Fluoride-ion-mediated reactions of trimethylsilylacetylene with carbonyl compounds and terminal acetylenes

Article abstract of DOI:10.1016/S0022-328X(99)00262-4

Fluoride-ion-mediated reaction of trimethylsilylacetylene with carbonyl compounds has been thoroughly studied. The products of addition to the C=O bond were obtained in 15-66% yield, their subsequent silylation and addition to the second molecule of the c

Full text of DOI:10.1016/S0022-328X(99)00262-4

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Journal of Organometallic Chemistry 586 (1999) 184–189
Fluoride-ion-mediated reactions of trimethylsilylacetylene with
carbonyl compounds and terminal acetylenes
Edgars Abele, Kira Rubina, Ramona Abele, Juris Popelis, Ilona Mazeika,
Edmunds Lukevics *
Lat6ian Institute of Organic Synthesis, 21 Aizkraukles Street, Riga, LV-1006, Lat6ia
Received 12 March 1999; received in revised form 4 May 1999
Abstract
Fluoride-ion-mediated reaction of trimethylsilylacetylene with carbonyl compounds has been thoroughly studied. The products
of addition to the CꢀO bond were obtained in 15–66% yield, their subsequent silylation and addition to the second molecule of
the carbonyl compound being observed. It has been found that terminal aryl and hetaryl acetylenes undergo silylation in a
two-phase-system Me3SiCꢁCH/CsF/18-crown-6 to afford aryl(hetaryl) trimethylsilylacetylenes with up to 100% yields. Combining
these two reactions, a novel one-pot fluoride-ion-mediated method for the synthesis of 1-trimethylsiloxy-3-aryl(hetaryl)-2-propynes
from trimethylsilylacetylene, terminal aryl or hetaryl acetylenes and carbonyl compounds has been elaborated. © 1999 Elsevier
Science S.A. All rights reserved.
Keywords: Trimethylsilylacetylene; Fluoride ion; Carbonyl compounds; Aryl and hetaryl acetylenes
prepared by InCl3-promoted addition of alkynyl stan-
nanes to aldehydes in the presence of trimethylchlorosi-
1. Introduction
lane [10]. However, trimethylsilylacetylene was used
only in the fluoride-ion-mediated reaction with 4-t-
butylcyclohexanone [3]. Therefore, the detailed study of
fluoride catalyzed reaction of trimethylsilylacetylene
with carbonyl compounds in nonpolar media was one
of the present work goals.
Aryl and hetaryl trimethylsilylacetylenes were usually
obtained in the reactions of aryl (hetaryl) acetylene with
BuLi/Me3SiCl or EtMgBr/Me3SiCl [11], ArCu with
trimethylsilyl-iodoacetylene [12] as well as in Pd cata-
lyzed alkynylation of aryl triflates [13] or halides [14].
Phenyltrimethylsilylacetylene was also a result of the
reaction of phenylacetylene in ethyl trimethylsilyl-
acetate/Bu4NF/THF [15] and trimethylsilylacetylene/
KF-Al2O3 [16] systems.
At present the reactions of organosilicon compounds
catalyzed by nucleophiles are under extensive study. In
the majority of cases a fluoride ion acting as a nucleo-
philic reagent is used for the activation of silicon bonds
[1,2]. Among these reactions the synthesis of 1-
trimethylsiloxy-3-aryl-2-propynes was described. It was
realized by the addition of 1-phenyl-2-(trimethylsi-
lyl)acetylene or other terminal silylacetylenes to car-
bonyl compounds in the Bu4NF/THF [3,4],
KF/18-crown-6/CH2Cl2 or THF [5], KF/DMF [6],
Ph4P+HF2−/DMF [7], Bu4N+HF2− [8] systems. An
intramolecular addition of silylacetylene to aldehyde in
the system CsF/18-crown-6/THF was also reported [9].
Derivatives of 1-trimethylsiloxy-2-propynes can be also
The investigation of CsF-mediated reaction of termi-
nal aryl and hetaryl acetylenes with trimethylsilyl-
acetylene in low-polarity media was the second goal of
the present work.
* Corresponding author. Tel.: +7-371-7551822; fax: +7-371-
7821038.
E-mail address: kira@osi.lanet.lv (E. Lukevics)
0022-328X/99/$ - see front matter © 1999 Elsevier Science S.A. All rights reserved.
