9
72 Organometallics, Vol. 27, No. 5, 2008
Giannoccaro et al.
under nitrogen atmosphere 4-APhOH (0.282 g, 2.59 mmol;
-APhOH/Pd ) 3). Nitrogen was pumped off and CO was admitted
MHz, 293 K): δ 20.29 (CH
3
), 49.14 (NCH
2
), 66.39 (CH-OH),
4
128.21 (virtual t, Cmeta, J ) 4.77 Hz), 130.26 (s, Cpara), 131.68
(virtual t, Cipso, J ) 22 Hz), 134.67 (virtual t, Cortho, J ) 6 Hz),
at atmospheric pressure. The mixture was allowed to react under
stirring at room temperature for 24 h. At this time, the color of the
product in suspension turned from yellow to dark gray and the CO
uptake was 20 mL (0.89 mmol), indicative that Pd complex had
reacted completely. The product was filtered under nitrogen, and
the residue on the filter was washed twice with a 1/1 mixture of
2
31
1
181.24 (t, CdO, JC-Pd-P ) 5 Hz). P{ H} NMR (CDCl
3
, 202 MHz,
293 K): δ 20.30.
trans-(PPh
Pd ) 4; reaction time, 5 h; yield, 53%. Anal. Calcd (%) for
Pd: Cl, 4.61; P, 8.06 Pd, 13.85. Found: Cl, 4.66; P,
3 2 2 2 2
) Pd(Cl)[C(O)NHCH CH CH OH] (10d). 3-AP/
40 2 2
C H38ClNO P
-1
CH
3
CN/Et
2
O and dried (0.406 g, 82%). Anal. Calcd (%) for
8.02; Pd, 13.81. IR (Nujol), 3458 and 3358 cm (νOH and νNH);
1602 (sh) and 1585 (s) cm- (ν CdO); 1186 cm (ν C-N). H
NMR (CDCl , 500 MHz, 293 K): δ 0.75 (quint, 2H, CH , J ) 5.9
Hz), 1.74 (unresolved t, br, 1H, OH), 2.09 (q, 2H, NCH , J ) 5.9
Hz), 2.89 (unresolved m, br, 2H, CH OH), 5.16 (t, broad, 1H, NH,
J ) 5.0 Hz), 7.31–7.41 (m, 18H, HPh), 7.69–7.78 (m, 13H, HPh).
1 -1 1
C H24ClN O PPd: Cl, 6.23; P. 5.44; Pd, 18.69. Found: Cl, 6,28,
26 2 2
-1
P, 5.39; Pd, 18.59. IR (Nujol): 3402 and 3273 cm (νOH and νNH);
606 (s), 1592 (s), 1592 (s), 1575 cm , 1224 (s), 1154 (s) cm . H
3
2
-1
-1 1
1
2
NMR (DMSO-d , 400 MHz, 293 K): δ 2.51 (m, 2H, CH2 (PN)), 3.40
6
2
(
6
dm, 2H, CH2(PN), J ) 28 Hz), 6.43 (d, 2H, HC6H4,ꢀ-OH, J ) 9 Hz),
1
3
.82 (d, 2H, HC6H4,γ-OH), 7.28–7.41 (m, 7H, HP(Ph)3 and Hꢀ,Py), 7.43
C NMR (CDCl
60.26 (CH OH), 128.17 (virtual t, Cmeta, J ) 4.77 Hz), 130.21 (s,
para), 131.70 (virtual t, Cipso, J ) 22 Hz), 134.67 (virtual t, Cortho,
3 2 2
, 125 MHz, 293 K): δ 30.98 (CH ), 39.18 (NCH ),
(
d, 1H, Hꢀ,Py, J ) 7.7), 7.62–7.70 (m, 4H, HP(Ph)3),7.85 (td, 1H, Hγ,Py
,
,
2
J ) 7.7 and 1.5 Hz), 8.91 (s, 1H, NH), 9.04 (d, slightly br, 1H, HR′,Py
C
13
2
31
1
J ) 4.8 Hz). C NMR (DMSO-d
6
, 100 MHz, 293 K): δ 24.41 (d,
J ) 6.67 Hz), 182.20 (t, C)O, JC-Pd-P ) 5 Hz). P{ H} NMR
(CDCl , 202 MHz, 293 K): δ 20.11.
