Rhodium-catalyzed reaction of aroyl chlorides with alkynes or alkenes in the presence of disilanes

Article abstract of DOI:10.1016/S0022-328X(98)00458-6

Internal alkynes effectively undergo aroylarylation, that is 1,2-addition of aroyl and aryl groups, on treatment with aroyl chlorides in the presence of a catalytic amount of [RhCl(cod)]₂ and PPh₃ using hexamethyldisilane as reducing agent to produce the corresponding 1,3-diaryl-2-propen-1-one derivatives in good yields. The reaction can also proceed using relatively reactive alkenes such as norbornenes in place of the alkynes. Similar treatment of a terminal alkyne, phenylacetylene, with aroyl chlorides brings about aroylsilylation to give 1-aryl-2-phenyl-3-trimethylsilyl-2-propene-1-ones.

Full text of DOI:10.1016/S0022-328X(98)00458-6

Journal of Organometallic Chemistry 560 (1998) 217–222
Rhodium-catalyzed reaction of aroyl chlorides with alkynes or alkenes
in the presence of disilanes
Ken Kokubo, Kenji Matsumasa, Masahiro Miura *, Masakatsu Nomura
Department of Applied Chemistry, Faculty of Engineering, Osaka Uni6ersity, Suita, Osaka 565, Japan
Received 16 December 1997; received in revised form 16 January 1998
Abstract
Internal alkynes effectively undergo aroylarylation, that is 1,2-addition of aroyl and aryl groups, on treatment with aroyl
chlorides in the presence of a catalytic amount of [RhCl(cod)] and PPh using hexamethyldisilane as reducing agent to produce
2
3
the corresponding 1,3-diaryl-2-propen-1-one derivatives in good yields. The reaction can also proceed using relatively reactive
alkenes such as norbornenes in place of the alkynes. Similar treatment of a terminal alkyne, phenylacetylene, with aroyl chlorides
brings about aroylsilylation to give 1-aryl-2-phenyl-3-trimethylsilyl-2-propene-1-ones. © 1998 Elsevier Science S.A. All rights
reserved.
Keywords: Rhodium catalyst; Aroyl chrolides; Alkynes; Alkenes; Disilanes
1
. Introduction
On the other hand, hydrosilanes [7] or disilanes [8]
are known to be capable of using for the rhodium- or
palladium-catalyzed reductive reactions of aroyl chlo-
rides to produce benzophenones, benzaldehydes, aroyl-
silanes, silylbenzenes, and biaryls. The reaction using
disilanes also was aptly extended to the palladium-cata-
lyzed decarbonylative 1,4-arylsilylation of dienes [5].
We herein report our new findings that by addition of
hexamethyldisilane to the reaction using internal alky-
nes in Scheme 1 as well as using alkenes such as
norbornenes, novel aroylarylation, that is 1,2-addition
of aroyl and aryl groups to the unsaturated bonds, can
take place (Scheme 2), and with a terminal alkyne
phenylacetylene, aroylsilylation also occurs [9].
Aroyl chlorides are known to smoothly react with
low-valent transition-metal species, including rhodium
and palladium complexes, to produce aroylmetal com-
plexes which may be further transformed into arylmetal
complexes by decarbonylation [1]. Thus, palladium-cat-
alyzed aroylation of alkenes [2] and alkynes [3] and
arylation of alkenes [4] and dienes [5] with aroyl chlo-
rides, which involve the complexes as the key intermedi-
ates, have been successfully developed. While such
reactions using rhodium species have been so far unex-
plored, they may be expected to be realized. Indeed, we
found that aroyl chlorides smoothly react with terminal
alkynes accompanied by decarbonylation in the pres-
ence of catalytic amounts of [RhCl(cod)] and PPh to
2
3
give the corresponding chloroarylation products regio-
and stereo-selectively in good yields, and with internal
alkynes 2,3-disubstituted-1-indenones can also be ob-
tained (Scheme 1) [6].
