896
C. Audin et al. / C. R. Chimie 13 (2010) 890–899
chromatography on silica gel with dichloromethane as
eluent. After evaporation of the solvent, 235 mg of 2b were
obtained as an orange waxy solid (yield = 70%). 1H NMR
JPC = 10.0 Hz: PPh2); 132.0 (d, JPC = 10.0 Hz: PPh2); 131.3
(d, JPC = 2.5 Hz: PPh2); 131.1 (d, JPC = 2.5 Hz: PPh2); 128.9 (s:
Ph); 127.9 (s: Ph); 128.1 (d, JPC = 12.5 Hz: PPh2); 128.0 (d,
(200.1 MHz, CDCl3),
d
(ppm): 7.67–7.58 (2H, m: PPh2);
J
J
PC = 12.5 Hz: PPh2); 88.0 (d, JPC = 12.0 Hz: quat Cp); 75.3 (d,
PC = 12.6 Hz: subst Cp); 74.7 (d, JPC = 94.9 Hz: quat Cp);
7.48–7.41 (3H, m: PPh2); 7.32–7.29 (5H, m: PPh2); 7.08
(2H, d, J = 8.1 Hz: Ph); 6.97 (2H, d, J = 8.1 Hz: Ph); 4.65 (1H,
dd, J = 10.9 Hz, JPH = 2.2 Hz: CpCH2); 4.60 (1H, m: subst Cp);
4.44 (1H, d, J = 10.9 Hz: CpCH2); 4.37 (2H, s: PhCH2O); 4.36
(1H, m: subst Cp); 4.08 (5H, s: Cp); 3.83 (1H, m: subst Cp);
74.6 (d, JPC = 9.3 Hz: subst Cp); 72.0 (s: PhCH2O); 70.7 (s:
Cp); 69.5 (d, JPC = 10.0 Hz: subst Cp); 67.1 (s: CpCH2O); 33.6
(s: CH2Br). 31P NMR (121.5 MHz, CDCl3),
d (ppm): 41.8. MS
(FAB > 0; MNBA), C31H28BrFeOPS, m/z: 616 ([M]+).
2.37 (3H, m: CH3). 13C NMR (50.3 MHz, CDCl3),
d (ppm):
140.8 (d, JPC = 9.3 Hz: quat PPh2); 138.3 (d, JPC = 8.2 Hz:
quat PPh2); 137.6 (s: quat Ph); 136.2 (s: quat Ph); 135.9 (d,
3.2.5. Synthesis and characterization of compounds 4a and 4c
In a Schlenk tube, 250 mg of tetraethylmethylenebi-
sphosphonate (0.87 mmol) were reacted with a suspension
of 250 mg of sodium hydride (60% dispersion in mineral
oil) in 5 mL of THF. After 1 h at room temperature, the
filtered solution was transferred via cannula on 500 mg of
compound 3 (0.81 mmol) dissolved in 20 mL of THF. After
1 day, 10 mL of a saturated aqueous solution of ammonium
chloride were added and the product was extracted with
ethyl acetate. The crude material was purified by flash
chromatography on silica gel with ethyl acetate/ethanol
(9/1) as eluent. Compounds 3, 4a and 4c were successively
recovered. After evaporation of the solvent, 270 mg of 4a
was obtained as an orange solid (yield = 40%). 1H NMR
JPC = 20.3 Hz: PPh2); 133.2 (d, JPC = 17.9 Hz: PPh2); 129.9 (s:
PPh2); 129.6 (s: Ph); 128.9 (d, JPC = 7.5 Hz: PPh2); 128.8 (d,
J
J
PC = 5.7 Hz: PPh2); 128.5 (s: PPh2); 128.4 (s: Ph); 90.1 (d,
PC = 24.6 Hz: quat Cp); 77.5 (d, JPC = 8.1 Hz: quat Cp); 73.5
(d, JPC = 3.4 Hz: subst Cp); 72.9 (s, PhCH2O); 72.7 (d,
PC = 3.7 Hz: subst Cp); 70.6 (s: subst Cp); 70.3 (s: Cp); 68.1
(d, JPC = 9.9 Hz: CpCH2); 22.0 (s: CH3). 31P NMR (81.0 MHz,
CDCl3),
J
d
(ppm): ꢀ22.9 (PPh2). HR MS (DCI CH4),
C31H29OPFe, calcd. mass [M + H]: 505.1375; exp. mass
[M + H]: 505.1384.
