Article
Organometallics, Vol. 29, No. 23, 2010 6507
C26H23FeO3P, found 470.0723. HPLC (OD, 2% i-PrOH, 0.6 mL/
min, 254 nm): tr/min = 10.2 (R), 12.4 (S).
(d,J= 7.1 Hz), 110.2 (d, J=5.9Hz),90.8(d,J=19.9Hz), 69.0(d,
J = 10.0 Hz), 68.6, 67.9 (d, J = 6.5 Hz), 67.3, 66.1, 40.8 (dd, J =
30.9 Hz, J = 4.7 Hz). 31P{1H} NMR (81 MHz, CDCl3): δ -17.6
(d, J = 1.5 Hz), -47.8 (d, J = 1.5 Hz). MS (EI): m/z 624 (Mþ, 11),
459 (100), 393 (5), 337 (11), 183 (4). HR-MS: m/z [M]þ calcd
624.1070 for C37H30FeO2P2, found 624.1053.
General Procedure 2. Ferrocene 6 was dissolved in degassed
acetic acid, and the appropriate phosphane was added dropwise.
The mixture was stirred at elevated temperature. The solvent
was removed under reduced pressure, and the crude product was
redissolved in DEE. The organic phase was washed with satu-
rated aqueous sodium hydrogen carbonate and brine and was
dried over MgSO4. The solvent was removed on a rotary
evaporator, and the crude product was purified by chromatog-
raphy on silica.
(R)-[(Diphenylphosphanyl)(2-(di-2-furylphosphanyl)phenyl)-
methyl]ferrocene ((R)-1d). According to general procedure 2 (R)-6b
(244 mg, 0.52 mmol) was reacted with diphenylphosphane (0.11 mL,
0.62 mmol, 1.2 equiv) in acetic acid (3 mL) at 65 ꢀC for 2 h. The
crude product was purified by chromatography with pentane/DEE
(30/1) as the eluent to give the product as a yellow-brown solid
(240 mg, 74% yield, 97% ee). Similarly, a racemic sample of 1d was
obtained as a yellow solid. Mp: 134 ꢀC. [R]D20=-102.8ꢀ (c 0.80,
CHCl3). 1H NMR (300 MHz, CDCl3):δ7.75-7.70(m, 1H), 7.57-
7.51 (m, 4 H), 7.43-7.25 (m, 5 H), 7.11-6.85 (m, 6 H), 6.68-6.66
(m, 1 H), 6.37-6.29 (m, 2 H), 5.65 (dd, J=11.3 Hz, J=6.5 Hz),
4.00-3.99 (m, 1 H), 3.91-3.89 (m, 1 H), 3.79-3.78 (m, 2 H), 3.55
(s, 5 H). 13C{1H} NMR (75 MHz, CDCl3): δ150.5 (dd, J=30.0 Hz,
8.8 Hz), 148.4 (dd, J=28.0 Hz, J=9.9 Hz), 147.4 (d, J=22.2 Hz, J=
2.3 Hz), 136.9 (dd, J=15.5 Hz, J=5.3 Hz), 134.6-110.7 (m), 92.0
(d, J=19.8 Hz), 70.0 (d, J=5.3 Hz), 68.4, 67.7 (d, J = 9.0 Hz), 67.3,
65.8, 41.4 (dd, J = 29.2 Hz, J = 14.9 Hz). 31P{1H} NMR (81 MHz,
CDCl3): δ 8.9 (d, J = 7.3 Hz), -61.5 (d, J = 7.3 Hz). MS (EI): m/z
625 (M þ 1, 7), 624 (Mþ, 16), 438 (199), 370 (50), 221 (17), 186 (59),
108 (74), 77 (3). HR-MS: m/z [M]þ calcd 624.1070 for C37H30-
FeO2P2, found 624.1029. HPLC (AD, 2% i-PrOH, 0.6 mL/min,
254 nm): tr/min =13.0 (S), 16.2 (R).
(R)-[(Dicyclohexylphosphanyl)(2-(di-2-furylphosphanyl)phenyl)-
methyl]ferrocene ((R)-1e). According to general procedure 2 (R)-6b
(200 mg, 0.43 mmol) was reacted with dicyclohexylphosphane
(0.10 mL, 0.51 mmol, 1.2 equiv) in acetic acid (3 mL) at 65 ꢀC for
15 min. The crude product was purified by chromatography with
pentane/DEE (20/1) as the eluent to give the product as a yellow
solid (213 mg, 78% yield). A racemic sample of 1e was obtained in
an analogous manner as a yellow solid. Mp: 115-117 ꢀC.