PII: S0022-328X(99)00262-4

E. Abele et al. / Journal of Organometallic Chemistry 586 (1999) 184–189
185
were found to be optimum quantity of the fluoride ion
source. The trimethylsilylacetylene adducts to the CꢀO
double bond 1b, 3–5b, 7–10b and the corresponding
desilylated products 2b, 6b were obtained as main prod-
ucts (15–66% yield) in all reactions. The silylated ad-
ducts 1c, 3c, 6c, 7c and 1d, 3–5d, 7–10d were formed as
by-products in the reaction of 1–10b with trimethylsilyl-
acetylene or with trimethylsilylacetylene and carbonyl
compounds, respectively (Scheme 2, Table 2).
2. Results and discussion
2.1. Reactions of phenyltrimethylsilylacetylene with
carbonyl compounds in the presence of fluoride ion
We found that the reactions of aromatic and het-
eroaromatic ketones 1–3 with phenyl trimethylsilyl-
acetylene readily proceed in the phase-transfer-catalytic
(PTC) system CsF/18-crown-6/benzene at room tem-
perature. The yields of silyl ethers 1–3a were quantita-
tive. High efficiency of PTC system CsF/18-
crown-6/benzene or CH2Cl2 was also recently demon-
strated in the hydrosilylation reaction [17] (Scheme 1,
Table 1).
2.3. Reactions of trimethylsilylacetylene with terminal
aryl and hetaryl acetylenes in the presence of CsF
The silylation of terminal aryl and hetaryl acetylenes
11–14 with trimethylsilylacetylene readily proceeds in
the presence of 20 mol. % of CsF and 10 mol. % of
18-crown-6 in benzene. Formation of 11–14e was selec-
tive and reached 57–100% (Scheme 3, Table 3).
Scheme 1.
2.2. Reactions of trimethylsilylacetylene with carbonyl
compounds in the presence of fluoride ion
Scheme 3.
The reactions of aromatic and heterocyclic aldehydes
and ketones 1–10 with trimethylsilylacetylene were car-
ried out in the presence of a catalytic amount of CsF as
a fluoride ion source and 18-crown-6 in benzene. A
total of 50 mol. % of CsF to carbonyl compounds 1–10
2.4. CsF-mediated one-pot synthesis of
1-trimethylsiloxy-3-aryl(hetaryl)-2-propynes 1a, 3a,
15–25a from trimethylsilylacetylene, terminal aryl or
hetaryl acetylene and carbonyl compound
Combining the reactions discussed in Sections 2.1,
2.2 and 2.3, we have developed a new simple method to
prepare 1-trimethylsiloxy-3-aryl(hetaryl)-2-propynes 1a,
3a, 15–25a from trimethylsilylacetylene, terminal aryl
or hetaryl acetylene and carbonyl compound. Carbonyl
compounds were added to 1-aryl(hetaryl)-2-trimethyl-
silylacetylene that resulted in situ from aryl-
(hetaryl)acetylenes and trimethylsilylacetylene in the
presence of the fluoride ion. The experiments showed
that 20 mol% of CsF to substrates 11, 13 was an
optimal amount of the catalyst (Scheme 4).
Table 1
Addition of phenyltrimethylsilylacetylene to ketones in the presence
of CsF under the PTC conditions at room temperature
(Ar(Het)COMe:Me3SiCꢁCPh:CsF:18-crown-6/1:1.5:0.2:0.1)
Starting ketone
Ar(Het)
Reaction
time (h)
Product
Isolated
yield (%)
1
2
3
Ph
2-Pyridyl
2-Thienyl 15
2
2
1a
2a
3a
100
100
100
Usually the formation of 1a, 3a, 15–25a occurred
selectively, sometimes affording also small quantities
(up to 10%) of trimethylsilylacetylene adducts to car-
bonyl compounds (R2R3C(OSiMe3)CꢁCH). Products
1a, 3a, 15–25a were separated by column chromatogra-
phy and identified by 1H-NMR and mass spectra
(Table 4).
Scheme 2.
Scheme 4.

