2146
R.G. Kultyshev, A. Miyazawa / Tetrahedron 67 (2011) 2139e2148
and the solvents were removed on the rotary evaporator. The
resulting orange powder was placed atop column prepared from 14
to 15 g of Wakogel 50C18 silica gel and acetonitrile. The desired
tertiary amine was the last colored band eluted after those of the
salts and unreacted secondary amine. It was stripped off the solvent
residue was dissolved in 1.0e1.5 mL of acetonitrile and placed atop
a column packed with Wakogel 50C18 silica gel (12e16 g) using the
same solvent. Upon elution with acetonitrile three colored bands
were typically observed, the second one being that of the desired
complex. While there was no clear-cut separation between the first
(lightly-colored) and the second band (dark), the third one did not
move at all. The complex was obtained by removal of acetonitrile
in vacuo.
ꢀ
on the rotary evaporator and pumped on through ꢁ196 C trap
overnight furnishing the desired tertiary amineebisphosphine.
0
0
00
0
3
)Pd(2c)]Cl. Fluffy orange solid, 76% yield. 1H NMR
), 7.52e7.47 (m, 3H, C ),
), 5.53 (quintet,
),
4
.2.9. N-Methyl-N-(3 -(1 -(triethoxysilyl)propyl))-1-[1 ,2-bis(diphe-
[(
(CDCl
7.28e7.24 (m, 3H, C
h
-C
): 8.29e8.21 (m, 2H, C
), 7.16e7.10 (m, 2H, C
J¼10.0, 1H, CHcentral), 5.13 (br s, 1H, CHCH ), 4.50 (br s, 1H, C
4.38 (t, J¼2.4, 1H, C ), 4.17 (br s, 1H, C ), 4.00 (s, 5H, C ), 3.71
(quartet, J¼7.0, 6H, SiOCH CH ), 2.41e2.33 (m, 4H, NCH
NCH ), 2.17 (br s, 1H, NCH ), 1.38e1.22 (m, 5H, CHCH
NCH CH CH CH
Si), 1.15 (t, J¼7.0, 9H, OCH
CH Si). ): 139.2e127.6 (P(C
(CHcentral), 96.25 (d, J¼15), 72.6e69.9 (C and C
3 5
H
nylphosphino)ferro-cenyl]ethylamine (3c). Prepared in 33% (method
3
6
H
5
6 5
H
1
A) or 45% yield (method B). H NMR (CDCl
3
): 7.52e7.46 (m, 2H,
), 7.18e7.05 (m, 5H, C ), 4.38 (br s,
), 4.23e4.14 (m, 1H, CHCH ), 4.10e4.05 (m,
), 3.74 (quartet, J¼7.0, 6H, SiOCH CH ), 3.66
), 3.47 (m, 1H, C ), 2.37e2.27 (m, 1H, NCH ), 2.21e2.11
m, 1H, NCH ), 1.66 (s, 3H, NCH CH ), 1.17
), 1.20 (t, J¼7.0, 9H, OCH
d, 3H, J¼6.4, CHCH ), 0.39e0.32 (m, 2H, CH Si). C{ H} NMR
CDCl ): 141.3e127.0 (P(C of C ),
), 98.29 (d, J¼23.4, CPPh
7.0e70.5 (C and C
), 58.34, 58.19, 57.30 (d, J¼6.5), 34.01,
0.81, 18.47, 9.26 (br), 8.00. P{ H} NMR (CDCl
6
H
5
6 5
H
3
C
1
2
6
H
5
), 7.32e7.21 (m, 13H, C
H, C ), 4.36 (m, 1H, C
H, C ), 3.92 (br s, 1H, C
6
H
5
6
H
5
3
5 3
H
p
p
3
5
H
3
5
H
3
5 5
H
p
p
2
3
2
3
3
, and
3
, and
(
(
(
(
br s, 1H, C
p
p
a
a
b
b
3
2
3
2
2
2
2
3
), 0.40e0.34 (m, 2H,
), 118.49
), 58.41, 57.95,
55.84, 41.17, 21.98, 18.42, 10.50, 8.38. P{ H} NMR (CDCl ): 11.1.