[R]D20 = -117.6ꢀ (c 0.77, CHCl3). 1H NMR (300 MHz, CDCl3):
δ 7.75-7.71 (m, 1 H), 7.62-7.58 (m, 3 H), 7.36-7.32 (m, 1 H),
7.16-7.12 (m, 1 H), 6.82-6.78 (m, 1 H), 6.65-6.64 (m, 1 H),
6.41-6.37 (m, 2 H), 5.01 (dd, J = 11.1 Hz, J = 7.2 Hz), 4.26 (bs, 1
H), 4.06 (bs, 1 H), 4.02 (bs, 1 H), 3.92 (bs, 1 H), 3.37 (s, 5 H),
1.68-0.66 (m, 22 H). 13C{1H} NMR (75 MHz, CDCl3): δ 151.6
(d, J=10.5 Hz), 151.2 (d, J=10.5 Hz), 151.0 (d, J=5.9 Hz), 150.5 (d,
J=10.5 Hz), 147.7 (d, J=2.3 Hz), 147.3 (d, J=2.9 Hz), 134.3
(d, J=2.9 Hz), 131.0 (dd, J=2.9 Hz, J=1.1 Hz), 130.7 (dd, J=14.9
Hz, J=5.3 Hz), 129.5, 126.0-125.9 (m), 121.4 (d, J=25.1 Hz), 120.9
(d, J=21.6 Hz), 110.9-110.8 (m), 94.3 (dd, J=16.9 Hz, J=1.1 Hz),
70.5 (d, J=2.3 Hz), 68.2, 67.5, 67.5-67.3 (m), 65.1, 36.8 (d, J=
19.3 Hz), 36.4 (d, J=18.7 Hz), 34.2 (dd, J=18.9 Hz, J=1.7 Hz),
34.0 (d, J=19.2 Hz), 31.6 (dd, J=15.4 Hz, J=2.3 Hz), 30.5 (dd,
J=8.2 Hz, J=2.3 Hz), 23.0 (dd, J=22.8 Hz, J=9.4 Hz), 28.1
(dd, J=9.2 Hz, J = 5.3 Hz), 27.2 (d, J=7.1 Hz), 26.9 (d, J=11.1
Hz), 26.5, 26.2. 31P{1H} NMR (81 MHz, CDCl3):δ32.3(d, J = 3.0
Hz), -63.0 (d, J=3.0 Hz). MS (EI): m/z 638 (M þ 1, 25), 637 (Mþ,
58), 554 (36), 553 (100), 440 (12), 439 (42), 438 (10), 373 (15), 372
(55), 371 (41), 305 (5), 253 (7), 186 (10), 121 (3). HR-MS: m/z [M]þ
calcd 636.2009 for C37H42FeO2P2, found 636.2032.
(R)-[Diphenylphosphanyl-(2-(diphenylphosphanyl)phenyl)methyl]-
ferrocene ((R)-1a). According to general procedure 2 (R)-6a
(700 mg, 1.42 mmol) was reacted with diphenylphosphane
(0.30 mL, 1.71 mmol, 1.2 equiv) in acetic acid (10 mL) at 65 ꢀC
for 1.5 h. The crude product was purified by chromatography
with pentane/DEE (10/1) as the eluent to give the product as an
orange solid (0.83 g, 90% yield, 97% ee). A racemic sample of 1a
was obtained as an orange solid. Mp: 137 ꢀC. [R]D20=þ28.8ꢀ (c
1
0.74, CHCl3). H NMR (300 MHz, CDCl3): δ 7.83-7.78 (m,
2 H), 7.65-7.61 (m, 1 H), 7.41-7.30 (m, 9 H), 7.16-6.92 (m, 9 H),
6.82-6.78 (m, 1 H), 6.59-6.54 (m, 2 H), 6.01 (dd, J=11.7 Hz,
J = 6.5 Hz, 1 H), 3.81-3.77 (m, 3 H), 3.68-3.67 (m, 1 H), 3.43 (s,
5 H). 13C{1H} NMR (75 MHz, CDCl3): δ 148.9 (dd, J = 25.4 Hz,
J=8.2 Hz), 137.7-126.3 (m), 92.0 (d, J=21.3 Hz), 69.7 (d, J=
9.9 Hz), 68.7 (d, J=3.2 Hz), 68.6, 66.9, 66.0, 40.8 (dd, J=30.0 Hz,
J= 15.8 Hz). 31P{1H} NMR (81 MHz, CDCl3): δ 7.6 (d, J =
1.9 Hz), -17.7 (d, J=1.9 Hz). MS (EI): m/z 645 (M þ 1, 9), 644
(Mþ, 20), 459 (100), 393 (7), 337 (44), 259 (6), 183 (23), 152 (6),
108 (8), 77 (3). HR-MS: m/z [M]þ calcd 644.1485 for C41H34FeP2,
found 644.1520. HPLC (AD, 2% i-PrOH, 0.6 mL/min, 254 nm):
tr/min = 9.3 (R), 10.4 (S).