186
E. Abele et al. / Journal of Organometallic Chemistry 586 (1999) 184–189
Table 2
Trimethylsilylethynylation of aryl and hetaryl aldehydes and ketones (1–10) promoted by CsF at room temperature
(Ar(Het)COR:Me3SiCꢁCH:CsF:18-crown-6/1:1.1:0.5:0.1)
Carbonyl compound
Ar(Het)
Ph
R
Reaction time (h)
1
Products
GC yields (%)
1
Me
1b
1c**
1d
2b***
3b
3c**
3d**
4b
4d**
5b
5d**
6b***
6c**
7b
7c**
7d**
8b
8d**
9b
52
15
19
17
51
6
6
15
7
54
17
69
16
53
5
20
66
22
62
26
57
34
2*
3
2-Pyridyl
2-Thienyl
Me
Me
5
5
4
5
6
7
3-Pyridyl
Me
Me
Me
Me
1
2
5
5
4-Pyridyl
2-Methyl-5-thienyl
2-Furyl
8
Ph
H
H
H
2
1
1
9
2,3-(MeO)2C6H3
2-Thienyl
9d
10b
10d
10
* Reaction temperature was 0–10°C.
** Product was detected by MS.
*** Products 2b and 6b were isolated as corresponding alcohols.
3. Experimental
added. Reaction was carried out at room temperature
(r.t.) (GC control at 170–250°C) for 2–15 h. The
reaction mixture was filtered over a thin layer of silica
gel and evaporated at reduced pressure. The residue
was chromatographed on a silica gel column (eluents:
benzene for 1a; 1:1 benzene–petroleum ether for 2a; 4:1
benzene–ethyl acetate for 3a).
1H-NMR spectra were recorded on a Varian 200
Mercury spectrometer (200 MHz) using CDCl3 as a
solvent and HMDSO as a secondary internal standard.
Mass spectra were registered on a GC–MS HP 6890
(70 eV) apparatus. GC analysis was performed on a
Chrom-5 instrument equipped with a flame-ionization
detector using a glass column packed with 5% OV-101/
Chromosorb W-HP (80–100 mesh, 1.2 m×3 mm).
Carbonyl compounds (Aldrich) and trimethylsilyl-
acetylene (Acros) were used without additional purifica-
tion. Benzaldehyde (8) was purified by distillation in
vacuo prior to use. CsF was calcined at ca. 200°C
1H-NMR (CDCl3, HMDSO) and MS spectra data
1
for the compounds obtained. (1a) H-NMR l (ppm):
0.15 (s, 9H, SiMe3), 1.87 (s, 3H, CH3), 7.2–7.7 (m, 10H,
Ph). MS: m/z (I, %) 294 (M+, 13), 279 (M+ –Me, 89),
217 (15), 205 (35), 189 (16), 178 (9), 159 (22), 127 (23),
105 (100), 73 (79), 45 (31).
1
(2a) H-NMR l (ppm): 0.25 (s, 9H, SiMe3), 1.92 (s,
,
during 1 h. Benzene was dried with 4A molecular
sieves.
3H, CH3), 7.18 (m, 1H, H-5), 7.29 (m, 5H, Ph), 7.45 (m,
1H, H-3), 7.72 (m, 1H, H-4), 8.61 (m, 1H, H-6). MS:
m/z (I, %): 295 (M+, 18), 294 (18), 281 (M+ –Me, 14),
280 (55), 265 (10), 220 (20), 218 (24), 217 (66), 206 (29),
205 (11), 204 (41), 178 (49), 159 (21), 150 (26), 149 (60),
132 (37), 106 (20), 78 (51), 77 (15), 75 (28), 74 (13), 73
(100), 51 (18), 45 (32), 43 (28).
3.1. The reaction of carbonyl compounds 1–3 with
phenyltrimethylsilylacetylene in the presence of fluoride
ion. General procedure of the synthesis of compounds
1–3a
1
(3a) H-NMR l (ppm): 0.28 (s, 9H, SiMe3), 2.04 (s,
Freshly calcined CsF (0.03 g, 0.2 mmol) was added to
a mixture of 1–3 (1 mmol) and 18-crown-6 (0.026 g, 0.1
mmol) in 1.5 ml of dry benzene under argon atmo-
sphere. The mixture was stirred for 5 min, then
phenyltrimethylsilylacetylene (0.295 ml, 1.5 mmol) was
3H, CH3), 7.00 (m, 1H, H-4), 7.27 (m, 1H, H-5),
7.30–7.50 (m, 5H, Ph), 7.59 (m, 1H, H-3). MS: m/z (I,
%) 300 (M+, 12), 285 (M+ –Me, 100), 233 (6), 211
(49), 184 (7), 159 (13), 127 (21), 111 (70), 73 (65), 45
(30).

