596
A.S.K. Hashmi / Journal of Organometallic Chemistry 694 (2009) 592–597
1490, 1480, 1435, 1276, 1182, 1100, 989, 828, 747, 709, 692 cmÀ1
;
121 MHz): d = 25.0 (d) ppm; HRMS (LIFDI) m/z (%) = 278 (100),
1H NMR (C6D6, 500 MHz): d = 8.48–8.52 (d, J = 19.2 Hz, 1H,
CH@CH–C6H5), 7.67 (d, J = 7.1 Hz, 2H, C6H5), 7.52 (d, J = 19.2 Hz,
1H, CH@CH–C6H5), 7.38–7.42 (m, 6H, P(C6H5)3), 7.22 (t,
J = 7.6 MHz, 2H, C6H5), 7.030–7.06 (tt, J = 8.4 Hz, 1H, C6H5), 6.90–
6.98 (m, 9H, P(C6H5)3); 13C NMR (C6D6, 125 MHz): d = 144.74 (s),
134.55 (d, JC-P = 13.8 Hz) 131.87 (s), 131.49 (s), 130.93 (s), 129.09
(d, JC-P = 10.6 Hz), 128.74 (s), 128.53 (s), 128.29 (s), 126.32 (s),
126.12(s); 31P NMR (C6D6, 121 MHz): d = 43.9 (s) ppm; HRMS (LIF-
DI) m/z (%) = 562 (100) [M]+, 830 (11), 913 (4), 387 (4), 262 (60),
206 (21)). The data is in accordance with some data published on
this compound before [14].
557 (65) [M]++3Na, 721.1 (77), 987.1 (65); Anal. Calc. for
C23H24AuP: found: C, 49.19; H, 4.13%. This data is in accordance
with some data published previously [15].
4.10. General procedure for Michael additions
In a dry NMR tube the gold(I) complex (1 equiv.) was dissolved
in deuterated benzene (500 lL) and methyl vinyl ketone (1 equiv.)
was added at room temperature. The possible conversion of the
starting materials was monitored by in situ 1H NMR, but no evi-
dence for a reaction was observed.
4.8. [(1E)- and (1Z)-Pent-1-en-1-yl](triphenyl-k5-phosphanyl)gold
(5h)
4.11. Reactions with electrophilic halogens
4.11.1. (E)-2-Phenyl-1-iodo-1-ethene
In dry isopropanol (5 mL) 1-pentenyl boronic acid (35.0 mg,
In deuterated benzene (500
l
L) gold(I) complex (10.0 mg,
mol) was dissolved and N-iodosuccinimide (4.01 mg,
mol) was added at room temperature. Conversion of the
303
added. To this suspension was added [(Ph3P)AuCl] (75.0 mg,
151 mol) under N2 and the resultant mixture was stirred at
lmol) was dissolved and Cs2CO3 (98.8 mg, 303
lmol) was
178
178
l
l
l
starting material is monitored by 1H NMR. Yield (NMR): >95%. 1H
NMR (CDCl3, 300 MHz): d = 6.41 (d, J = 14.9 Hz, 1H, CH@CHI),
7.17–7.19 (m, 1H, CH@CHI), 7.26–7.34 (m, 5H, C6H5); 13C NMR
(CDCl3, 75 MHz): d = 126.24 (s), 126.78 (s), 128.69 (s), 133.18 (s),
145.11 (s). This data is in accordance with the published data [16].
50 °C for 24 h and taken to dryness via rotary evaporation. The so-
lid was extracted with benzene, filtered through Celite, concen-
trated in vacuo to dryness, washed with pentane and dried. The
solid was re-extracted into a minimum of benzene, filtered, and
was washed with pentane to get reddish brown sticky substance,
which was washed with methanol, pentane and dried. The product
was found to be mixture of (E) and (Z) isomers from NMR analysis.
4.11.2. (E)-2-Phenyl-1-bromo-1-ethene
In deuterated benzene (500
l
L) gold(I) complex (10.0 mg,
mol) was dissolved and N-bromosuccinimide (3.16 mg,
mol) was added at room temperature. Conversion of the
E:Z = 4:1. Yield: 65.0 mg (82%). IR (film):
m
= 2954, 2927, 1480,
178
178
l
l
1459, 1436, 1330, 1309, 1183, 1100, 998, 910, 812, 746, 710,
692 cmÀ1; (E Isomer): 1H NMR (C6D6, 500 MHz): d = 7.58 (d,
J = 11.4 Hz, 1H, (CH@CH(C3H7))), 7.40 (m, 6H, P(C6H5)3), 6.92–
6.97 (m, 9H, P(C6H5)3), 2.83 (q, J = 14.2 Hz, 3H, CH3), 1.77 (td,
J = 14.8 Hz, 2H, CH2), 1.30-1.37 (m, 2H, CH2) 1.11 (t, J = 7.4 Hz,
3H, (CH@CH(C3H7))); 13C NMR (C6D6, 125 MHz): d = 146.41 (s),
134.52 (d, JC-P = 13.8 Hz), 132.35 (d, J = 9.6 Hz), 132.14 (s), 131.76
(s), 130.84 (s), 129.03 (d, JC-P = 10.5 Hz), 42.65 (s), 30.15 (s), 24.51
(s), 14.35 (d, J = 29.0 Hz); (Z Isomer): 1H NMR (C6D6): d 7.58 (d,
J = 18.4 Hz, 1H, (CH@CH(C3H7))), 7.40 (m, 6H, P(C6H5)3), 6.92–
6.97 (m, 9H, P(C6H5)3), 2.50 (q, J = 14.6 Hz, 3H, CH3), 1.77 (td,
J = 14.7 Hz, 2H, CH2), 1.11 (t, J = 7.3 Hz, 1H, (CH@CH(C3H7))), 0.88
(m, 2H, CH2); 13C NMR (C6D6, 125 MHz): d = 144.47 (s), 134.52
(d, JC-P = 13.7 Hz), 132.35 (d, J = 9.62 Hz), 132.14 (s), 131.53 (s),
130.84 (s), 129.03 (d, JC-P = 10.5 Hz), 41.45 (s), 30.15 (s), 23.82 (s),
14.35 (d, J = 29.0 Hz); 31P NMR (C6D6): d = 43.9 (s) ppm; HRMS (LIF-
DI) m/z (%) = 262 (1), 494 (1), 528 (100) [M]+, 987 (95); Anal. Calc.
