Synthesis and Comparison of the Reactivity of Allyl Fluorides and ...

III
Appendix
by PPh3, hindered full analysis of the spectrum. After several days, the NMR sample became
crystalline, analysis by X-ray crystallography determined the product to be PdCl2(PPh3)2.
Formation of this complex indicates that an intermediate product is forming which may then
be decomposing, hence as NMR spectroscopy of the product was conducted in CDCl3,
formation of PdCl2(PPh3)2 occurred.
Reaction of 2-fluorobut-3-enyl benzoate with Pd(dba)2 at r.t
A 50 cm 3 , two-necked round-bottom flask was equipped with a magnetic stirring bar and
Rotaflo tap and attached to a Schlenk line. After flame-drying under high vacuum, the flask
was cooled and filled with nitrogen. Pd(dba)2 (50 mg, 0.09 mmol) was added to the flask in
the dry box, and then reattached to the Schlenk line. Anhydrous DCM (10 cm 3 ) and 2fluorobut-3-enyl
benzoate (100 mg, 0.52 mmol) were added and the reaction mixture was
stirred at room temperature for 12 h. Analysis by 1 H and 19 F NMR revealed no reaction had
occurred.
Repeating the reaction with toluene also resulted in no reaction.
Conducting the reaction in THF at -78 ºC with warming to room temperature over 48 h,
afforded only starting material
Reaction of 2-fluorobut-3-enyl benzoate with Pd(PPh3)4 at -78 ºC
A 50 cm 3 , two-necked round-bottom flask was equipped with a magnetic stirring bar and
Rotaflo tap and attached to a Schlenk line. After flame-drying under high vacuum, the flask
was cooled and filled with nitrogen. Pd(PPh3)4 (104 mg, 0.09 mmol) was added to the flask
in the dry box, and then reattached to the Schlenk line. Anhydrous toluene (10 cm 3 ) and 2fluorobut-3-enyl
benzoate (100 mg, 0.52 mmol) were added and the reaction mixture was
stirred at -78 ºC for 1 h, the precipitate formed was isolated and analysis by 1 H and 19 F NMR
revealed no starting material to be present.
Reaction of 2-(2-fluorobut-3-enyl)isoindoline-1,3-dione with Pd(PPh3)4 at -78 ºC
A 50 cm 3 , two-necked round-bottom flask was equipped with a magnetic stirring bar and
Rotaflo tap and attached to a Schlenk line. After flame-drying under high vacuum, the flask
was cooled and filled with nitrogen. Pd(PPh3)4 (93 mg, 0.08 mmol) was added to the flask in
the dry box, and then reattached to the Schlenk line. Anhydrous toluene (10 cm 3 ) and 2-(2fluorobut-3-enyl)isoindoline-1,3-dione
(156 mg, 0.46 mmol) were added and the reaction