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

V
Appendix
therefore, the temperature was increased to 35 ºC, and stirred for a further 2 hours, however,
no notable change was observed. Therefore, the temperature was increased further to 40 ºC
for 1 hour and then stirred at 50 ºC for 3 hours, before finally refluxing at 70 ºC for 24 hours.
After which a yellow solution was observed with a dark precipitate. The yellow solution was
transferred via cannula and dried in vacuo. Both 1 H and 19 F NMR spectroscopy showed that
only starting material and dba were present.
A3 Attempted reactions in Chapter 4
Synthesis of 5-fluoro-5,5-bis(phenylsulfonyl)pent-2-enyl 4-(trifluoromethyl) benzoate
A 50 cm 3 , two-necked round-bottomed 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(C3H5)Cl]2 (3 mg, 0.008
mmol) was added to the reaction flask in a dry box. Subsequently, the flask was reattached to
the Schlenk line, filled with nitrogen and charged with PPh3 (83 mg, 0.32 mmol) and
anhydrous DCM (3 cm 3 ) and stirred at room temperature for 15 minutes. After which, 2chlorobut-3-enyl
4-(trifluoromethyl)benzoate (89 mg, 0.32 mmol), sodium 1-fluorobis(phenylsulfonyl)methane
(323 mg, 0.96 mmol) and 15-crown-5 (0.19 cm 3 , 0.96 mmol)
were added and the reaction mixture left to stir. After stirring overnight, the reaction was
quenched with water (10 cm 3 ) and the aqueous phase extracted with diethyl ether (3 x 10
cm 3 ). The combined organic phases were dried over MgSO4, concentrated in vacuo.
Purification by column chromatography failed to fully isolate the product.
Synthesis of 5-fluoro-5,5-bis(phenylsulfonyl)pent-2-enyl 4-(trifluoromethyl) benzoate
A 50 cm 3 , two-necked round-bottomed flask was
equipped with a magnetic stirring bar, and Rotaflo
tap and attached to a Schlenk line. After flamedrying
under high vacuum, the flask was cooled
and filled with nitrogen. [Pd(C3H5)Cl]2 (3 mg,
0.008 mmol) was added to the reaction flask in a
dry box. Subsequently, the flask was reattached to the Schlenk line, filled with nitrogen and
charged with PPh3 (83 mg, 0.32 mmol) and anhydrous DCM (3 cm 3 ) and stirred at room
temperature for 15 minutes. After which, 2-chlorobut-3-enyl benzoate (67 mg, 0.32 mmol),
sodium 1-fluoro-bis (phenylsulfonyl)methane (323 mg, 0.96 mmol) and 15-crown-5 (0.19
cm 3 , 0.96 mmol) were added and the reaction mixture left to stir. After stirring overnight, the
reaction was quenched with water (10 cm 3 ) and the aqueous phase extracted with diethyl ether
(3 x 10 cm 3 ). The combined organic phases were dried over MgSO4, concentrated in vacuo.
However no desired product was found.
Fluoride reactions
A 50 cm 3 , two-necked round-bottomed 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(C3H5)Cl]2 (3 mg, 0.008 mmol) was added to the
reaction flask in a dry box. Subsequently, the flask was reattached to the Schlenk line, filled
with nitrogen and charged with PPh3 (83 mg, 0.32 mmol) and anhydrous DCM (3 cm 3 ) and