Anal. Calcd for C37 SiPClFePd: C, 54.56; H, 6.31; N, 1.72.
Found: C, 54.43; H, 6.31; N, 1.66.
13
1
13
1
3
2
2
C{ H} NMR (CDCl
3
6 5 2
H )
3
6
H
5
)
2
2
5
H
3
5
H
3
5 5
H
3
1
1
7
2
5
H
3
H
5 4
3
31
1
3
): ꢁ17.0, ꢁ23.3.
H51NO
3
Anal. Calcd for C46
3
H55NO SiP
2
Fe: C, 67.72; H, 6.80; N, 1.72. Found: C,
3
)Pd(2d)]Cl. Glassy dark-red solid, 85% yield. 1H NMR
), 7.52e7.46 (m, 3H, C ),
), 5.52 (quintet,
),
6
8.01; H, 6.74; N, 1.65.
[(
CDCl
7.30e7.20 (m, 3H, C
h
-C
): 8.28e8.20 (m, 2H, C
), 7.14e7.06 (m, 2H, C
J¼10.0, 1H, CHcentral), 5.20 (br s, 1H, CHCH ), 4.50 (br s, 1H, C
4.39 (t, J¼2.4, 1H, C ), 4.17 (br s, 1H, C ), 3.98 (s, 5H, C ), 3.79
(quartet, J¼7.0, 6H, SiOCH CH ), 2.45 (s, 3H, NCH
1H, NCH ), 2.15e2.04 (br s, 1H, NCH
), 1.35 (d, J¼6.4, 3H, CHCH
1.32e0.98 (m, 8H, NCH (CH CH CH
Si), 1.20 (t, J¼7.0, 9H, OCH
0.58e0.51 (m, 2H, CH
(C
), 118.40 (CHcentral), 95.94 (d, J¼17.0), 72.6e69.9 (C
), 58.25, 58.16, 52.57, 42.18, 33.16, 28.68, 27.29, 22.73, 18.31,
3 5
H
(
3
6
H
5
6 5
H
0
0
00
0
4
.2.10. N-Methyl-N-(6 -(1 -(triethoxysilyl)hexyl))-1-[1 ,2-bis(diphe-
6
H
5
6 5
H
1
3
nylphosphino)ferroce-nyl]ethylamine (3d). Yield 48% (method C). H
NMR (CDCl ): 7.51e7.45 (m, 2H, C ), 7.31e7.20 (m, 13H, C ),
.16e7.04 (m, 5H, C ), 4.38e4.33 (m, 2H, C
), 4.15 (qd, J¼7.0,
), 4.07 (septet, J¼1.2, 1H, C ), 4.05 (br t, 1H, C ),
.94e3.91 (m, 1H, C CH ), 3.63 (br
), 3.80 (quartet, J¼7.0, 6H, SiOCH
), 3.48e3.46 (m, 1H, C ), 2.27e2.18 (m, 1H, NCH ), 2.11e2.03
), 1.64 (s, 3H, NCH ), 1.31e0.70 (m, 8H,
), 1.22 (t, J¼7.1, 9H, OCH CH ), 1.14 (d, J¼6.6, 3H,
3
5 3
H
3
6
H
5
6
H
5
5
H
3
5
H
3
5 5
H
7
6
H
5
p
2
3
3
), 2.35 (td, J¼11.6,
J¼2.6, 1H, CHCH
3
p
p
a
b
3
),
),
3
p
2
3
2
2
)
4
2
2
3
1
3
1
s, 1H, C
p
p
a
2
Si). C{ H} NMR (CDCl
3
): 138.7e127.5 (P
and
(
m, 1H, NCH
NCH (CH CH
CHCH ), 0.59e0.53 (m, 2H, CH
41.2e127.1 (P(C
), 98.28 (d, J¼22.7, CPPh
and C
), 58.36, 57.32 (J¼7.3), 54.43, 34.15, 33.35, 27.58,
7.24, 22.78, 18.45, 10.54, 9.05 (br). P{ H} NMR (CDCl
23.3. Anal. Calcd for C49 SiP Fe: C, 68.60; H, 7.17; N, 1.63.
Found: C, 69.11; H, 7.16; N, 1.60.
b
3
6
H
5
)
2
5 3
H
2
2
)
4
2
2
3
5 5
C H
1
3
1
31
1
3
2
Si).