2
. Results and discussion
The reaction of benzoyl chloride (1a) (4 mmol) with
-octyne (2a) (2 mmol) was first examined using hexam-
4
ethyldisilane (4 mmol) in the presence of [RhCl(cod)]2
0.01 mmol) with or without addition of a phosphorous
ligand in xylene at 120°C for 20 h under nitrogen
(
*
Corresponding author. Tel.: +81
6 8797361; fax: +81 6
8
0
797362.
022-328X/98/$19.00 © 1998 Elsevier Science S.A. All rights reserved.
PII S0022-328X(98)00458-6

218
K. Kokubo et al. / Journal of Organometallic Chemistry 560 (1998) 217–222
Table 1
(
Table 1). Without using the ligand 1,3-diphenyl-2-
a
Reaction of 1a with 2a in the presence of hecamethyldisilane
propyl-2-hexen-1-one (3) was obtained as the cross-cou-
pling product in a yield of 16% (based on the amount
of 2a used) together with a trace amount of benzophe-
none (4) and biphenyl (5) (30%) (entry 1). Addition of
PPh up to 2 equivalent of Rh increased the yield of 3
3
to 51% (entries 2–4). Although a bidentate ligand,
dppp [1,3-bis(diphenylphosphino)propane], could be
Entry
Ligand/mmol
Solvent
Yield (%)b
(Z)/(E)
used as well as PPh , P(OPh)3 and PBu3 were less
3
3
4
5
effective (entries 5–7). An increase in the amount of 1a
and the disilane to 6 mmol afforded 64% yield of 3. A
further enhancement of the product yield to 83% was
attained by using 1,1,2,2-tetrachloroethane (TCE) as
solvent in place of xylene, while octane was less effec-
tive. At a lower or higher reaction temperature of 100
or 140°C the yield of 3 was considerably decreased. It is
noted that in each entry, (a) the product 3 was a
mixture of two possible stereoisomers, forming the (Z)
isomer preferentially and (b) the yield of 2,3-dipropyl-1-
indenone, which is the predominant product in the
reaction in the absence of the disilane, was B5%.
The results of the reaction of 1a and 2a using a
number of reducing agents are recorded in Table 2.
When dichlorotetramethyldisilane was employed in
place of hexamethyldisilane, 3 was still produced in a
yield of 53%, whereas hexaphenyldisilane, triethylsilane,
hexamethylditin, and hydrogen were far less effective or
ineffective, suggesting that the identity of reducing
agents is also one of the significant factors determining
the reaction efficiency.
1
2
3
4
5
6
7
8
9
1
PPh /0
Xylene
Xylene
Xylene
Xylene
Xylene
Xylene
Xylene
Xylene
Octane
16 (94/6)
42 (90/10)
51 (96/4)
45 (89/11)
47 (92/8)
30 (37/63)
28 (86/14)
64 (94/6)
58 (81/19)
83 (89/11)
tr
tr
tr
30
20
19
16
18
14
14
46
46
25
3
PPh /0.02
3
PPh /0.04
3
PPh /0.06
8
3
dppp/0.02
P(OPh) /0.04
23
16
7
21
26
19
3
PBu /0.04
3
c
PPh
/0.04
3
c
PPh /0.04
3
0c
PPh /0.04
TCE
d
3
a
The reaction was carried out in the presence of [RhCl(cod)]2 (0.01
mmol) at 120°C for 20 h under N
. [1a]:[2a]:[Me SiSiMe ]=4:2:4 (in
3 3
2
mmol).
b
[
[
1
(mmol of product/2)×100]. Determined by GLC.
c
1a]:[2a]:[Me SiSiMe ]=6:2:6 (in mmol).
3 3
d
,1,2,2-Tetracholorethane.
chlorobenzoyl chlorides (1c) with 2a gave the corre-
sponding compounds 6 and 7, as did that of 1a.
Qualitative analysis of the reactions of 1a–c with 2a by
GLC indicated that the rate of consumption of 1a–c
decreased in the order of 1c\1a\1b. 5-Decyne (2b)
and 2,9-dimethyl-5-decyne (2c) reacted with 1a to give
the corresponding unsaturated ketones 8 and 9, respec-
tively. All these products 3 and 6–9 were produced as
mixtures of the corresponding (Z) and (E) isomers, and
the (Z) isomers were the major ones. Note that the
configuration of the products was determined by their
Table 3 summarizes the results for a number of
reactions of aroyl chlorides with internal alkynes as well
as alkenes. The reactions of 4-methyl- (1b) and 4-
1
H-NMR spectra with the aid of NOE measurements.
