7
62 J . Org. Chem., Vol. 61, No. 2, 1996
Malet et al.
data matrix size with 2-4 scans (no dummy scans) per t
and a recycle time of 1 s. The delay was set to 50 ms. The
data were zero-filled once in the t dimension, and a sine bell
1
value
(62.5 MHz, C
2
D
6
SO) δ 64.93 (C-3), 85.70 (C-1), 113.63 (C-2),
121.27 (1C), 130.21 (2C), 131.76 (2C), 136.71 (1C). Anal. Calcd
1
for C18
2.23.
2 2 2
H16Br Cl Pd : C, 31.99; H, 2.39. Found: C, 31.90; H,
filter was used before Fourier transformation in both dimen-
sions. A gradient combination of 1.238:1.238:1 was used to
select the desired coherence.
(1-(Dim eth yla m in o)-2-(d ip h en ylp h osp h in o)eth a n e)(η3-
1-(4-n itr op h en yl)a llyl)p a lla d iu m Tetr a flu or obor a te, 3a .
2
6
9
Phase-sensitive ROESY experiment resulted from a 2 ×
12 × 1024 data matrix size with 16-32 scans per t value.
The recycle time was 1 s. As a mixing time, a continuous off-
resonance low-power pulse (2.6-KHz R field strength) during
00 ms was used. Quadrature detection in the t dimension
was achieved by the TPPI method. The data were zero-filled
once in the t dimension, and a cosine bell filter was used
A solution of 4a (0.175 g, 0.288 mmol) in acetone (15 mL) was
5
1
added over a solution of silver tetrafluoroborate (0.112 g, 0.576
mmol) in acetone (5 mL). The mixture was magnetically
stirred in the dark at room temperature. The formed precipi-
tate was filtered off, and aminophosphine 1 (0.163 g, 0.633
mmol) was added to the solution. The mixture was stirred
for 12 h at room temperature and filtered, and the solvent was
evaporated to afford a foam that was digested with diethyl
f
5
1
1
before Fourier transformation in both dimensions.
High-quality 1D GROESY spectra were obtained with a
ether to afford 3a (0.237 g, 68%): mp 173-178 °C; IR (KBr)
2
7
-1
recently proposed pulse sequence using a 500 ms T-ROESY
3057, 2973, 2924, 1595, 1518, 1433, 1335, 1103, 1053 cm ;
2
8
1
mixing time. Twenty and 40 ms Gaussian pulses were used
as selective 90° and 180° pulses, and a 1:-1:2 gradient
combination affords the desired coherence selection.
H NMR (250 MHz, CDCl
3
) δ (major trans isomer) 2.39 (s,
N(CH ), 2.55-2.80 (m, 4H), 3.40-3.55 (m, H-3a and H-3s),
3 2
)
5.54 (dd, J H-1a/H-2 ) 13.2 Hz, J H-1a/P ) 9.1 Hz, H-1a), 6.31-6.52
(m, H-2), 7.08-7.69 (m, 10H), 7.79 (d, J ) 7.7 Hz, 2H), 8.19
(d, J ) 7.7 Hz, 2H); δ (minor cis isomer, only well defined
0
All B field gradient pulses had a Gaussian shape truncated
at 5% and a length of 1 ms. Only peak amplitudes were varied
according to the required ratios described above.
Saturated solutions of compounds 3 in CDCl were used
3
throughly in NMR determinations.
signals) 3.02 (s, NCH
9.1, H-3s), 4.80-4.86 (m, H-1a and H-3a), 6.80 (dd, J HP ) 11.9
3 3
), 3.05 (s, NCH ), 4.27 (dd, J ) 13.9 and
1
3
Hz, J ortho ) 7.5 Hz, 2H ortho in one phenyl ring); C NMR
(62.5 MHz, CDCl ) δ (major trans isomer) 29.04 (d, J ) 26.6
Hz, P-CH ), 50.03 (s, N(CH ), 51.23 (d, J ) 4.6 Hz, C-3), 61.79
(d, J ) 6.5 Hz, N-CH ), 96.08 (d, J ) 27.7 Hz, C-1), 117.01 (br,
C-2), 123.95-146.88 (18C); δ (minor cis isomers, only well
defined signals) 30.72 (d, J ) 26.6, PCH ), 52.91 (s, NCH ),
53.52 (s, NCH ), 61.40 (d, J ) 7.4 Hz, NCH ), 69.65 (d, J )
5.5 Hz, C-1), 80.96 (d, J ) 24.8 Hz, C-3), 120.68 (d, J ) 5.6
Hz, C-2). Anal. Calcd for C25 PPd: C, 49.01; H,
4.61; N, 4.57. Found: C, 49.11; H, 4.69; N, 4.44.
