Anthony KERMAGORET - THESES ET MEMOIRES DE L'UDS

Chapitre VI
To a solution of 13.000 g (57.00 mmol) of 2-bromo-1-(2-methoxyphenyl)ethanone in 100 mL
of toluene, was added a solution of triphenylphosphine (14.900 g, 57.00 mmol) in 100 mL of
toluene and the solution was stirred for 2 h at reflux. The white phosphonium salt precipitated
rapidly. After reaction, it was filtered and dried under vacuum. Yield: 26.600 g, 95%. 1 H
NMR (300 MHz, CD2Cl2): δ 3.99 (3H, s, OCH3), 5.83 (2H, d, P-CH2), 6.95–7.10 (2H, m,
aromatic H), 7.50-8.00 (17H, m, aromatic H). This phosphonium salt (13.500 g, 27.50 mmol)
was dissolved in a saturated water solution of Na2CO3 and the solution was stirred for a few
minutes. 12 was extracted with chloroform (3× 50 mL) and, after elimination of the solvents,
dried under vacuum to afford an orange oil which was dissolved in 30 mL of toluene and
precipitated to form a pale yellow powder. Yield: 9.000 g, 80%. 1 H NMR (300 MHz, CDCl3):
δ 3.93 (3H, s, OCH3), 4.55 (1H, d, 2 JPH = 28.3 Hz), 6.96-7.01 (2H, m, aromatic H), 7.32 (1H,
m, aromatic H), 7.53 (6H, m, aromatic H), 7.62 (3H, m, aromatic H) and 7.78 (7H, m,
aromatic H); 13 C{ 1 H} NMR (CDCl3, 75.5 MHz): δ 55.3 (d, 1 JPC = 106.6 Hz, P-CH), 55.9 (s,
OCH3), 111.5 (s, CH of OC-Ph), 120.3 (s, CH of OC-Ph), 126.7 (s, CH of OC-Ph), 128.0 (s,
CH of OC-Ph), 128.8 (d, 3 JPC = 12.2 Hz, m-C of P-Ph), 129.7 (d, 1 JPC = 13.0 Hz, ipso-C of P-
Ph), 131.9 (d, 4 JPC = 2.6 Hz, p-C of P-Ph), 132.0 (d, 3 JPC = 14.2 Hz, ipso-C of OC-Ph), 133.2
(d, 2 JPC = 10.0 Hz, o-C of P-Ph), 157.4 (s, OCH3), 184.0 (s, CO); 31 P{ 1 H} NMR (CDCl3,
121.5 MHz): δ 16.0.
[NiPh{Ph 2PCH⋅⋅⋅C(⋅⋅⋅O)(o-OMe-C 6H 4)}(PPh 3)] 13
A solution of 0.170 g (0.62 mmol) of [Ni(COD)2] in 30 mL of toluene was added to a
solution of 0.160 g (0.62 mmol) of PPh3 and 0.250 g (0.62 mmol) of 12 in 50 mL of toluene
and the mixture was stirred for 24 h at room temperature. The red solution was evaporated
under reduced pressure to afford complex 13 as a yellow powder. The 1 H NMR spectrum
indicated a yield of 90% based on 12. 1 H NMR (300 MHz, C6D6): δ 3.42 (3H, s, OCH3), 5.97
(1H, s, P-CH), 6.50-6.77 (5H, m, aromatic H), 6.91-7.15 (18H, br m, aromatic H), 7.45 (1H,
m, aromatic H), 7.59 (5H, br m, aromatic H), 7.75 (5H, br m, aromatic H); 31 P{ 1 H} NMR
(C6D6, 121.5 MHz): AB spin system with the appearance of two singlets at δ 23.6 and 23.4
ppm.
[NiPh{Ph(t-Bu)PCH⋅⋅⋅C(⋅⋅⋅O)Ph}(PPh 3)] 15
A solution of 0.073 g (0.27 mmol) of [Ni(COD)2] in 5 mL of toluene was added to a
solution of 0.071 g (0.27 mmol) of PPh3 and 0.098 g (0.27 mmol) of 8 in 5 mL of toluene and
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