E. Abele et al. / Journal of Organometallic Chemistry 586 (1999) 184–189
187
Table 3
Synthesis of trimethylsilylacetylenes 11–14e promoted by cesium fluoride (Ar(Het)CꢁCH:Me3SiCꢁCH:CsF:18-crown-6/1:1.5:0.2:0.1)
Starting ketone
Ar(Het)
Reaction temperature (°C)
Reaction time (min)
Product
Isolated yield (%)
11
12
13
14
Ph
2-Pyridyl
2-Methyl-5-pyridyl
2-Thienyl
50
50
50
20
180
180
210
5
11e
12e
13e
14e
100
57
74
100
1
(4b) H-NMR l (ppm): 0.16 (s, 9H, SiMe3), 1.74 (s,
3H, CH3), 2.64 (s, 1H, CꢁCH), 7.26 (m, 1H, H-5), 7.87
(m, 1H, H-4), 8.52 (m, 1H, H-6), 8.85 (m, 1H, H-2).
MS: m/z (I, %): 219 (M+, B1), 204 (M+ –Me, 100),
130 (M+ –OSiMe3, 28), 73 (SiMe3, 37).
3.2. The reaction of carbonyl compounds 1–10 with
trimethylsilylacetylene in the presence of fluoride ion.
General procedure of the synthesis of compounds 1–10b
Freshly calcined CsF (0.075 g, 0.5 mmol) was added
to a mixture of 1–10 (1 mmol) and 18-crown-6 (0.026
g, 0.1 mmol) in 1.5 ml of dry benzene under argon
atmosphere. The mixture was stirred for 5 min, then
trimethylsilylacetylene (0.139 ml, 1 mmol) was added.
Reaction was carried out at r.t. (GC control at 170–
250°C) for 1–5 h. The reaction mixture was filtered
over a thin layer of silica gel and evaporated at reduced
pressure. The residue was chromatographed on silica
gel column (eluents: benzene for 1b, 6b, 8b; 4:1 ben-
zene–ethyl acetate for 2b, 4b; 2:1 benzene–petroleum
ether for 3b; 20:9 benzene–ethyl acetate for 5b; 10:1
benzene–ethyl acetate for 7b; 30:0.02 benzene–ethyl
acetate for 9b; 1:1 benzene–petroleum ether for 10b).
1H-NMR (CDCl3, HMDSO) and MS spectra data
for the compounds obtained.
(4d) MS: m/z (I, %): 412 (M+, 2), 73 (SiMe3, 100).
1
(5b) H-NMR l (ppm): 0.18 (s, 9H, SiMe3), 1.70 (s,
3H, CH3), 2.71 (s, 1H, CꢁCH), 7.50 (dd, 2H, J1=4.8
Hz, J2=1.8 Hz, H-3, H-5), 8.58 (dd, 2H, J1=4.8 Hz,
J2=1.8 Hz, H-2, H-6). MS: m/z (I, %): 219 (M+, B1),
204 (M+ –Me, 100), 130 (M+ –OSiMe3, 23), 73 (SiMe3,
40).
(5d) MS: m/z (I, %): 412 (M+, 1), 397 (M+ –Me,
62), 73 (SiMe3, 100).
(6b) MS: m/z (I, %): 238 (M+, 6), 223 (M+ –Me,
100), 149 (M+ –OSiMe3, 47), 134 (M+ –Me–OSiMe3,
12), 73 (SiMe3, 36). 1H-NMR of corresponding alcohol,
l (ppm): 1.94 (s, 3H, CH3), 2.54 (s, 3H, CH3), 2.58 (s,
1H, CꢁCH), 6.73(m, 1H, H-4), 7.56 (m, 1H, H-3). MS
of corresponding alcohol: m/z (I, %): 166 (M+, 21),
151 (M+ –Me, 100), 149 (M+ –OH, 14).
1
(1b) H-NMR l (ppm): 0.13 (s, 9H, SiMe3), 1.73 (s,
3H, CH3), 2.67 (s, 1H, CꢁCH), 7.25–7.60 (m, 5H, Ph).
MS: m/z (I, %): 218 (M+, B1), 203 (M+ –Me, 100).
(1c) MS: m/z (I, %): 275 (M+ –Me, 100), 105 (PhCO,
65), 73 (SiMe3, 61).
