stabilization of carbocation).

1.2.9 Effect of fluorine substituents to the structure, stability, and reactivity of.

fluoroalkyl radicals.

1.3 Steric effects of fluorine substituents.

2. Unique reactions induced by fluorine.

2.1 Nucleophilic substitution on fluoroaromatic rings.

2.2 SN2’ reactions of alkenes bearing trifluoromethyl group.

2.3 Nucleophilic substitution on gem-difluoromethylene carbon.

2.4 Single electron transfer (SET) reaction of perfluoroalkyl halides.

2.5 Fluorine-activated electrophilic reagents (F-X and XFn).

3. Reactions activated by a strong interaction between fluorine and other atoms.

3.1 Reaction induced by F-Li interaction.

3.2 Reaction induced by F-Al interaction.

3.3 Reaction induced by F-Si interaction.

3.4 Reaction induced by F-B interaction.

3.5 Other examples (Sm, Yb, Zr, Hf).

4. Hydrogen bonding in organofluorine compounds.

5. Fluorinated ligands for selective catalytic reactions.

6. Fluorine in drug designs.

7. Methods for introduction of fluorine-functionality into molecules.

(Summary from publications for the latest fifteen years).

7.1 Monofluorination.

7.2 Difluorination.

7.3 Trifluoromethylation.

7.4 Perfluoroalkylation.

Index