for C23H24AuP: found: C, 52.28; H, 4.58%.
starting material is monitored by 1H NMR. Yield (NMR): >95%. 1H
NMR (CDCl3, 300 MHz): d = 6.34 (d, J = 14.0 Hz, 1H, CH@CHBr),
7.26–7.33 (m, 6H, C6H5); 13C NMR (CDCl3, 75 MHz): d = 106.88
(s), 126.34 (s), 128.80 (s), 129.03 (s), 137.36 (s), 147.73 (s). This
data is in accordance with the published data [17].
4.11.3. (E)-2-Phenyl-1-chloro-1-ethene
In deuterated benzene (500
l
L) gold(I) complex (10.0 mg,
mol) was dissolved and N-chlorosuccinimide (2.38 mg,
mol) was added at room temperature. Conversion of the
178
178
l
l
starting material is monitored by 1H NMR. Yield (NMR): >95%. 1H
NMR (CDCl3, 300 MHz): d = 7.71–7.78 (m, 2H, C6H5), 7.30 (d, 2H,
J = 7.4 Hz, C6H5), 7.23 (d, J = 15.1 Hz, 1H, CH@CHCl), 6.99–7.11
(m, 6H, P(C6H5)3), 6.80–6.93 (m, 9H, P(C6H5)3), 6.49 (d,
J = 15.1 Hz, 1H, CH@CHCl); 13C NMR (CDCl3, 75 MHz): d = 126.78
(s), 128.62 (s), 128.63 (s), 129.65 (s), 133.18 (s).
4.11.4. (E)-2-Phenyl-1-iodo-1-ethene via Barluenga reagent
4.9. Ethyl(triphenyl-k5-phosphanyl)gold (5i)
In deuterated benzene (500
178 mol) was dissolved and bis(pyridine)iodonium tetrafluorobo-
rate (6.62 mg, 178 mol) was added at room temperature. Conver-
lL) the gold(I) complex (10.0 mg,
l
In dry isopropanol (5 mL) ethyl boronic acid (22.5 mg,
l
303
added. To this suspension was added [(Ph3P)AuCl] (75.0 mg,
152 mol) under N2 and the resultant mixture was stirred under
lmol) was dissolved and Cs2CO3 (98.8 mg, 303
l
mol) was
sion of the starting material is monitored by 1H NMR and the
product formed was purified via column chromatography on silica
with petrol ether and ethyl acetate as eluents. Yield: 65 mg (88%).
1H NMR (CDCl3, 300 MHz): d = 6.86 (d, J = 14.9 Hz, 1H, CH@CHI),
7.33–7.35 (m, 5H, C6H5), 7.46 (d, 1H, J = 14.9 Hz CH@CHI); 13C
NMR (CDCl3, 75 MHz): d = 125.98 (s), 128.70 (s), 128.36 (s), 145.0 (s).
l
argon at 50 °C for 24 h and taken to dryness via rotary evaporation.
The solid was extracted with benzene, filtered through Celite, con-
centrated in vacuo to dryness, washed with pentane and dried. The
solid was re-extracted into a minimum of benzene, filtered, and
was washed with pentane to get brownish sticky mass, which
was washed with methanol, pentane and dried. Yield: 62 mg
4.11.5. (E,E)-1,4-Diphenyl-1,3-butadiene
In deuterated benzene (500
382 mol) was dissolved and N-fluorobenzenesulfonimide
(12.0 mg, 382 mol) was added at room temperature. Conversion
lL) gold(I) complex (21.5 mg,
(84%). IR (film):
m
= 2926, 1479, 1435, 1336, 1197,1092, 1026,
l
997, 888, 796, 745, 695 cmÀ1
;
1H NMR (C6D6, 500 MHz):
l
d = 7.70–7.77 (m, 3H, P(C6H5)3), 7.34–7.40 (m, 4H, P(C6H5)3),
of the starting material is monitored by 1H NMR. Yield (NMR):
>95%. Isolated Yield: 5.0 mg (64%). 1H NMR (CDCl3, 300 MHz):
d = 7.35 (d, 4H, J = 8.6 Hz, ArH), 7.31–7.23 (m, 4H, ArH), 7.16–7.13
(m, 2H, ArH), 6.91–6.86 (dd, 2H, J = 12.0 Hz, J = 14.8 Hz, CH),
6.62–6.58 (dd, 2H, J = 11.9 Hz, J = 14.8 Hz, CH); 13C NMR (CDCl3,
6.95–7.03 (m, 8H, P(C6H5)3), 1.21–1.39 (m, 3H, CH3), 0.86–0.91
(m, 2H, CH2); 13C NMR (C6D6, 125 MHz): d = 134.55 (d, JC-P
=
13.8 Hz), 132.42 (d, J = 9.68 Hz), 131.55 (s), 131.52 (s), 129.09
(d, JC-P = 10.6 Hz), 128.78 (s), 31.69 (s), 30.20 (s); 31P NMR (C6D6,