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

6.3.2 Preparation of Bis[�-chloro-bis(butenyl-(1,2,3-�)oxy)methyl) benzene]
dipalladium (126)
165
Chapter Six
The novel compound was prepared following the method
outlined by Granberg et al. [13] 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 (0.85 g, 1.47 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 ((2-chlorobut-3-enyloxy)methyl)benzene (0.29 g, 1.47
mmol) and DMSO (15 cm 3 ). The reaction mixture was stirred for 2 h and then quenched
with water (15 cm 3 ) and chloroform (20 cm 3 ). The organic phase was separated, washed
with water (3 x 10 cm 3 ), dried over MgSO4 and concentrated in vacuo to give a yellow
solid. Purification by column chromatography [DCM: hexane (70:30)] afforded the product
as a yellow solid (0.28 g, 63 %). δH 2.91 (1H, d, 3 JHH = 12.1 Hz, Ha), 3.51 (1H, dd, 2 JHH =
13.3 Hz, 3 JHH = 6.3 He), 3.62 (1H, dd, 2 JHH = 13.3 Hz, 3 JHH = 3.1 Hz, Hf), 3.78 (1H, ddd,
3 JHH = 10.6 Hz, 3 JHH = 6.3 Hz, 3 JHH = 3.1 Hz, Hd), 3.93 (1H, d, 3 JHH = 6.7 Hz, Hb), 4.48
(1H, d, 2 JHH = 11.7 Hz, CHHAr), 4.57 (1H, d, 2 JHH = 11.7 Hz, CHHAr), 5.45 (1H, ddd, 3 JHH
= 12.1 Hz, 3 JHH = 11.0 Hz, 3 JHH = 6.7 Hz, Hc), 7.22-7.30 (5H, m, ArH); δC 60.3 (CHCH2),
69.0 (OCH2), 73.2 (ArCH2), 79.5 (OCH2CH), 109.5 (CHCH2), 127.8 (ArCH-3), 128.0
(ArCH-2), 128.5 (ArCH-4), 138.0 (ArC-1). m/z (FAB + ) 571 ([M-Cl] + ), 100 %, 606 ([M] + ,
10 %).
6.3.3 Preparation of Bis[�-chloro-bis(butenyl-(1,2,3-�)-4-methylbenzoate] dipalladium
(131)
The novel compound was prepared following the method
outlined by Granberg et al. [13] 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 (0.56 g, 0.97 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 2-chlorobut-3-enyl 4-