(6c) MS: m/z (I, %): 295 (M+ –Me, 100), 221 (M+
–
OSiMe3, 18), 73 (SiMe3, 48).
(7b) MS: m/z (I, %): 208 (M+, 2), 193 (M+ –Me,
100), 119 (M+ –OSiMe3, 44), 73 (SiMe3, 36).
1
(1d) H-NMR l (ppm): 0.13 and 0.20 (both s, 9H,
(7c) MS: m/z (I, %): 265 (M+ –Me, 100), 191 (M+
–
SiMe3), 1.68 (s, 6H, both CH3), 7.25–7.60 (m, 10H,
OSiMe3, 24), 73 (SiMe3, 64).
both Ph). MS: m/z (I,%): 410 (M+, B1), 395 (M+
–
(7d) MS: m/z (I, %): 375 (M+ –Me, 47), 73 (SiMe3,
Me, 43), 105 (PhCO, 22), 73 (100).
100).
1
(2b) MS: m/z (I, %): 219 (M+, 8), 204 (M+ –Me,
(8b) H-NMR l (ppm): 0.07 (s, 9H, SiMe3), 2.58 (d,
100), 189 (M+ –2Me, 44), 130 (M+ –OSiMe3, 27), 73
1H, CꢁCH), 5.48 (d, 1H, CH), 7.65 (m, 5H, Ph). MS:
m/z (I, %): 204 (M+, 31), 189 (M+ –Me, 53), 115 (100),
105 (PhCO, 10), 73 (SiMe3, 29).
1
(SiMe3, 50). H-NMR of the corresponding alcohol, l
(ppm): 1.79 (s, 3H, CH3), 2.55 (s, 1H, CꢁCH), 5.55 (s,
1H, OH), 7.27 (m, 1H, H-5), 7.64 (m, 1H, H-3), 7.76
(m, 1H, H-4), 8.52 (m, 1H, H-6). MS of the corre-
(8d) MS: m/z (I, %): 383 (M+, B1), 292 (13), 202
(10), 179 (20), 147 (35), 102 (21), 75 (15), 73 (SiMe3,
100), 45 (22).
sponding alcohol: m/z (I, %): 147 (M+, 47), 130 (M+
–
1
OH, 100).
(9b) H-NMR l (ppm): 0.18 (s, 9H, SiMe3), 2.51 (d,
1
(3b) H-NMR l (ppm): 0.18 (s, 9H, SiMe3), 1.72 (s,
3H, CH3), 2.54 (s, 1H, CꢁCH), 6.96 (m, 1H, H-4), 7.44
(m, 1H, H-5), 7.96 (m, 1H, H-3). MS: m/z (I, %): 209
(M+ –Me, 100), 135 (M+ –OSiMe3, 41), 73 (SiMe3,
39).
1H, J=2.2 Hz, CꢁCH), 3.86 (s, 3H, OMe), 3.89 (s, 3H,
OMe), 5.84 (d, 1H, J=2.2 Hz, CH), 6.87 (dd, 1H,
J1=8.2 Hz, J2=1.4 Hz, H-6), 7.08 (t, 1H, J=8.2 Hz,
H-5), 7.26 (dd, 1H, J1=8.2 Hz, J2=1.4 Hz, H-4). MS:
m/z (I, %): 264 (M+, 36), 249 (M+ –Me, 74), 234
(M+ –2Me, 32), 233 (M+ –OMe, 32), 219 (M+ –3Me,
12), 175 (M+ –OSiMe3, 39), 73 (100).
(3c) MS: m/z (I, %): 281 (M+ –Me, 100), 207 (M+
–
OSiMe3, 12), 73 (SiMe3, 45).
(3d) MS: m/z (I, %): 407 (M+ –Me, 43), 73 (SiMe3,
(9d) H-NMR l (ppm): 0.15 and 0.17 (both s, 9H,
1
100).