The following data for (Z)- and (E)-6 are the
representatives.
Table 2
Aroylarylation of 1a with 2a in the presence of various reducing
agents
Scheme 1.
a
Entry
Reducing agent
Me SiSiMe
% Yield of 3 (Z)/(E)
1
2
3
4
5
6
83 (89/11)
53 (87/13)
0
10 (90/10)
3 (84/16)
0
3
3
ClMe SiSiMe Cl
2
2
Ph SiSiPh
3
3
HSiEt3
Me SnSnMe
3
3
H2
a
The reaction was carried out in 1,1,2,2-tetrachloroethane at 120°C
for 20 h under N . [[RhCl(cod)] ]:[PPh ]:[1a]:[2a]:[Reducing agent]=
2
2
3
Scheme 2.
0.01:0.04:6:2:6 (in mmol).

K. Kokubo et al. / Journal of Organometallic Chemistry 560 (1998) 217–222
219
Table 3
Aroylarylation of 1 with 2, 10 and 11 in the presence of hexamethyl-
disilanea
Substrates
Product, % yieldb
(Z)/(E)
Scheme 3.
1
2
Scheme 4.
It is conceivable that each (E) isomer may be, at least
in part, formed by isomerization of the corresponding
(
Z) isomer during the reaction. Indeed, it was confirmed
that treatment of 3 with a (Z)/(E) ratio of 85:15 under
the reaction conditions for 24 h gave the compound with
a
ratio of 68:32. The reactions of 1a with
norbornene (10) and dicyclopentadiene (11) also gave
1
aroylarylation products 12 and 13, respectively. H-
NMR spectra of them suggested that both benzoyl and
phenyl groups were introduced in the exo-positions
(
coupling constant between vicinal protons at the car-
bons attached benzoyl and phenyl groups in both com-
pounds 12 and 13 was observed to be uniformly 10.3 Hz),
while the product 13 was obtained as a mixture of two
possible double-bond isomers. This is in harmony with
the selective cis-addition of aroyl and aryl groups to
internal alkynes. The reaction of benzoyl bromide in
place of 1a with 2a did not give any cross-coupling
products, only giving 4 (32%) and 5 (21%).
In the reaction of 1a with 1-octyne as a terminal alkyne
in the presence of hexamethyldisilane under the present
conditions, (Z)-2-chloro-1-phenyl-1-octene was formed
as a sole characterizable cross-coupling product in 14%
yield, no benzoylphenylation product being detected. It
was of interest that the reaction of 1a with pheny-
a
The reaction was carried out in 1,1,2,2,-tetrachloroethane at 120°C
for 20 h under N2 unless otherwise noted. [[RhCl(cod)] ]:[PPh ]:
2
3
[
1]:[2]:[Me SiSiMe ]=0.01:0.04:6:2:6 (in mmol).
3 3
b
GLC yield based on 2 used. Value in parentheses indicates yield
lacetylene (2d) using PPh as ligand in TCE at 140°C gave
3
after isolation.
also no benzoylphenylation product, but (Z)-1,2-
diphenyl-3-trimethylsilyl-2-propenone (16) (5%), which
may be regarded as a benzoylsilylation product, was
obtained along with (Z)-1-chloro-1,2-diphenylethene
c
Reaction for 30 h.
Reaction for 14 h.
d
e
[
[RhCl(cod)] ]:[PPh ]=0.01:0.02 (in mmol).
2 3
f
Mixture of double-bond isomers.

220
K. Kokubo et al. / Journal of Organometallic Chemistry 560 (1998) 217–222
(
15) (11%) (Scheme 3). Treatment of 1a with 2d using
3. Experimental section
tricyclohexylphosphine as ligand in refluxing octane
was found to induce benzoylphenylation to produce
compound 14 (16%) together with 15 (6%) and 16
1
13
H- and C-NMR spectra were recorded at 400 or
270 MHz and 100 or 68 MHz, respectively, for CDCl3
solutions. MS data were obtained by EI. GLC analysis
was carried out using a silicone OV-17 glass column (ƒ
(
19%). In the reactions of 1a and 1b (2 mmol) with an
excess amount of 2d (6 mmol), 16 and 17 were obtained
as the major products (Scheme 4).