Su bstitu en t Con sta n ts. Substituent constant values were
3
2
9
taken from the textbook by March.
Gen er a l. Products 2 and 4 have been described except for
b.
2
3 2
)
9
2
4
1
-(Dim eth yla m in o)-2-(d ip h en ylp h osp h in o)eth a n e, 1.
2
3
A mixture of diphenylphosphine (0.389 g, 2.088 mmol), potas-
sium tert-butoxide (0.562 g, 5.011 mmol), and anhydrous THF
65 mL) was magnetically stirred under nitrogen for 15 min
3
2
(
4 2 2
H28BF N O
at room temperature. Then 2-chloro-N,N-dimethylethylamine
hydrochloride (0.361 g, 2.506 mmol) was added, and the
mixture was refluxed for 6 h. Saturated aqueous ammonium
chloride (100 mL) was added at room temperature, and the
mixture was extracted with chloroform (3 × 70 mL). The
organic layer was washed with distilled water (2 × 150 mL),
dried, and evaporated to give a dense oil (0.299 g, 56%)
characterized as 1 practically pure. A sample distilled at 175-
3
(1-(Dim eth yla m in o)-2-(d ip h en ylp h osp h in o)eth a n e)(η -
1-(4-br om oph en yl)allyl)palladiu m Tetr aflu or obor ate, 3b.
It was obtained in 69% yield by the same method as for 3a
from 4b (0.181 g, 0.268 mmol), silver tetrafluoroborate (0.104
g, 0.536 mmol), and 1 (0.138 g, 0.536 mmol): mp 158-161 °C;
IR (KBr) 3057, 2973, 1623, 1482, 1440, 1187, 1159, 1060, 878,
-
1 1
751, 695 cm ; H NMR (250 MHz, CDCl
N(CH ), 2.50-2.73 (m, 4H), 3.37-3.48 (br, H-3a), 4.09 (d, J H-
2/H-3s ) 7.7 Hz, H-3s), 5.48 (dd, J H1-a/H-2 ) 13.5 Hz, J H1-a/P ) 9.1
3
) δ 2.10-2.52 (br s,
16
1
(
7
80 °C/0.4 mmHg (lit. bp 146-149 °C/0.08 mmHg): 1H NMR
250MHz, CDCl ) δ 2.11-2.22 (m, 8H), 2.28-2.37 (m, 2H),
.23-7.49 (m, 10H).
-Br om ocin n a m yl a lcoh ol was prepared in 83% yield by
reduction of ethyl 4-bromocinnamate with diisobutylaluminum
3 2
)
3
1
3
Hz), 5.97-6.21 (m, H-2), 7.09-8.19 (m, 14H); C NMR (62.5
4
MHz, CDCl
3
) δ 28.81 (d, J ) 24.8 Hz, PCH
2
), 49.76-50.48
), 99.32 (d, J )
(N(CH and C-3), 61.72 (d, J ) 7.3 Hz, NCH
3 2
)
2
-
1
hydride in toluene at -78 °C: oil; IR (film) 3277 (br), 969 cm
;
25.7 Hz, C-1), 114.49 (C-2), 125.34-134.81 (16C).
1
3
H NMR (250 MHz, CDCl
3
) δ 1.77 (br s), 4.27 (d, J ) 5.5 Hz,
(1-(Dim eth yla m in o)-2-(d ip h en ylp h osp h in o)eth a n e)(η -
1-(4-m eth oxyp h en yl)a llyl)p a lla d iu m Tetr a flu or obor a te,
3e. It was obtained from 4e9 (0.155g, 0.268 mmol), silver
tetrafluoroborate (0.104 g, 0.536 mmol), and 1 (0.138 g, 0.536
mmol), by the same method as for 3a . The salt 3e (76%) had
mp 135-140 °C: IR (KBr) 3036, 2924, 2846, 1602, 1503, 1461,
2
1
H), 6.31 (dt, J ) 15.9 and 5.5 Hz, 1H), 6.52 (d, J ) 15.9 Hz,
H), 7.20 (d, J ) 8.4 Hz, 2H), 7.40 (d, J ) 8.4 Hz, 2H).
4
-Br om ocin n a m yl ch lor id e was prepared in 80% yield
by reaction of 4-bromocinnamyl alcohol with thionyl chloride
1
in benzene at room temperature: oil; H NMR (250 MHz,
-
1
1
CDCl
Hz, 1H), 6.56 (d, J ) 15.7 Hz, 1H), 7.22 (d, J ) 8.4 Hz, 2H),
.42 (d, J ) 8.4 Hz, 2H).