trans-(PPh Pd(Cl)[C(O)NH-CH(CHOH)CH
Pd ) 2; reaction time, 10 h; yield, 53%. Anal. Calcd (%) for
Pd: Cl, 4.53; P, 7.91 Pd, 13.60. Found: Cl, 4.59; P,
CH P, JCP ) 29.0 Hz), 34.06 (d, CH
2
2
Py, JCP ) 4.6 Hz), 122.87 and
3
1
24.86 (Cꢀ,Py atoms), 128.37 (d, Cmeta,Ph, JCP ) 10.7 Hz), 130.39
3
)
2
2 3
CH ](10e).2-A1B/
(
Cpara,Ph), 132.29 (d, Cipso,Ph, JCP ) 47.2 Hz), 132.78 (d, Cortho,Ph, JCP
)
10.1 Hz), 139.19 (Cγ,Py), 151.98 (CR′,Py) and 159.81 (CR,Py); 114.19
41 2 2
C H40ClNO P
-1
(C
2,OH), 119.44 (C3,OH), 131.81 (C4,OH), 153.72 (C1,OH), 172.41 (d,
7.86; Pd, 13.55. IR (Nujol), 3417 and 3346 cm (νOH and νNH);
31
1
-1 -1 1
C(O)O, JCP ) 13.7 Hz). P{ H} NMR (DMSO-d
K): δ 25.90.
6
, 162 MHz, 293
3
1610 (s) cm (ν CdO); 1186 cm (ν C-N). H NMR (CDCl ,
3
400 MHz, 293 K): δ 0.41 (t, 3H, CH
3
, JHCCH ) 7.3 Hz), 0.51 (m,
), 0.75 (m, 1H, diastereotopic CH CH ),
.28–2.40 (m, 2H, overlapped CH and diastereotopic CH OH), 2.69
OH, J ) 9.9 Hz), 2.74 (br, 1H, OH),
1
2
H, diastereotopic CH
2
CH
3
2
3
Synthesis of trans-(PPh
PdCl (PPh ) (0.300 g, 0.43 mmol) in CH
2 3 2 3
3
)
2
Pd(Cl)[C(O)NHCH
CN (6 mL) and
-aminoethanol (2-AE, 0.078 g, 1.28 mmol; 2-AE/Pd ) 3) were
2 2
CH OH] (10b).
2
(
d, br, 1H, diastereotopic CH
2
2
4
.89 (br, 1H, NH), 7.32–7.44 (m, 18H, HPh), 7.68–7.80 (m, 12H,
allowed to react with CO at atmospheric pressure and room
temperature. The mixture was reacted for 6–7 h, and upon reaction,
the initial yellow suspension became white-cream. The crude
1
3
H
CH
)
1
Ph). C NMR (CDCl
), 51.20 (NCH), 64.21 (CH
5 Hz), 130.26 (s, Cpara), 131.46 (virtual t, Cipso, J ) 22 Hz),
3
, 100 MHz, 293 K): δ 9.71 (CH
3
), 23.69
(
2
2
-OH), 128.21 (virtual t, Cmeta, J
product was filtered, washed with a mixture of CH
Et O (3/1/3), to remove the impurities of the salt HO-(CH
NH · HCl, and dried (0.220 g; yield 68%). The compound was
purified from CHCl /CH CN: it was dissolved in CHCl (4 mL),
and the resulting solution was filtered, and concentrated to 2 mL.
By adding CH CN (6 mL), pure 10b was obtained as microcrys-
talline product (0.180 g, yield 55%).
