Pt-Catalyzed Hydrosilylation of 1,3-Diynes with Triorganosilanes: Regio- and Stereoselective Synthesis of Mono- or Bis-silylated Adducts

Article abstract of DOI:10.1021/acs.joc.8b03143

An efficient method has been successfully developed for the functionalization of various 1,3-diynes by the hydrosilylation reaction with triethyl- or triphenylsilane catalyzed by Pt catalysts (Pt₂(dvs)₃, PtO₂, or Pt(PPh₃)₄). Comprehensive optimization studies were performed for the first time to find suitable process conditions for the stereo- and regioselective formation of mono- or bis-silylated adducts from commercially available substrates and catalysts. Silyl-substituted 1,3-enynes or bis-silyl-functionalized buta-1,3-dienes were obtained with excellent yields and fully characterized.

Full text of DOI:10.1021/acs.joc.8b03143

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Note
Pt-catalyzed hydrosilylation of 1,3-diynes with triorganosilanes –
regio- and stereoselective synthesis of mono- or bissilylated adducts
Jedrzej Walkowiak, Katarzyna Salamon, Adrian Franczyk,
Kinga Stefanowska, Jakub Szyling, and Ireneusz Kownacki
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.8b03143 • Publication Date (Web): 22 Jan 2019
Downloaded from http://pubs.acs.org on January 24, 2019
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Pt-catalyzed hydrosilylation of 1,3-diynes with
triorganosilanes – regio- and stereoselective
synthesis of mono- or bissilylated adducts
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*,†
Jędrzej Walkowiak, Katarzyna Salamon, Adrian Franczyk, Kinga Stefanowska, Jakub
†,‡
†
†,‡
†,‡
Szyling and Ireneusz Kownacki
†,‡
†
Center for Advanced Technology, Adam Mickiewicz University in Poznan, Umultowska 89c,
61-614 Poznan, Poland.
‡
Faculty of Chemistry, Adam Mickiewicz University in Poznan, Umultowska 89b, 61-614
Poznan, Poland.
* E-mail: jedrzej.walkowiak@amu.edu.pl
For a Table of Contents use only
R3Si
H
1 eqiv.
R3SiH
• The first mono- or bishydrosilylation of 1,3-diynes
with equimolar reagents ratio,
R
R
H
[Pt]
• Commercially available reagents and Pt catalysts,
• High products yields and processes selectivities.
R
R
R
SiR3
2 eqiv. R3SiH
H
SiR3
R
[Pt] = Pt2(dvs)3, Pt(PPh3)4, PtO2
SiR3 = SiEt3, SiPh3
R
= CH3, (CH2)8COOCH3, t-Bu, (CH3)3SiOC(CH3)2, Ph
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ABSTRACT: An efficient method has been successfully developed for the functionalization of
various 1,3-diynes by the hydrosilylation reaction with triethyl- or triphenylsilane catalyzed by Pt
catalysts (Pt2(dvs)3, PtO2 or Pt(PPh3)4). Comprehensive optimization studies were performed for the
first time to find suitable process conditions for the stereo- and regioselective formation of mono-
or bissilylated adducts from commercially available substrates and catalysts. Silylsubstituted 1,3-
enynes or bissilyl-functionalized buta-1,3-dienes were obtained with excellent yields and fully
characterized.
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Conjugated 1,3-diynes constitute useful and versatile building blocks in the synthesis of natural
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1-11
compounds, pharmaceuticals, π-conjugated polymers and optoelectronic materials. Their
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8
functionalization occurs mostly via the addition reaction to the unsaturated C-C bonds and can
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3,12,13
lead to multisubstituted products. The regio- and stereoselectivity of such processes depends on
the structure of 1,3-diyne, the second reagent, the catalyst, and the process conditions.