2
.6 mm×1.5 m) or a CBP-1 capillary column (ƒ 0.5
Based on the observed results, a possible reaction
mechanism for the present aroylarylation reaction with
aroyl chloride 1 is illustrated in Scheme 5 using internal
alkyne 2 as substrate. For the addition of both aroyl
and aryl groups to 2, it would involve two-fold oxida-
tive additions of 1 to the metal center. Although the
transformation of Rh(I) to Rh(III) by oxidative addi-
tion is very common, Rh(III) species does not seem to
undergo further oxidative addition to form Rh(V) spe-
cies. Therefore, it is reasonable to consider that the
second oxidative addition may occur via aroyl- and
aryl-rhodium(I) intermediates. This leads us to deduce
initial formation of trimethylsilylrhodium(I) species B
by the reaction of the disilane with chlororhodium(I)
species A, which is generated in the reaction medium
from [RhCl(cod)]2 in the presence of PPh3 and 2,
accompanied elimination of trimethylsilyl chloride. The
subsequent oxidative addition of 1 gives intermediate
C, followed by the second elimination of trimethylsilyl
chloride to afford arylrhodium species D. Oxidative
addition of another aroyl chloride molecule, after aryl-
rhodation to the coordinated alkyne molecule in the
complex D to form E, gives aroylvinyl species F. Then,
reductive elimination of aroylarylation product regener-
ates complex A. While the catalytic cycle proceeds,
ligand L% is possibly CO, since it is known that com-
plete removal of CO from rhodium(I) species is rather
difficult ([1]b) [10]. However, the second CO seems to
be capable of being replaced by alkyne 2 [6]. On the
other hand, oxidative addition of 2 to D, before forma-
tion of E, may also occur to lead to formation of
diarylketone and biaryl as byproducts. It is noted that
aroyl chlorides are known to be reduced by a hydrosi-
lane in the presence of a rhodium catalyst to give the
corresponding diarylketones [7]. Since no diarylation
product could not be detected in each reaction, the
reductive elimination in F appears to be a rather fast
step. Another possible path via aroylrhodation to the
coordinated alkyne in C is unlikely involved [6].
mm×25 m). The following experimental details given
below may be regarded as typical in methodology and
scale.
3
.1. Reaction of benzoyl chloride (1a) with 4-octyne
(
2a)
To a flask containing [RhCl(cod)]2 (4.9 mg, 0.01
mmol) and PPh (10.4 mg, 0.04 mmol) under nitrogen
3
(
with a balloon) was added a solution of 1a (843 mg, 6
mmol), 2a (220 mg, 2 mmol), hexamethyldisilane (876
mg, 6 mmol), and 1-methylnaphthalene (ca. 100 mg) as
internal standard in 1,1,2,2-tetrachloroethane (5 ml)
and the resulting mixture was stirred at 120°C for 20 h.
GLC and GLC-MS analyses of the mixture confirmed
formation of 1,3-diphenyl-2-propyl-2-hexen-1-one (3)
(
485 mg, 83%, (Z)/(E)=89:11), benzophenone (4) (69
Formation of the benzoylsilylation products 16 and
17 may be explained by considering the mechanism
involving silylrhodation in the intermediate B followed
by oxidative addition of 1. It is noted that the regiose-
lectivity in the aroylsilylation is consistent with that
observed in the rhodium-catalyzed silylformylation re-
actions of terminal alkynes [11]. The results shown in
Schemes 3 and 4 suggest that the precedence of the
steps B to C and silylrhodation depends on the relative
amount of 1 to 2 as well as the structure of alkynes.
Scheme 5.