(R)-[(Dicyclohexylphosphanyl)(2-(diphenylphosphanyl)phenyl)-
methyl]ferrocene ((R)-1b). According to general procedure 2 (R)-
6a (710 mg, 1.45 mmol) was reacted with dicyclohexylphosphane
(0.35 mL, 1.74 mmol, 1.2 equiv) in acetic acid (10 mL) at 65 ꢀC for
1.5 h. The crude product was purified by chromatography with
pentane/DEE(10/1) asthe eluent togivethe desiredproductasan
orange solid (724 mg, 76% yield). A racemic sample of 1b was
isolated as an orange solid. Mp: 103 ꢀC. [R]D20 = -94.1ꢀ (c 0.75,
1
CHCl3). H NMR (300 MHz, CDCl3): δ 7.74-7.70 (m, 1 H),
7.55-7.49 (m, 2 H), 7.36-7.07 (m, 11 H), 5.17 (dd, J = 11.4 Hz,
J = 6.6 Hz, 1 H), 4.27 (bs, 1 H), 4.00-3.98 (m, 1 H), 3.85 (bs,
2 H), 3.33 (s, 5 H), 1.74-0.66 (m, 22 H). 13C{1H} NMR (75 MHz,
CDCl3): δ 152.4 (dd, J = 26.3 Hz, J = 9.3 Hz), 138.0 (d, J = 10.5
Hz), 137.1 (d, J = 11.6 Hz), 134.9-133.4 (m), 131.0 (dd, J = 12.5
Hz, J = 4.5 Hz), 129.1-128.2 (m), 126.0 (d, J = 1.1 Hz), 94.8 (d,
J = 16.9 Hz), 70.6 (d, J = 3.5 Hz), 68.3, 68.0 (d, J = 12.2 Hz),
67.2, 65.1, 36.1 (dd, J = 29.2 Hz, J = 19.3 Hz), 33.9 (d, J = 19.2
Hz), 33.3 (dd, J = 18.7 Hz, J = 2.3 Hz), 31.8 (dd, J = 18.7 Hz,
J = 1.1 Hz), 30.2-26.2 (m). 31P{1H} NMR (81 MHz, CDCl3): δ
33.4, -17.7. MS (EI): m/z 656 (Mþ, 2), 574 (39), 573 (100), 459
(18), 393 (4), 337 (11), 305 (2), 259 (3), 183 (5). HR-MS: m/z [M]þ
calcd 656.2424 for C41H46FeP2, found 656.2396.
(R)-[(Di-2-furylphosphanyl)(2-(diphenylphosphanyl)phenyl)-
methyl]ferrocene ((R)-1c). According to general procedure 2 (R)-6a
(405 mg, 0.83 mmol) was reacted with di-2-furylphosphane (206
mg, 1.24 mmol, 1.5 equiv) in acetic acid (6 mL) at 65 ꢀC for 1.5 h.
The crude product was purified by chromatography with pentane/
DEE (10/1) as the eluent to give the product as an orange solid
(408 mg, 79% yield). A racemic sample of 1c was obtained in an
analogous manner as an orange solid. Mp: 65 ꢀC. [R]D20 = þ33.5ꢀ
(c 0.86, CHCl3). 1H NMR (300 MHz, CDCl3): δ 7.69-7.68 (m, 1
H), 7.52-7.48 (m, 1 H), 7.36-7.15 (m, 10 H), 7.03-6.87 (m, 5 H),
6.39-6.35 (m, 2 H), 6.15 (dd, J = 11.7 Hz, J = 8.0 Hz, 1 H), 6.06-
6.04 (m, 1 H), 3.82-3.79 (m, 3 H), 3.67 (s, 5 H), 3.40-3.39(m, 1H).
13C{1H} NMR (75 MHz, CDCl3): δ 151.2-150.7 (m), 147.9 (dd,
J = 26.8 Hz, J = 8.8 Hz), 147.0-146.5 (m), 138.0 (d, J = 11.7 Hz),
137.2 (d, J = 12.2 Hz), 135.9-127.8 (m), 126.3 (d, J = 1.7 Hz),
121.9 (d, J = 26.7 Hz), 121.0 (dd, J = 21.6 Hz, J = 1.7 Hz), 110.9
Dichloro{(R)-[(diphenylphosphanyl-KP)((2-(diphenylphosphanyl)-
phenyl)methyl-KP)]ferrocene}palladium(II) ([PdCl2((R)-1a)]). A
solution of (R)-1a (65 mg, 100 μmol) in benzene (2 mL) was added
to a suspension of dichlorobis(acetonitrile)palladium(II) (26 mg,
100 μmol) in benzene (1 mL), and the resulting mixture was stirred
at room temperature for 16 h. After filtration, the beige precipitate
was washed with benzene and DEE and was dried in vacuo. Crystals
suitable for X-ray diffraction were grown by vapor diffusion of
hexane into a chloroform solution. Yield: 51 mg (62 μmol, 62%).
Mp: > 230 ꢀC dec. [R]D20 = þ97.2ꢀ (c 0.18, CHCl3). H NMR
1
(400 MHz, DMSO-d6): δ 8.42-8.30 (m, 2H), 8.08-7.92 (m, 3H),
7.80-7.70 (m, 2H), 7.70-7.64 (m, 1H), 7.63-7.24 (m, 13H), 7.09-
6.99(m, 1H), 6.87-6.77 (m, 2H), 5.64 (dd, J= 16.7 Hz, J=7.4Hz,