Fluorine-containing heterocyclic and carbocyclic compounds attract widespread attention as important components of agrochemicals, pharmaceuticals, materials, and catalysts. To provide a general route to these compounds, we have developed a new methodology to construct fluorocarbon-bearing cyclic systems based on ring closure of functionalized 2-trifluoromethyl-1-alkenes, readily obtained from commercially available CH
2=C(CF
3)Br or CF
3CO
2Et. Their intramolecular reactions, such as nucleophilic substitution or addition, alkene insertion, and electrocyclization, provide a wide variety of five- and six-membered heterocycles and carbocycles bearing a fluorinated one-carbon unit (a =CF
2, CHF
2, or CF
3 group). To construct five-membered rings, we successfully accomplished a nucleophilic 5-
endo-
trig cyclization and 5-
endo alkene insertion, normally disfavored processes, as well as fluorine-directed Nazarov cyclization.
View full abstract