K. Kokubo et al. / Journal of Organometallic Chemistry 560 (1998) 217–222
221
mg, 19%), and biphenyl (5) (77 mg, 25%). Product 3
426 mg, 73%) was also isolated by column chromatog-
raphy on silica gel using hexane-ethyl acetate (99.5:0.5,
v/v) as eluent. Elaborated column chromatography of 3
afforded its (Z)- and (E)-isomers having \90%
content.
3H, J=7.3 Hz; Z), 0.96 (t, 3H, J=7.3 Hz; Z), 1.14–
1.50 (m, 4H), 2.07–2.14 (m, 4H; E), 2.49–2.56 (m, 4H;
Z), 6.94 (dt, 2H, J=8.3, 2.2 Hz; Z), 7.02 (dt, 2H,
J=8.3, 2.2 Hz; Z), 7.20 (d, 2H, J=8.3 Hz; Z), 7.31–
(
7
.50 (m, 4H; E), 7.57 (d, 2H, J=8.3 Hz; Z), 7.63–7.69
(
3
m, 2H; E), 7.95 (d, 2H, J=8.3 Hz; E); MS m/z 360,
62, 364 (M ). Anal. Calcd for C H Cl O: C, 69.81;
21 22 2
+
3.2. Products
H, 6.14; Cl, 19.62. Found: C, 69.61; H, 6.17; Cl, 19.59.
1
2
-Butyl-1,3-diphenyl-2-hepten-1-one (8): oil; H-
NMR (400 MHz) ((Z)/(E)=97:3) l 0.64 (t, 3H, J=
.3; E), 0.70 (t, 3H, J=7.3 Hz; E), 0.85–0.92 (m, 6H;
Z), 1.30–1.47 (m, 8H), 2.13–2.19 (m, 4H; E), 2.55–
.61 (m, 4H; Z), 6.94–7.00 (m, 5H; Z), 7.17 (t, 2H,
J=7.3 Hz; Z), 7.25–7.29 (m, 1H; Z), 7.60–7.62 (m,
Compounds 14 [12], 15 [6], and 16 [13] are known
and were compared with those authentic specimens.
The analytical data of other products 3, 6–9, 12, 13,
and 17 are as follows. The purity of these compounds
7
2
1
13
was judged to be \95% by GC and/or H- and C-
NMR analyses.
+
2
H; Z), 8.03 (d, 2H, J=8.3 Hz; E); HRMS m/z (M )
calcd for C23 28O 320.2140, found 320.2140.
,3-Diphenyl-6-methyl-2-(3-methylbutyl)-2-hepten-1-
one (9): oil; H-NMR (400 MHz) ((Z)/(E)=78:22) l
0.58 (d, 6H, J=6.4 Hz; E), 0.66 (d, 6H, J=6.4 Hz; E),
0.88 (d, 6H, J=6.4 Hz; Z), 0.91 (d, 6H, J=6.4 Hz; Z),
1
,3-Diphenyl-2-propyl-2-hexen-1-one (3): (Z)-isomer;
1
H
oil; H-NMR (400 MHz) l 0.92 (t, 3H, J=7.3 Hz),
.98 (t, 3H, J=7.3 Hz), 1.32–1.40 (m, 2H), 1.45–1.54
m, 2H), 2.53–2.60 (m, 4H), 6.94–7.01 (m, 5H), 7.18 (t,
H, J=7.8 Hz), 7.29 (t, H, J=7.3 Hz), 7.62 (d, 2H,
J=7.3 Hz); C-NMR (100 MHz) l 13.97, 14.33,
1
0
(
2
1
1
1
3
1
4
.18–1.40 (m, 4H), 1.53–1.63 (m, 2H), 2.13–2.17 (m,
2
1
2
1.49, 22.14, 33.59, 35.62, 126.96, 127.70, 127.15,
28.80, 129.10, 132.03, 137.86, 138.17, 141.42, 142.95,
H; E), 2.53–2.59 (m, 4H; Z), 6.94–8.04 (m, 10H); MS
+
+
m/z 348 (M ). Anal. Calcd for C H O: C, 86.16; H,
01.55; HRMS m/z (M ) calcd for C H O 292.1827,
25 32
21
24
1
9
.25. Found: C, 85.89; H, 9.26.