12-21
Straightforward and 100% atom efficient hydrosilylation of alkynes, which occurs via the
addition of the Si-H bond to the C≡C bond, facilitates the modification of 1,3-diynes to
22-26
silylfunctionalized 1,3-enyes or disilylsubstituted 1,3-butadienes or allenes. The ability to form
nine different isomers shows the process complexity. The reactivity of silyl groups in desilylation
or coupling processes leads to such products representing useful (enyne and diene) synthons in
27-36
advanced organic synthesis. The high tolerance of the hydrosilylation process to various
functional groups, its simplicity and diversity of the selectivity makes this method the first choice
when the incorporation of a silyl group into the molecule is required. A number of scientific articles
13-16,33,37,38
discuss the modification of monoynes with organosilicon compounds,
but the
functionalization of conjugated 1,3-diynes, due to their much more complex structure, is far more
difficult to control according to the regio- and stereoselectivity, and is limited to just a few
23-26
examples. In the reported works, the hydrosilylation of conjugated diynes has been catalyzed by
23-26
homogeneous or heterogeneous catalysts containing Ru, Rh, Ni, Pd, Pt. Depending on the type
of the catalyst, reagents and reaction conditions, substituted but-3-en-1-ynes, buta-1,3-dienes,
allenes or polymeric systems, cross-linked with silyl moieties have been obtained. Several
molecular catalysts (e.g. commercially used Pt Karstedt’s complex – Pt2(dvs)3 (Platinum (0)-1,3-
divinyl-1,1,3,3-tetramethyldisiloxane complex)), as well as nanoparticles, have been examined in
the hydrosilylation of conjugated diynes but, unfortunately the previously published articles do not
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contain detailed studies on the process conditions (reagents molar ratio, temperature, reaction time)
or their efficiency. The results showed that it is possible to form different silylated enynes or
bissilylated dienes in a more or less predictable manner, but the utility of the method is limited
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only to several diynes, which did not exhaust the subject of their Si-functionalization.
In light of this research, we have noticed that there is still a lack of comprehensive studies on
the formation of mono- and bisadducts in the hydrosilylation of 1,3-diynes using a stoichiometric
quantity of reagents and commercially available catalysts. Moreover, the aim of our study was to
develop straightforward and efficient protocols for the preparation of such compounds which can
be further used as building blocks in organic synthesis.
Therefore, we examined mono- and bishydrosilylation of structurally and electronically different
1,3-diynes, i.e.: hexa-2,4-diyne (2a), 10,12-docosadiyndioic acid dimethyl ester (2b) 2,2,7,7-
tetramethyl-3,5-octadiyne (2c), 1,4-(1,1-dimethyloxy-trimethylsilyl)buta-1,3-diyne (2d) and 1,4-
diphenylbuta-1,3-diyne (2e) with Et3SiH (1a) or Ph3SiH (1b), using stoichiometric quantities of
reagents in the presence of commercially available catalysts: Pt2(dvs)3 (I), Pt(PPh3)4 (II) or PtO2
(III). In the previously reported studies, the best selectivities were achieved in the reactions with
using the silanes or 1,3-diynes in excess. Moreover, no optimization concerning the reagent ratio
or concentration was discussed. Due to the high atom efficiency of the hydrosilylation reaction,
the equimolar ratio of reagents has a positive impact on the process economy and the post-reaction
mixture separation.
At the beginning of our research, we used free of steric hindrance Et3SiH (1a) as a reagent and
Pt2(dvs)3 (I), which is the first choice in the hydrosilylation reaction, and in the industrial scale.
-4
The initial catalytic tests were carried out with 4x10 mol of Pt/1 mol Si-H ratio at 100 C. The
o
monohydrosilylation of linear diynes 2a and 2b in the presence of I, due to the easy access of
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silane to unsaturated bonds was nonselective (Table 1, entry 1, 8). The application of the equimolar
amount of reagents under standard reaction conditions led to the mixture of mono- and bisadduct.
Lowering the reaction temperature to r.t. and a 10-fold excess of diyne over silane led to the
obtaining of monoadduct in the vast majority of cases (Table 1, entry 2). The application of more
sterically crowded and less reactive 1 mol% of [Pt(PPh3)4] (II) revealed the formation of a single
product 3ac under the same process conditions for the first time (Table 1, entry 4). The total
conversion of reagents used in 1:1 molar ratio was achieved after 24 h. The same Pt-complex
selectively catalyzed the monohydrosilylation of 2b (Table 1, entry 6). Raising the temperature to
40°C immediately affected the reaction selectivity by increasing the amount of bisadduct
formation, for the processes catalyzed by II and III. Typical reaction conditions were sufficient
for bishydrosilylation of 2a with 2 equiv. of 1a in 6 hours (Table 1, entry 3). However, doubling
the Pt2(dvs)3 (I) concentration and extending the reaction time to 24 h was required for the
quantitative synthesis of product 4ab (Table 1, entry 10).
