Anthony KERMAGORET - THESES ET MEMOIRES DE L'UDS

Chapitre V
mode; capillary voltage: 4.8 kV; nebulizer pressure: 0.2 bar; desolvation temperature: 180 °C;
desolvation gas flow rate: 4.5 L/min).
The ligands and complexes NOPON Me , 2, [Pd(Me)Cl(COD)], [PdCl2(NCPh)2],
39, 41, 79, 80
[Pd(MeCN)4(BF4)2] have been synthesized according to the literature.
Synthesis of phenyl-bis(2-picolyl)phosphine 1
A n-BuLi solution (96.0 mmol, 1.6 M in hexane) was added drop wise to a degassed solution
of 2-picoline (8.94 g, 96.0 mmol) in 100 mL of THF at -78 °C. After complete deprotonation,
the red anion precipitated out and after further 1 h of stirring at -78 °C, degassed
chlorotrimethylsilane (10.43 g, 96.0 mmol) was added drop wise to the solution. The brown
mixture was allowed to reach room temperature overnight and the THF was evaporated under
reduced pressure. The residue was distilled at 120 °C and 12 mbar to obtain the pure liquid
picolyltrimethylsilane compound (yield: 6.61 g, 40.0 mmol, 42%).
1 H NMR (300 MHz, CDCl3): δ 0,00 (s, 9H, Si(CH3)], 2,32 (s, 2H, SiCH2), 6,93 (t, 2 JH-H =
7,65 Hz, 2H, Py), 7,45 (td, 1H, 2 JH-H = 1,85 Hz, 2 JH-H = 7,65 Hz, Py), 8,39 (d, 1H, 3 JH-H = 4,17,
HCN). 13 C{ 1 H} NMR (CDCl3, 75.5 MHz): δ -1,7 (s, SiCH3), 30,2 (s, SiCH2), 119,0 (s, C of
Py), 122,1 (s, C of Py), 135,7 (s, C of Py), 148,9 (s, C of Py), 161,3 (s, C of Py).
Pure picolyltrimethylsilane (6.61 g, 40.0 mmol) was dissolved in a mixture of 50 mL THF
and 50 mL diethylether cooled down to -78 °C and PPhCl2 (3.58 g, 20.0 mmol) was added.
The reaction mixture was allowed to reach room temperature overnight, the solvents were
evaporated under reduced pressure and the resulting orange oil was dried in vacuum at 60 °C
(yield: 4.02 g, 13.6 mmol, 68%).
1 H NMR (300 MHz, CDCl3): δ ABX spin system (A = B = H, X = P) 3.24 (2H, dd, JAB = 13.3
Hz, 2 JXB = 1.8 Hz) 3.31 (2H, d, JAB = 13.3 Hz, 2 JXA = 0.0 Hz), 3.78 (4H, s), 6.93 – 6.89 (4H,
m, aromatic H), 7.15 – 7.22 (3H, m, aromatic H), 7.30 – 7.39 (4H, m, aromatic H), 8.33 –
8.35 (2H, m, aromatic H); 13 C{ 1 H} NMR (75.5 MHz, CDCl3): δ 37.65 (d, 1 JPC = 18.4 Hz, P-
CH2), 120.8 (s, CH of Pyridyl (substitution)), 123.6 (d, 3 JPC = 5.1 Hz, CH of Pyridyl), 128.25
(d, 3 JPC = 6.9 Hz, m-CH of Aryl), 129.1 (s, p-CH of aryl), 132.6 (d, 2 JPC = 19.9 Hz, o-CH of
aryl), 136.0 (s, CH of Pyridyl), 136.7 (d, 1 JPC = 18.4 Hz, C-P of aryl), 149.15 (s, CH of
pyridyl), 158.1 (d, 2 JPC = 5.7 Hz, NC-CH2 of pyridyl); 31 P{ 1 H} NMR (121.5 MHz, CDCl3): δ
-12.55.
HRMS : Mass Calcd for C18H18N2P : 293.1208. Found. 293.1247 [(N,P,N)+H] + .
Synthesis of bis(2-oxazolin-2,5,5-trimethyl)phenylphosphine 3
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