Bis(µ-ch lor o)b is(1-(4-b r om op h en yl)-η -a llyl)d ip a lla -
d iu m , 4b. A degassed solution of 4-bromocinnamyl chloride
291 mg, 1.260 mmol) in anhydrous benzene (10 mL) was
added under an argon atmosphere over a degassed suspension
of Pd (dba) (HCCl ) (452 mg, 0.504 mmol) in anhydrous
3
) δ 4.19 (d, J ) 6.9 Hz, 2H), 6.27 (dt, J ) 15.7 and 6.9
1440, 1250, 1180, 1060, 878, 835 cm ; H NMR (250 MHz,
CDCl ) δ 2.02 (s, NCH ), 2.62 (s, NCH ) 2.50-2.81 (m, 4H),
3
3
3
7
2.93 (d, J
) 13.5 Hz, H-3a), 3.79 (s, OCH ), 3.78-3.84
H-3a/H2
3
3
(m, H-3s), 5.51 (dd, J H-1a/H2 ) 13.5 Hz, J
H-1a/P
) 8.8 Hz, H-1a),
6.01-6.14 (m, H-2), 6.92 (d, J ) 8.8 Hz, 2H), 7.44-7.67 (m,
12H); 13C NMR (62.5 MHz, CDCl ) δ 28.56 (d, J ) 26.8, PCH ),
(
3
2
48.94 (s, NCH ), 48.94 (d, J ) 2.8 Hz, C-3), 49.87 (s, NCH ),
3
3
2
3
3
55.33 (s, OCH ), 61.63 (d, J ) 8.3 Hz, NCH ), 101.95 (d, J )
3
2
benzene (10 mL). The mixture was kept under vigorous
magnetic stirring at room temperature for 22 h 30 min. The
green precipitate was filtered off and washed with benzene
24.9 Hz, C-1), 111.97 (d, J ) 5.5 Hz, C-2), 15.09 (s, 2C),
127.45-132.96 (15C), 160.36 (s, 1C). Anal. Calcd for
C H BF NOPPd: C, 52.24; H, 5.23; N, 2.34. Found: C,
2
6
31
4
(
1
0.264 mg, 78%): mp 195-199 °C; IR (KBr) 3064, 2938, 1588,
52.10; H, 5.30; N, 2.28.
-1
1
(1-(Dim eth yla m in o)-2-(d ip h en ylp h osp h in o)eth a n e)(η3-
1-p h en yla llyl)p a lla d iu m Tetr a flu or obor a te, 3c. A solu-
tion of bis(dibenzylideneacetone)palladium(0) (0.172 g, 0.3
mmol) and 1 (0.077 g, 0.3 mmol) in anhydrous benzene (10
mL) was added to a solution of pyridinium salt 2c9 (0.146 g,
0.3 mmol) in anhydrous benzene (5 mL). The mixture was
kept at room temperature for 6 h and filtered, the solvent was
evaporated, and the residue was digested with diethyl ether
to afford pure 3c (0.148 g, 85%): mp 175-180 °C; IR (KBr)
3
482, 1447, 1398, 1075, 1011 cm ; H NMR (250 MHz, CDCl )
δ 3.03 (d, J ) 12.1 Hz, H-3a), 3.97 (d, J ) 6.6 Hz, H-3s), 4.52
d, J ) 11.0 Hz, H-1a), 5.74 (dt, J ) ca. 12 and 6.6 Hz, H-2),
.31 (d, J ) 8.2 Hz, 2H), 7.37 (d, J ) 8.2 Hz, 2H); 13C NMR
(
7
(26) (a) Bothner-By, A. A.; Stephens, R. L.; Lee, J .-M.; Warren, C.
D.; J eanloz, R.W. J . Am. Chem. Soc. 1984, 106, 811. (b) Bax, A.; Davis,
D. G. J . Magn. Reson. 1985, 63, 207.
(27) Adell, P.; Parella, T.; S a´ nchez-Ferrando, F.; Virgili, A. J . Magn.
Reson., in press.
-
1
1
3
057, 3022, 2917, 1489, 1461, 1433, 1053, 871, 765 cm ; H
NMR (250 MHz, CDCl ) δ 1.97 (br s, NCH ), 2.58 (s, NCH ),
2.39-2.66 (m, 4H), 2.94-3.04 (m, H-3a), 3.80-3.82 (m, H-3s),
(
(
28) Hwang, T. L.; Shaka, A. J . J . Am. Chem. Soc. 1992, 114, 3157.
29) March, J . Advanced Organic Chemistry. Reactions, Mechanisms
3
3
3
and Structure, 4th ed.; J ohn Wiley and Sons: New York, 1992.