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The Pt Karstedt’s catalytic system worked well in the monohydrosilylation of bulky 2,2,7,7-
tetramethyl-3,5-octadiyne (2c) and electron rich 1,4-bistrimethylsiloxy-1,3-butadiyne (2d). The
reaction occurred quantitatively with the syn-addition of silane and formation of internal alkenyl
silanes 3ac and 3ad (Table 1, entries 11, 13).
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Table 1. Hydrosilylation of 1,3-diynes (2a-e) with
triethylsilane (1a) in the presence of Pt catalysts (I-
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a
III).
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Et3Si
Et3Si
(1a)
+
H
R
SiEt3
Side products:
H
[Pt] (I-III)
toluene
R
monoadducts (5aa-ae)
bisadducts (6aa-ae)
other by-products (7aa-7ae)
H
+
+
H
R
R
SiEt
3 R
(4aa-ae)
(2a-e)
R
(3aa-ae)
R = CH3, (CH2)8COOCH3, t-Bu, (CH3)3SiOC(CH3)2, Ph
[Pt] = [Pt2(dvs)3]. [Pt(PPh3)4], [PtO2]
(a)
(b)
(c)
(d)
(e)
(I)
(II)
(III)
Conv.
of 1a
Selectivity
3/4/5/6/7
t
[h]
Ent.
2
[Pt]/[1a]/[2]
Cat.
T [°C]
[%]
99
99
99
99
99
99
99
64
80
99
99
75
99
50
99
95
[%]
1
2a
2b
4x10-4/1/1
4x10-3/1/10
4x10-4/2/1
10-2/1/1
I
100
r.t.
24
6
31/64/0/5/0
94/1/4/0/0
0/99/0/0/0
99/0/0/0/0
89/10/0/0/0
99/0/0/0/0
89/10/0/0/0
56/0/3/0/5
45/0/35/0/0
0/99/0/0/0
99/0/0/0/0
42/52/5/0/0
99/0/0/0/0
99/0/0/0/0
99/0/0/0/0
95/0/0/0/0
2
I
3
I
100
r.t.
6
4
II
II
II
II
I
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24
24
48
24
70
24
24
48
24
24
24
24
5
10-2/1/1
40
6
10-2/1/1.1
10-2/1/1
r.t.
7
r.t.
8
4x10-3/1/1
4x10-2/1/1
8x10-4/2/1
4x10-4/1/1
8x10-4/2/1
4x10-4/1/1
8x10-4/2/1
2x10-1/1/1
9.7x10-2/1/1
100
40
9
III
I
10
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12
13
14
15
16
140b
100
140b
100
100
40
2c
2d
2e
I
I
I
I
III
III
40
17
18
19
20
21
9.7x10-2/1/1
6x10-2/1/1
6x10-2/1/1
4x10-4/1/1
4x10-3/1.1/1
8x10-4/2/1
III
II
II
I
60
24
72
24
48
48
24
98
98
99
91
98
99
95/1/1/1/0
91/7/0/0/0
89/10/0/0
64/23/2/2/0
96/1/1/0/0
0/93/0/6/0
40
60
100
60
I
22
I
140b
a
Reaction conditions: toluene (2 mL). Conversions of
reagents were determined by GC and GC-MS analysis;
1
process selectivity was confirmed by H, Si NMR, GC-
b
MS; reaction carried out in xylene.
29
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The synthesis of bisadduct was not successful for the hydrosilylation of 2d, while the
employment of silane to 2c led to a mixture of mono- (3ac) and bisadduct (4ac), even when a two-
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-4
fold excess of 1a, 8x10 mol of Pt2(dvs)3 (I) and a higher temperature of 140°C were applied (Table
1, entry 12). Nevertheless, the formation of bisadduct with this bulky reagent 2c was not detected
in any previously published works when a higher excess of silane was used. The selective
hydrosilylation of electronically different 1,4-diphenylbuta-1,3-diyne (2e) to form defined
silylated product is difficult to implement. The equimolar hydrosilylation in the presence of I under
various concentrations and temperatures occurred with a poor selectivity (Table 1, entry 20-22).