found 292.1837. (E)-isomer; oil; H-NMR (400 MHz) l
0
1
.66 (t, 3H, J=7.3 Hz), 0.73 (t, 3H, J=7.3 Hz),
.15–1.34 (m, 4H), 2.11–2.18 (m, 4H), 7.25 (dd, 2H,
exo - 2 - Benzoyl - exo - 3 - phenylbicyclo[2.2.1]heptane
1
(12): white solid; m.p. 87.0–88.0°C; H-NMR (270
MHz) l 1.40–1.52 (m, 2H), 1.69–1.73 (m, 2H), 2.43–
2.49 (m, 2H), 2.69 (s, 1H), 3.29 (d, 1H, J=10.3 Hz),
3.84 (d, 1H, J=10.3 Hz), 6.88–6.96 (m, 5H), 7.21 (t,
2H, J=7.3 Hz), 7.34 (t, 1H, J=7.3 Hz), 7.54 (d, 2H,
J=7.3, 1.5 Hz), 7.31 (td, 1H, J=7.3, 1.5 Hz), 7.40 (t,
H, J=7.3 Hz), 7.51 (t, 2H, J=7.3 Hz), 7.60 (t, 1H,
2
13
J=7.3 Hz), 8.04 (dd, 2H, J=7.3, 1.5 Hz); C-NMR
100 MHz) l 13.81, 13.97, 21.03, 21.95, 33.95, 38.13,
(
13
1
1
26.87, 128.19, 128.30, 128.34, 128.65, 129.32, 133.24,
37.17, 140.73, 141.29, 200.98; HRMS m/z (M ) calcd
J=7.3 Hz); C-NMR (68 MHz) l 28.95, 31.15, 37.38,
9.17, 43.52, 53.90, 56.19, 125.80, 127.60, 127.85,
127.97, 128.38, 131.94, 138.50, 141.78, 201.66; MS m/z
+
3
for C H O 292.1827, found 292.1823.
2
1
24
1
,3-Di(4-methylphenyl)-2-propyl-2-hexen-1-one (6):
+
2
76 (M ). Anal. Calcd for C H O: C, 86.92; H, 7.29.
20 20
1
(
Z)-isomer; oil; H-NMR (400 MHz) l 0.91 (t, 3H,
J=7.3 Hz), 0.94 (t, 3H, J=7.3 Hz), 1.33–1.48 (m,
H), 2.14 (s, 3H), 2.28 (s, 3H), 2.48–2.56 (m, 4H), 6.83
d, 2H, J=8.1 Hz), 6.93 (d, 2H, J=8.1 Hz), 7.01 (d,
Found: C, 86.75; H, 7.33.
exo-8-Benzoyl-exo-9-phenyl- and exo-9-Benzoyl-exo-
4
(
2
8
-phenyl-tricyclo[5.2.1.02, 6]dec-3-enes (13): white solid;
1
m.p. 118.5–119.0°C; H-NMR (400 MHz) (mixture of
double bond isomers in a ratio of 2:1) l 1.73 (t, 1H,
J=10.3 Hz), 2.32–2.77 (m, 6H), 3.25–3.45 (m, 1.33H),
1
3
H, J=8.1 Hz), 7.58 (d, 2H, J=8.1 Hz); C-NMR (68
MHz) l 13.99, 14.28, 20.99, 21.51, 22.10, 33.67, 35.53,
1
1
28.41, 128.57, 129.39, 135.06, 136.42, 137.83, 138.50,
3
.44 (d, 0.67H, J=10.3 Hz), 3.84 (d, 0.67H, J=10.3
+
41.89, 142.76, 201.16; HRMS m/z (M ) calcd for
Hz), 3.91 (d, 0.33H, J=10.3 Hz), 5.70–5.72 (m, 1H),
1
C H O 320.2140, found 320.2139. (E)-isomer; oil; H-
2
3
28
5
2
.92–5.94 (m, 1H), 6.87–6.97 (m, 5H), 7.16–7.25 (m,
NMR (400 MHz) l 0.65 (t, 3H, J=7.3 Hz), 0.72 (t,
H), 7.29–7.37 (m, 1H), 7.48 (d, 0.67H, J=8.3
3
2
H, J=7.3 Hz), 1.14–1.31 (m, 4H), 2.11–2.16 (m, 4H),
.38 (s, 3H), 2.44 (s, 3H), 7.13 (d, 2H, J=8.1 Hz), 7.20
13
Hz), 7.57 (d, 1.33H, J=8.3 Hz); C-NMR (100 MHz)
