Synthesis of 2-chloro-1,1-difluoroallyl mesylates through novel rearrangement and CC bond formation by their Pd-catalyzed reaction with diethylzinc

Reactions Using Freons and Halothane as Halofluoroalkyl/Halofluoroalkenyl Building Blocks

“…to be reactive electrophiles that could couple with diethylzinc with a palladium catalyst to form fluorine‐containing conjugated alkenes 68 in moderate to good yields (Figure 29A). [129] In general, nucleophilic attacks on alkoxides and amines at a carbon–oxygen bond next to a CF 2 group are very difficult, so Ando et al. used a nucleophilic reaction to 67 via a π‐allyl palladium complex with a carbon nucleophile (e. g., diethylzinc).…”

“…When halothane was used, 1,1-difluoroallyl methanesulfonates 67 were found by Ando et al to be reactive electrophiles that could couple with diethylzinc with a palladium catalyst to form fluorine-containing conjugated alkenes 68 in moderate to good yields (Figure 29A). [129] In general, nucleophilic attacks on alkoxides and amines at a carbon-oxygen bond next to a CF 2 group are very difficult, so Ando et al used a nucleophilic reaction to 67 via a π-allyl palladium complex with a carbon nucleophile (e. g., diethylzinc). 67 was produced by reacting halothane with carbonyl compounds under basic conditions to give difluoroallylalcohols and then mesylating the allylic alcohol.…”