3.2.3. Synthesis and characterization of 4-
(bromomethyl)benzyl alcohol
(200.1 MHz, CDCl3), d (ppm): 7.87–7.62 (4H, m: PPh2);
At 0 8C, in a Schlenk tube, 65 mL of BH3.THF (1 M in THF,
65 mmol) were added to 11.6 g of 4-(bromomethyl)ben-
zoic acid (54 mmol) in 20 mL of freshly distilled THF, under
argon. After 2 h stirring at room temperature, 20 mL of
methanol were added slowly. The clear solution was
concentrated. The crude product was solubilized in ether
and washed with an aqueous saturated solution of
NaHCO3. After concentration, 10.4 g of a white solid were
obtained (yield = 96%) without further purification. 1H
7.50–7.16 (6H, m: PPh2); 7.14 (2H, d, J = 8.1 Hz: Ph); 6.96
(2H, d, J = 8.1 Hz: Ph); 4.38 (1H, d, J = 11.0 Hz: CpCH2). 4.89
(1H, dd, J = 11.0 Hz: CpCH2); 4.63 (1H, m: subst Cp); 4.31
(2H, s: PhCH2O); 4.31 (5H, s: Cp); 4.27 (1H, m: subst Cp);
4.20–4.00 (8H, m: CH2 phosphonates); 3.82 (1H, m: subst
Cp); 3.21 (2H, t of d, J = 6.0 Hz, JPH = 16.7 Hz: PhCH2); 2.62
(1H, t of t, J = 6.2 Hz, JPH = 23.9 Hz: CHP2); 1.28 (12H, t of d,
J = 7.1 Hz,
(50.3 MHz, CDCl3),
PPh2); 139.4 (dd, JPC = 7.3 Hz: quat Ph); 134.3 (d,
J
PH = 2.6 Hz: CH3 phosphonates). 13C NMR
(ppm): 135.7 (d, JPC = 87.6 Hz: quat
d
NMR (200.1 MHz, CDCl3),
4.73 (2H, s: CH2Br); 4.54 (2H, s: CH2OH). 13C NMR
(50.3 MHz, CDCl3), (ppm): 142.0 (s: quat Ar); 138.0 (s:
d (ppm): 7.46–7.30 (4H, m: Ar);
J
J
J
PC = 86.3 Hz: quat PPh2); 137.5 (s: quat Ph); 132.9 (d,
PC = 10.1 Hz: PPh2); 132.8 (d, JPC = 10.1 Hz: PPh2); 132.0 (d,
PC = 2.4 Hz: PPh2); 131.8 (d, JPC = 2.4 Hz: PPh2); 129.4 (s:
d
quat Ar); 130.0 (s: Ar); 128.1 (s: Ar); 65.66 (s: CH2OH);
34.01 (s: CH2Br). Anal. Calcd. for C8H9BrO: C, 47.79%; H,
4.51%. Found: C, 47.85%; H, 4.53%.