Anal. Calcd (%) for C39
4.10. Found: Cl, 4.81; P, 8.19; Pd, 14.02. IR (Nujol), 3577 and
3 3
CN/CH OH/
2
34.52 (virtual t, Cortho, J ) 6.1 Hz), 183.97(t, CdO, JC-Pd-P ) 5
2
2 2
) -
31 1
Hz). P{ H} NMR (CDCl
trans-(PPh Pd(Cl)[C(O)NHCH
Pd ) 2; reaction time, 15 h; yield, 47%. Anal. Calcd (%) for
Pd: Cl, 4.53; P, 7.91 Pd, 13.60. Found: Cl, 4.59; P,
3
, 162 MHz, 293 K): δ 20.61.
2
3
)
2
2
CH CH CH OH] (10f). 4-AB/
2
2
2
3
3
3
41 2 2
C H40ClNO P
3
-1
7
1
5
.85; Pd, 13.53. IR (Nujol), 3385 and 3344 cm (νOH and νNH);
599 (s) cm- (ν CdO); 1199 cm (ν C-N). H NMR (CDCl
1 -1 1
,
3
2 2
H36ClNO P Pd: Cl, 4.70; P, 8.21 Pd,
00 MHz, 293 K): δ 0.58 (quint, 2H, CH
H, CH ), 1.6–1.8 (br, OH), 1.98 (m, br, 2H, NCH
HCNH ≈ 5 Hz), 3.29 (t, 2H, CH
2
, J ) 7.5 Hz), 0.98 (m,
1
3
3
2
2
2
, JHCCH ) 7.1,
-
1
-1
224 cm (νOH and νNH); 1620 (s) cm (ν CdO); 1182 (s)
3
J
2
OH, J ) 6.4 Hz), 4.81 (unresolved
-1
1
cm (ν C-N). H NMR (CDCl
H, OH), 2.10 (q, 2H, NCH , J ) 5.0 Hz), 2.63 (t, slightly br, 2H,
CH OH, J ) 4.5 Hz), 5.16 (t, br, 1H, NH, J ) 5 Hz), 7.33–7.42
m, 18H, HPh), 7.72–7.78 (m, 12H, HPh). C NMR (CDCl
MHz, 293 K): δ 44.39 (NCH ), 61.54 (CH OH), 128.23 (virtual t,
meta, J ) 4.77 Hz), 130.30 (s, Cpara), 131.64 (virtual t, Cipso, J )
3
, 500 MHz, 293 K): δ 1.5 (br,
t, br, 1H, NH), 7.31–7.43 (m, 18H, HPh), 7.68–7.80 (m, 12H, HPh).
1
2
13
C NMR (CDCl
1.43 (NCH ), 62.13 (CH
Hz), 130.19 (s, Cpara), 131.73 (virtual t, Cipso, J ) 21.9 Hz), 134.69
3
, 125 MHz, 293 K): δ 24.93 (CH
2 2
), 29.49 (CH ),
2
4
2
2
OH), 128.16 (virtual t, Cmeta, J ) 4.8
1
3
(
3
, 125
2
2
2
(
virtual t, Cortho, J ) 6 Hz), 181.21(t, CdO, JC-Pd-P ) 5.7 Hz).
C
2
)
31
1
P{ H} NMR (CDCl
3
, 202 MHz, 293 K): δ 20.13.
2
2 Hz), 134.67 (virtual t, Cortho, J ) 6 Hz), 183.88 (t, CO, JC-Pd-P
3
1
1
trans-(PPh ) Pd(Cl)[C(O)NHCH CH CH CH CH OH] (10g).
3
2
2
2
2
2
2
5 Hz). P{ H} NMR (CDCl
3
, 202 MHz, 293 K): δ 20.38.