C{ H} NMR (CDCl
3
):
10.35 (overlap of two signals). P{ H} NMR (CDCl
3
): 11.6. MS (ESI):
þ
1
6
H
5
)
2
2
of C ), 77.0e70.5
5
H
3
m/z 820.5 [MꢁCl] . Anal. Calcd for C40
3
H57NO SiPClFePd: C, 56.08;
(C
5
H
3
5
H
4
H, 6.71; N, 1.63. Found: C, 55.27; H, 6.47; N, 1.54.
31
1
3
)Pd(2e)]Cl. Glassy dark-red solid, 81% yield. 1H NMR
), 7.50e7.43 (m, 3H, C ),
), 5.55 (quintet,
),
2
ꢁ
3
): ꢁ16.8,
[(
(CDCl
7.28e7.20 (m, 3H, C
h
-C
): 8.26e8.18 (m, 2H, C
), 7.15e7.08 (m, 2H, C
J¼10.0, 1H, CHcentral), 5.00 (br s, 1H, CHCH ), 4.49 (br s, 1H, C
4.36 (unresolved t, 1H, C ), 4.10 (br s, 1H, C ), 4.03 (s, 5H,
), 3.78 (quartet, J¼7.0, 6H, SiOCH CH ), 3.25e3.11 (m, 4H,
OCH ), 2.69e2.60 (m, 1H, NCH ), 2.52e2.41 (br s, 1H, NCH ),
2.24 (s, 3H, NCH ), 1.60e1.52 (m, 2H, OCH CH CH
), 1.31 (d, J¼6.4,
3H, CHCH CH ), 0.57e0.51 (m, 2H, CH Si).
), 1.19 (t, J¼7.0, 9H, OCH
C{ H} NMR (CDCl ): 139.63e127.54 (P(C ), 118.42 (CHcentral),
96.42 (d, J¼17.6), 73.61 (CH OCH ), 72.9e69.8 (C and C ),
70.39 (CH OCH ), 58.51, 57.34, 51.70, 39.92, 23.14, 18.46, 10.21,
P{ H} NMR (CDCl ): 10.3. Anal. Calcd for C39
3 5
H
H61NO
3
2
3
6
H
5
6 5
H
6
H
5
6 5
H
3
3
5 3
H
0
0
00
00
0
4
.2.11. N-Methyl-N-(6 -(1 -(triethoxysilyl)-4 -oxahexyl))-1-[1 ,2-bis
5
H
3
5 3
H
(
diphenylphosphino)-ferrocenyl]ethylamine (3e). Yield 24% (method
C
5
H
5
2
3
1
A). H NMR (CDCl
3
): 7.50e7.44 (m, 2H, C
), 7.19e7.06 (m, 5H, C ), 4.37e4.33 (m, 2H, C
H, CHCH ), 4.07 (m, 1H, C ), 4.04 (br s, 1H, C ), 3.96 (br s, 1H, C
.81 (quartet, J¼7.0, 6H, SiOCH CH ), 3.62 (br s, 1H, C ), 3.49 (m, 1H,
), 3.17e3.04 (m, 2H, OCH CH CH ), 2.94e2.83 (m, 1H,
CH O), 2.68e2.58 (m, 1H, NCH CH O), 2.54e2.43 (m, 1H,
), 2.37e2.26 (m, 1H, NCH ), 1.71 (s, 3H, NCH ), 1.59e1.49 (m,
H, OCH CH CH CH ), 1.15 (d, 3H, J¼6.8,
), 1.22 (t, J¼7.0, 9H, OCH
CHCH ), 0.58e0.52 (m, 2H, CH
41.1e127.2 (P(C
), 97.85 (d, J¼22.7, CPPh
and C ), 73.29 (CH O), 69.48 (CH
O), 58.49, 57.79 (d, J¼7.0),
3.10, 35.39, 23.08, 18.47, 9.05 (br), 6.64. P{ H} NMR (CDCl
17.0, ꢁ23.6. Anal. Calcd for C48 SiP Fe: C, 67.05; H, 6.92; N,
6
H
5
), 7.32e7.20 (m, 13H,
), 4.20e4.11 (m,
),
CH
2
2
a
b
C
1
3
C
NCH
NCH
6
H
5
6
H
5
p
3
2
2
2
3
p
p
p
3
2
3
2
13
1
2
3
p
3
6 5 2
H )
p
2
2
2
2
2
5
H
3
5 5
H
2
a
2
b
2
2
3
1
1
a
b
3
6.70.