SiMe3), 3.86 (m, 12H, OMe), 5.91 (s, 2H, CH), 6.90,

188
E. Abele et al. / Journal of Organometallic Chemistry 586 (1999) 184–189
Table 4
Fluoride-ion-mediated synthesis of silyl ethers 1a, 3a, 15–25a from trimethylsilylacetylene, aryl acetylene and carbonyl compound
(R1CꢁCH:Me3SiCꢁCH:CsF:18-crown-6:R2COR3/1:1:0.2:0.1:1)
R1
R2
R3
Reaction time (h)
Product
Isolated yield (%)
Ph
Ph
Ph
Ph
Ph
Ph
Ph
2-Thienyl
Et
Me
Me
Me
H
Me
Me
Me
H
Me
Me
Me
Me
Me
8
11
5
6
8
5
6
6
9
6
6
9
5
1a
3a
61
47
57
61
58
51
65
61
58
57
58
55
55
15a
16a
17a
18a
19a
20a
21a
22a
23a
24a
25a
Ph
3-Pyridyl
4-Pyridyl
Et
Ph
Ph
2-Thienyl
2-Pyridyl
3-Pyridyl
4-Pyridyl
2-Methyl-5-pyridyl
2-Methyl-5-pyridyl
2-Methyl-5-pyridyl
2-Methyl-5-pyridyl
2-Methyl-5-pyridyl
2-Methyl-5-pyridyl
2-Methyl-5-pyridyl
1
(13e) H-NMR, l ppm: 0.06 (s, 9H, SiMe3), 2.33 (s,
3H, CH3), 6.87 (d, 1H, J=8 Hz, H-3), 7.42 (dd, 1H,
J1=8 Hz, J2=2 Hz, H-4), 8.39 (d, 1H, J=8 Hz, H-6).
MS: m/z (I, %): 189 (M+, 18), 175 (16), 174 (M+ –Me,
100), 144 (5), 77 (5), 73 (3), 53 (5), 43 (7).
7.10 and 7.30 (m, 2H, protons of Ph). MS: m/z (I, %):
502 (M+, 5), 73 (100).
1
(10b) H-NMR l (ppm): 0.22 (s, 9H, SiMe3), 2.63 (s,
1H, CꢁCH), 5.70 (m, 1H, CH), 6.95 (m, 1H, H-4), 7.12
(m, 1H, H-3), 7.27 (m, 1H, H-5). MS: m/z (I, %): 210
(M+, 34), 195 (M+ –Me, 18), 121 (M+ –OSiMe3, 100),
73 (SiMe3, 35).
1
(14e) H-NMR, l ppm: 0.20 (s, 9H, SiMe3), 6.69 (m,
1H, H-4), 6.95 (s, 1H, H-5), 7.00 (s, 1H, H-3). MS: m/z
(I,%): 180 (M+, 23), 167 (10), 166 (14), 165 (M+ –Me,
100), 135 (M+ –3Me, 6), 77 (8), 75 (6), 53 (6), 43 (9).
(10d) MS: m/z (I, %): 394 (M+, 7), 73 (SiMe3, 100).
3.3. The reactions of terminal aryl and hetaryl
acetylenes 11–14 with trimethylsilylacetylene in the
presence of the fluoride ion. General procedure of the
synthesis of aryl and hetaryl trimethylsilylacetylenes
11–14e
3.4. General procedure for the one-pot fluoride-ion-
mediated synthesis of 1-trimethylsiloxy-3-aryl(hetaryl)-
2-propynes 1a, 3a, 15–25a from trimethylsilylacetylene,
terminal acetylene and carbonyl compound
Freshly calcined CsF (0.03 g, 0.2 mmol) was added to
a mixture of 11–14 (1 mmol) and 18-crown-6 (0.026 g,
0.1 mmol) in 1.5 ml of dry benzene under argon
atmosphere. After 5 min stirring the trimethylsilyl-
acetylene (0.207 ml, 1.5 mmol) was added. Reaction
was carried out for 5–210 min (GC control, 130°C).
The reaction mixture was filtered over a thin layer of
silica gel and evaporated at reduced pressure. The
residue was chromatographed on silica gel column
using 10:1 petroleum ether–benzene (11e), 6:1 benzene–
ethyl acetate (12e), 5:1 benzene–ethyl acetate (13e) and
2:1 benzene–petroleum ether (14e) as eluents.
Freshly calcined CsF (0.0302 g, 0.2 mmol) and
trimethylsilylacetylene (0.139 ml, 1 mmol) were added
to a solution of terminal acetylene (phenyl acetylene
(11) or 2-methyl-5-ethynylpyridine (13), 1 mmol) and
18-crown-6 (0.026 g, 0.1 mmol) in dry benzene (1.5 ml).