5
-APE/Pd ) 2.5; reaction time, 3 h; yield 44%. Anal. Calcd (%)
Pd: Cl, 4.45; P, 7.77 Pd, 13.36. Found: Cl, 4.51;
Synthesis of 10c-h Complexes. Such complexes were prepared
2 2
for C42H42ClNO P
according to the procedure described above by reacting
PdCl (PPh (0.300 g, 0.43 mmol) and the relevant amino alcohol
in CH CN (6 mL) with CO at atmospheric pressure. The reaction
-1
P, 7.71; Pd, 13.31. IR (Nujol), 3360 and 3327 cm (νOH and
2
3 2
)
-1
-1
1
νNH); 1589 (s) cm (ν CdO); 1190 cm (ν C-N). H NMR
CDCl , 400 MHz, 293 K): δ 0.52 (m, 2H, NCH CH ), 0.78 (quint,
CH OH), 1.80 (v br,
, JHCCH ) 7.3 Hz), 3.37
3
(
2
3
2
2
time, the molar ratio amino-alcohol/Pd complex, and the yield, as
well as the analytical and spectroscopic data (IR, NMR), are
reported below.
3
H, CH
2
, JHCCH ) 7.7 Hz), 1.20 (m, 2H, CH
2
2
3
1
(
4
H, OH), 1.96 (m, slightly br, 2H, NCH
2
3
3
tr, 2H, CH
2
OH, JHCCH ) 6.6 Hz), 4.68 (t, br, 1H, NH, JHNCH
)
trans-(PPh
Pd complex ) 3; reaction time, 20 h; yield, 54%. Anal. Calcd (%)
Pd: Cl, 4.61; P, 8.06 Pd, 13.85. Found: Cl, 4.71;
3 2 2 3
) Pd(Cl)[C(O)NHCH CH(OH)CH ] (10c). 1-A2P/
1
3
.6 Hz), 7.30–7.42 (m, 18H, HPh), 7.70–7.78 (m, 12H, HPh).
, 100 MHz, 293 K): δ 22.69 (CH ), 28.19 (CH ), 31.96
(CH ), 41.66 (NCH ), 62.18 (CH OH), 128.05 (virtual t, Cmeta, J
C
NMR (CDCl
3
2
2
2 2
for C40H38ClNO P
P, 7.99; Pd, 13.79. IR (Nujol), 3417 and 3350 cm (νOH and
-
1
2
2
2
-1
-1
1
) 5 Hz), 130.10 (s, Cpara), 131.61 (virtual t, Cipso, J ) 22 Hz),
νNH); 1606 (s) cm (ν CdO); 1186 cm (ν C-N). H NMR
2
3
134.56 (virtual t, C , J ) 6.1 Hz), 180.85 (t, CdO, J
)
ortho
C-Pd-P
(
CDCl
3
, 500 MHz, 293 K): δ 0.62 (d, 3H, CH
3
, JHCCH 3) 6.40
3
1
1
3
3
6.1 Hz). P{ H} NMR (CDCl , 162 MHz, 293 K): δ 20.23.
Hz), 1.69 (m, 1H, diastereotopic NCH
2
, JHCCH ) 8.9 Hz, J HCNH
)
4.1 Hz), 1.2–1.6 (v br, OH), 2.18 (ddd, 1H, diastereotopic NCH
HCH ) 13.3 Hz, JHCCH ) 2.5 Hz, JHCNH ) 6.4 Hz), 2.65 (m,
2
,
trans-(PPh
(10h). 6-AHX/Pd ) 2.5); reaction time, 4 h; yield, 44%. Anal. Calcd
(%) for C43 Pd: Cl, 4.37; P, 7.64 Pd, 13.13. Found: Cl,
4.42; P, 7.61; Pd, 13.10. IR (Nujol), 3323 and 3311 cm (νOH
3 2 2 2 2 2 2 2
) Pd(Cl)[C(O)NHCH CH CH CH CH CH OH]
2
3
3
J
1H, CH), 5.15 (poorly resolved t, br, 1H, NH, J ≈ 5 Hz), 7.31–7.43
2 2
H44ClNO P
1
3
-1
(
3
m, 18H, HPh), 7.68–7.80 (m, 12H, HPh). C NMR (CDCl , 125