Ph); 128.9 (d, JPC = 12.8 Hz: PPh2); 128.8 (d, JPC = 12.4 Hz:
PPh2); 128.3 (s: Ph); 89.0 (d, JPC = 11.9 Hz: quat Cp); 75.0 (d,
J
PC = 11.8 Hz: subst Cp); 75.3 (d, JPC = 95.3 Hz: quat Cp);
3.2.4. Synthesis and characterization of compound 3
75.2 (d, JPC = 9.3 Hz: subst Cp); 72.0 (s: PhCH2O); 71.47 (s:
Cp); 70.2 (d, JPC = 10.4 Hz: subst Cp); 67.5 (s: CpCH2O); 63.4
(d, JPC = 7.4 Hz: CH2 phosphonates); 63.2 (d, JPC = 7.7 Hz:
CH2 phosphonates); 39.8 (t, JPC = 132.5 Hz: CHP2); 31.6 (t,
In a Schlenk tube, 1.5 g of 2-thiodiphenylphosphino(-
hydroxymethyl)ferrocene 1 (3.47 mmol) was dissolved in
15 mL of dry dichloromethane. Then 1.5 mL of a 54%
solution of tetrafluoroboric acid in ether (10.86 mmol) was
added. After 1 min stirring, a solution of 5.12 g of 4-
(bromomethyl)benzylalcohol in 12 mL of dry dichloro-
methane was added. After 1 min of stirring, the crude
material was filtered on silica gel with ether as an eluent.
After evaporation of the solvent, 1.5 g of 3 was obtained as
J
PC = 4.3 Hz: PhCH2); 17.1 (d, JPC = 6.4 Hz: CH3 phospho-
nates). 31P NMR (81.0 MHz, CDCl3),
d
(ppm): 24.3
(phosphonates); 43.0 (PPh2). MS (FAB > 0; MNBA),
C
40H49FeO7P3S, m/z: 845 ([M + Na]+), 822 ([M]+).
After evaporation of the solvent, 60 mg of 4c were
recovered as a waxy solid. 1H NMR (200.1 MHz, CDCl3),
d
a yellow solid (yield = 70%). 1H NMR (300.1 MHz, CDCl3),
d
(ppm): 7.93–7.68 (8H, m: PPh2); 7.56–7.33 (12H, m: PPh2;
4H, d, J = 7.8 Hz: Ph); 7.02 (4H, d, J = 7.8 Hz: Ph); 4.91 (2H, d,
J = 11.0 Hz: CpCH2); 4.69 (2H, m: subst Cp); 4.50 (2H, d,
J = 11.0 Hz: CpCH2); 4.37–4.34 (4H, s: PhCH2O; 10H, s: Cp;
2H, m: subst Cp); 4.00–4.10 (8H, m: CH2 phosphonates);
3.88 (2H, m: subst Cp), 3.34 (4H, dd, JPH = 16.1 Hz: PhCH2);
1.19 (12H, dd, J = 7.0 Hz: CH3 phosphonates). 13C NMR
(ppm): 7.87–7.80 (2H, m: PPh2); 7.72–7.65 (2H, m: PPh2);
7.55–7.40 (4H, m: PPh2); 7.39–7.30 (2H, m: PPh2); 7.23
(2H, d, J = 8.0 Hz: Ph); 6.98 (2H, d, J = 8.0 Hz: Ph); 5.01 (1H,
d, J = 10.8 Hz: CpCH2); 4.65 (1H, m: subst Cp); 4.48 (2H, s:
CH2Br); 4.44 (1H, d, J = 10.8 Hz: CpCH2); 4.34 (5H, s: Cp);
4.34 (2H, s: PhCH2O); 4.30 (1H, m: subst Cp); 3.84 (1H, m:
subst Cp). 13C NMR (75.5 MHz, CDCl3),
d
(ppm): 138.9 (s:
(50.3 MHz, CDCl3),
PC = 6.1 Hz: quat Ph); 134.9 (d, JPC = 87.8 Hz: quat PPh2);
133.6 (d, JPC = 85.7 Hz: quat PPh2); 132.2 (d, JPC = 10.0 Hz:
d (ppm): 136.7 (s: quat Ph); 135.6 (dd,
quat Ph); 136.6 (s: quat Ph); 134.9 (d, JPC = 87.4 Hz: quat
PPh2); 133.6 (d, JPC = 86.5 Hz: quat PPh2); 132.2 (d,
J