The reaction mixture was heated at 50°C for 3 h under
argon. Then the reaction mixture was cooled to r.t. The
carbonyl compound (1 mmol) was added and the reac-
tion mixture was stirred for 5–11 h at r.t. (GLC
control). The reaction mixture was evaporated under
reduced pressure. The residue was purified by column
chromatography (eluent: benzene for compounds 1a,
3a, 15a, 16a, or benzene–ethyl acetate in different
ratios for compounds 17–25a).
1H-NMR and MS data for the compounds isolated.
1
(11e) H-NMR, l ppm: 0.31 (s, 9H, SiMe3), 7.44 (m,
5H, Ph). MS: m/z (I, %): 174 (M+, 17), 160 (16), 159
(M+ –Me, 100), 129 (8), 105 (8), 79 (5), 77 (3), 53 (6),
43 (9).
1H-NMR and MS data for compounds isolated.
1
(15a) H-NMR l (ppm): 0.18 (s, 9H, SiMe3), 0.98 (t,
3H, J=7.0 Hz, CH2CH3), 1.46 (s, 3H, CCH3), 1.62 (q,
2H, J=7.0 Hz, CH2CH3), 7.24 (m, 5H, Ph). MS: m/z
(I, %) 245 (M+ −1, B1), 231 (11), 217 (100), 159 (19),
141 (9), 129 (14), 115 (11), 73 (57), 57 (10), 43 (25).
1
(12e) H-NMR, l ppm: 0.27 (s, 9H, SiMe3), 7.22 (m,
1H, H–3), 7.45 (m, 1H, H-4), 7.63 (m, 1H, H-5), 8.56
(m, 1H, H-6). MS: m/z (I, %): 175 (M+, 24), 160
(M+ –Me, 100), 145 (M+ –2Me, 4), 132 (11), 106 (12),
43 (8).
1
(16a) H-NMR l (ppm): 0.13 (s, 9H, SiMe3), 7.10–
7.70 (m, 11H, Ph and CH). MS: m/z (I, %) 280 (M+,

E. Abele et al. / Journal of Organometallic Chemistry 586 (1999) 184–189
189
35), 265 (M+ –Me, 14), 206 (15), 191 (100), 159 (40),
129 (7), 105 (14), 73 (82), 45 (29).
(17a) H-NMR l (ppm): 0.16 (s, 9H, SiMe3), 1.77 (s,
205 (12), 190 (61), 178 (49), 149 (58), 140 (30), 106 (25),
78 (43), 73 (100), 45 (32).
(24a) H-NMR l (ppm): 0.16 (s, 9H, SiMe3), 1.73 (s,
1
1
3H, CH3), 2.49 (s, 3H, CH3 in ring), 7.04 (m, 1H, H-3),
7.24 (m, 6H, Ph, H%-5), 7.56 (m, 1H, H-4), 7.80 (m, 1H,
H%-4), 8.49 (m, 2H, H-6 and H%-6), 8.85 (m, 1H, H%-2).
MS: m/z (I, %) 310 (M+, 10), 309 (20), 295 (M+ –Me,
100), 232 (9), 221 (30), 205 (9), 190 (9), 174 (23), 106
(51), 73 (97), 45 (32).
3H, CH3), 7.24 (m, 6H, Ph and H-5), 7.73 (m, 1H,
H-4), 8.42 (m, 1H, H-6), 8.93 (m, 1H, H-2). MS: m/z (I,
%) 295 (M+, 10), 294 (15), 280 (M+ –Me, 98), 217
(11), 206 (36), 178 (10), 159 (29), 127 (11), 106 (49), 73
(100), 45 (33).
1
(18a) H-NMR l (ppm): 0.16 (s, 9H, SiMe3), 1.69 (s,
1
(25a) H-NMR l (ppm): 0.16 (s, 9H, SiMe3), 1.73 (s,
3H, CH3), 7.25 (m, 5H, Ph), 7.40 (m, 2H, H-3 and
H-5), 8.49 (m, 2H, H-2 and H-6). MS: m/z (I, %) 295
(M+, 11), 280 (M+ –Me, 96), 217 (21), 206 (25), 178
(15), 159 (40), 106 (15), 73 (100), 45 (29).
3H, CCH3), 2.53 (s, 3H, CH3 in ring), 7.02 (m, 1H,
H-3), 7.48 (m, 2H, H%-3 and H%-5), 7.62 (m, 1H, H-4),
8.51 (m, 3H, H-6, H%-2 and H%-6). MS: m/z (I, %) 310
(M+, 9), 309 (12), 295 (M+ –Me, 100), 232 (15), 221
(24), 190 (13), 174 (35), 106 (16), 73 (99), 45 (27).