3
H55NO
4-
2
2
2
2
2
3
SiPClFePd: C, 54.55; H, 6.46; N, 1.63. Found: C, 54.94; H, 6.32;
1
3
1
3
2
Si).
C{ H} NMR (CDCl
3
):
N, 1.56.
3-C
H
5
)Pd(2f)]Cl. Fluffy orange solid, yield undetermined. H
1
1
6
H
5
)
2
2
of C ), 77.0e70.5
5
H
3
[(
h
3
(C
5
H
3
H
5 4
2
2
NMR (CDCl
3
): 8.20e8.10 (m, 2H, C
), 7.06e7.00 (m, 2H, C
J¼10.0, 1H, CHcentral), 5.11 (br s, 1H, CHCH ), 4.44 (s, 1H, C
(s, 1H, C ), 4.11 (s, 1H, C ), 3.88 (s, 5H, C ), 2.40 (s, 3H, NCH
.24 (m,1H, NCH ), 2.03 (br s,1H, NCH
),1.35 (d, J¼6.4, 3H, CHCH
1.30e1.00 (m, 4H, (CH CH
), 0.60 (t, J¼7.0, 3H, CH
NMR (CDCl ): 134.66e126.53 (P(C ), 117.39 (CHcentral), 95.00
(weak signal), 71.32e68.90 (C and C ), 57.00, 53.53, 40.64,
20.82, 10.73, 0.83. P{ H} NMR (CDCl ): 12.0.
)Pd(2g)]Cl. Fluffy orange solid, yield undetermined. H
): 8.25e8.16 (m, 2H, C ), 7.51e7.45 (m, 3H, C ),
), 7.12e7.05 (m, 2H, C ), 5.54 (quintet,
J¼10.0, 1H, CHcentral), 5.22 (br s, 1H, CHCH ), 4.50 (s, 1H, C ), 4.39
(s, 1H, C ), 4.18 (s, 1H, C ), 3.94 (s, 5H, C ), 2.52 (s, 3H, NCH ),
2.35 (partially resolved td, 1H, NCH ), 2.10 (br s, 1H, NCH ), 1.35 (d,
6
H
5
), 7.45e7.40 (m, 3H, C
), 5.47 (quintet,
), 4.32
6 5
H ),
31
1
5
3
):
7.22e7.12 (m, 3H, C
6
H
5
6 5
H
3
ꢁ
H59NO
4
2
3
5 3
H
1
.63. Found: C, 66.79; H, 6.85; N, 1.57.
5
H
3
5
H
3
5
H
5
3
3
),
),
3
2
a
b
13
1
4.2.12. General procedure for the syntheses of P,N-allyl palladium
2
)
2
3
2 3
CH ). C{ H}
complexes. A 2-neck 50 mL round-bottomed flask equipped with
a magnetic stirbar was charged with a solution of a ligand
3
6 5 2
H )
H
5 3
5 5
H
31
1
(
0.25e0.50 mmol) in CH
2
Cl
2
. The side neck was plugged with
3
3
1
a septum, the central neck was attached to a vacuum line, and the
solvent was removed by pumping on the stirred solution through
[(
h
-C
3
H
5
NMR (CDCl
3
6
H
5
6 5
H
ꢀ
3
a ꢁ196 C trap. [(
h
-C
3
H
5
)PdCl]
2
was added via the side neck (2:1
7.30e7.19 (m, 3H, C
6
H
5
6 5
H
3
ligand-dimer molar ratio). After evacuation and refill with nitrogen
3
5 3
H
CH
2
Cl
2
(5e10 mL) was added via a syringe followed by stirring for
5
H
3
5
H
3
5
H
5
3
1
h at ambient temperature and solvent removal in vacuo. The
a
b