l 32.41, 32.54, 40.19, 40.37, 41.92, 42.12, 43.35, 43.41,
45.30, 46.27, 48.06, 48.14, 48.63, 51.26, 52.79, 54.22,
(
d, 2H, J=8.1 Hz), 7.29 (d, 2H, J=8.1 Hz), 7.93 (d,
1
3
2
2
1
1
3
H, J=8.1 Hz); C-NMR (68 MHz) l 13.84, 13.99,
1.08, 21.19, 21.72, 21.96, 34.05, 38.15, 128.20, 128.84,
29.33, 129.48, 134.76, 136.37, 137.14, 137.75, 140.73,
1
1
1
25.72, 125.76, 127.58, 127.61, 127.77, 127.94, 127.98,
28.03, 128.52, 128.72, 131.76, 131.84, 132.06, 132.08,
+
32.24, 132.41, 138.46, 141.82, 142.05, 201.85;
44.04, 200.78; HRMS m/z (M ) calcd for C H O
23
28
+
20.2140, found 320.2148.
HRMS m/z (M ) calcd for C23H22O 314.1670, found
1
,3-Di(4-chlorophenyl)-2-propyl-2-hexen-1-one (7):
314.1676.
1
oil; H-NMR (270 MHz) ((Z)/(E)=85:15) l 0.67 (t,
H, J=7.3 Hz; E), 0.78 (t, 3H, J=7.3 Hz; E), 0.91 (t,
(Z)-1-(4-Methylphenyl)-2-phenyl-3-trimethylsilyl-2-
propen-1-one (17): oil; H-NMR (400 MHz) l 0.01 (s,
1
3

222
K. Kokubo et al. / Journal of Organometallic Chemistry 560 (1998) 217–222
(
(
1980) 1653. (b) J.D. Rich, J. Am. Chem. Soc. 111 (1989) 5886.
c) J.D. Rich, Organometallics 8 (1989) 2606. (d) J.D. Rich, T.E.
9
7
H), 2.37 (s, 3H), 6.45 (s, 1H), 7.19 (d, 2H, J=8.1 Hz),
.24–7.30 (m, 3H), 7.36–7.39 (m, 2H), 7.82 (d, 2H,
Krafft, Organometallics 9 (1990) 2040. (e) T.E. Krafft, J.D.
Rich, P.J. McDermott, J. Org. Chem. 55 (1990) 5430.
1
3
J=8.1 Hz); C-NMR (100 MHz) l −0.53, 21.71,
1
1
25.97, 128.22, 128.61, 129.26, 130.10, 132.04, 134.33,
38.66, 144.31, 155.25, 198.78; MS m/z 294 (M ).
[9] Palladium-catalyzed reaction of alkynes with disilanes: (a) H.
Sakurai, Y. Kamiyama, Y. Nakadaira, J. Am. Chem. Soc. 97
+
(
1975) 931. (b) H. Okinoshima, K. Yamamoto, M. Kumada, J.
Anal. Calcd for C H OSi: C, 77.50; H, 7.53. Found:
C, 77.54; H, 7.61.
1
9
22
Organomet. Chem. 86 (1975) C27. (c) K. Tamao, T. Hayashi, M.
Kumada, J. Organomet. Chem. 114 (1976) C19. (d) H. Watan-
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1
86 (1980) 51. (e) D. Seyferth, E.W. Goldman, J. Escudie, J.
Organomet. Chem. 271 (1984) 337. (f) Y. Ito, M. Suginome, M.
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Catellani, M. Tanaka, Chem. Lett. (1991) 241. (h) M. Mu-
rakami, T. Yoshida, Y. Ito, Organometallics 13 (1994) 2900. (i)
F. Ozawa, M. Sugawara, T. Hayashi, Organometallics 13 (1994)
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