1
(19a) H-NMR l (ppm): 0.16 (s, 9H, SiMe3), 0.96 (t,
3H, J=7.2 Hz, CH2CH3), 1.47 (s, 3H, CCH3), 1.64 (q,
2H, J=7.2 Hz, CH2CH3), 2.49 (s, 3H, CH3 in ring),
7.04 (m, 1H, H-3), 7.47 (m, 1H, H-4), 8.44 (m, 1H,
H-6). MS: m/z (I, %) 261 (M+, 1), 246 (M+ –Me, 11),
232 (100), 190 (63), 174 (15), 144 (8), 129 (9), 73 (64), 45
(21).
References
[1] C. Chuit, R.J.P. Corriu, C. Reye, J.C. Young, Chem. Rev. 93
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[2] G.G. Furin, O.A. Vyazankina, B.A. Gostevsky, N.S. Vyazankin,
Tetrahedron 44 (1988) 2675.
1
(20a) H-NMR l (ppm): 0.29 (s, 9H, SiMe3), 2.28 (s,
3H, CH3), 7.11 (m, 1H, H-3), 7.47 (m, 1H, H-4),
7.50–7.90 (m, 6H, Ph and CH), 8.51 (m, 1H, H-6). MS:
m/z (I, %) 295 (M+, 43), 280 (M+ –Me, 26), 221 (21),
206 (93), 190 (10), 174 (50), 152 (11), 139 (21), 105 (13),
89 (9), 73 (100), 45 (27).
[3] I. Kuwajima, E. Nakamura, K. Hashimoto, Tetrahedron 39
(1983) 975.
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(1976) 498.
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Akinde, D.R.M. Walton., J. Chem. Soc. Chem. Commun. (1979)
840.
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Synlett (1997) 693.
[9] T. Nishikawa, S. Shibuya, M. Isobe, Synlett (1994) 482.
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(1995) 9497.
[11] C. Eaborn, D.R.M. Walton, J. Organomet. Chem. 2 (1964) 95.
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[13] T. Okita, M. Isobe, Synlett (1994) 589.
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[15] E. Nakamura, T. Murofushi, M. Shimizu, I. Kuwajima, J. Am.
Chem. Soc. 98 (1976) 2346.
1
(21a) H-NMR l (ppm): 0.17 (s, 9H, SiMe3), 1.79 (s,
3H, CCH3), 2.50 (s, 3H, CH3 in ring), 7.16 (m, 1H,
H-3), 7.56 (m, 1H, H-4), 8.51 (m, 1H, H-6). MS: m/z (I,
%) 310 (M+, 3), 308 (13), 294 (84), 220 (36), 204 (10),
174 (18), 142 (9), 105 (100), 73 (88), 45 (29).
1
(22a) H-NMR l (ppm): 0.28 (s, 9H, SiMe3), 2.06 (s,
3H, CCH3), 2.71 (s, 3H, CH3 in ring), 7.01 (m, 1H,
H%-4), 7.22 (m, 1H, H-3), 7.33 (m, 1H, H%-5), 7.64 (m,
1H, H%-3), 7.80 (m, 1H, H-4), 8.73 (m, 1H, H-6). MS:
m/z (I, %) 315 (M+, 16), 300 (M+ –Me, 100), 226 (51),
210 (7), 174 (13), 142 (10), 111 (93), 73 (97), 45 (36).
1
(23a) H-NMR l (ppm): 0.09 (s, 9H, SiMe3), 1.64 (s,
3H, CCH3), 2.31 (s, 3H, CH3 in ring), 7.09 (m, 2H, H-3
and H%-5), 7.42 (m, 3H, H-4, H%-3 and H%-4), 8.34 (m,
2H, H-6 and H%-6). MS: m/z (I, %) 310 (M+, 27), 309
(34), 295 (M+ –Me, 67), 280 (12), 232 (56), 221 (31),
[16] T. Baba, A. Kato, H. Yuasa, F. Toriyama, H. Handa, Y. Ono,
Catal. Today 44 (1998) 271.
[17] Yu. Goldberg, E. Abele, M. Shymanska, E. Lukevics, J.
Organomet. Chem. 410 (1991) 127.
.
.