Similar results were obtained when pre-catalyst (II) was used at 60°C and 40°C (Table 1, entry
18, 19). The incomplete conversion of reagents and the recurring presence of bisadduct in the post-
reaction mixture were observed. The exclusive synthesis of monosilylated product 3ae was
-1
possible when 2x10 mol of III was used and the reaction was carried out at 40°C for 24 h (Table
1, entry 15). However, in order to obtain bissilylated product, the reagents and catalyst I were used
-4
in the ratio [I]:[1a]:[2e] = 8x10 :1:2. After 24 h at 140°C, the complete conversion of substrates
was achieved and two isomeric products were formed (4ae/6ae = 93/6) – Table 1, entry 22. The
synthesis of bisadducts with different silanes has already been described in the literature but in all
cases, an excess of silane or diyne were used. No equimolar quantity of reagents was used, which
is reported for the first time in this document.
Table 2. Hydrosilylation of 1,3-diynes (2a-e) with
triphenylsilane (1b) in the presence of Pt catalysts (I-
a
III).
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Ph3Si
Ph3Si
(1b)
+
H
R
SiPh3
Side products:
monoadducts (5ba-be)
+
bisadducts (6ba-be)
H
[Pt] (I-III)
H
+
H
toluene
R
R
R
other by-products (7ba-7be)
SiPh
3R
(4ba-be)
(2a-e)
R
(3ba-be)
6
7
R = CH3, (CH2)8COOCH3, t-Bu, (CH3)3SiOC(CH3)2, Ph
(a) (b) (c) (d) (e)
[Pt] = [Pt2(dvs)3]. [Pt(PPh3)4], [PtO2]
(I)
(II)
(III)
8
9
Selectivity
3/4/5/6/7
[%]
Conv.
of 1b
[%]
t
T
[°C]
Ent.
2
[Pt]/[1b]/[2]
Cat.
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12
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[h]
1
2
2a 4x10-4/1/1
I
I
100
60
24
24
99
99
92/8/0/0/0
95/5/0/0/0
4x10-4/1/1
3
8x10-3/1/1
4x10-3/2/1
I
r.t.
48
48
24
120
24
48
24
24
48
72
24
99
99
83
99b
99
99
90b
99
77
99
99
99/0/0/0/0
90/0/10/0/0
19/57/0/0/0
93/0/7/0/0
47/0/53/0
4
I
100
100
r.t.
5
4x10-4/2/1
I
6
2b 4x10-2/1/1
9.7x10-2/1/1
4x10-3/1/1
II
III
I
7
100
r.t.
8
93/0/7/0/0
10/80/0/10/0
99/0/0/0/0
50/0/0/0/27
99/0/0/0/0
99/0/0/0/0
9
4x10-4/2/1
I
100
100
100
100
100
10
11
12
13
2c 4x10-3/1/1
4x10-4/2/1
I
I
2d 4x10-4/1/1
2e 4x10-3/1/1
I
I
14
8x10-4/2/1
I
100
24
77
50/0/0/0/27
a
Reaction conditions: toluene (2 mL). Conversions of
reagents were determined by GC and GC-MS analysis;
1
process selectivity was confirmed by H, Si NMR, GC-MS;
29
b
reaction carried out in xylene.
The same optimization was carried out for mono- and bisaddition of more hindered Ph3SiH (1b)
to 1,3-diynes (2a-e). The hydrosilylation of hexa-1,3-diyne (2a) under standard reaction conditions
led to the formation of monoadduct 3ba in high excess to the bisilylated hexa-1,3-diene (4ba)
(Table 2, entry 1). Lowering the process temperature to r.t., as well as increasing that of the Pt2(dvs)3
catalyst (I) concentration by an order of magnitude, and doubling the reaction time, exclusively
yielded product 3ba with a complete conversion of reagents used in the 1:1 ratio (Table 2, entry
3). The product 3ba was easily crystallized from the n-hexane, by its slow evaporation and the X-
ray structure was measured. The analysis of the crystal structure clearly showed that the process
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occurred regioselectively with the syn-addition of the Si-H bond into the C-C triple bond and the
formation of β-E-product (for details see SI). The selective synthesis of bissilylated buta-1,3-
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8
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diene was not possible. A mixture of mono- and bissilylated products were obtained irrespective
of the process conditions (Table 2, entry 4, 5). The bulkier silane 1b did not affect the selectivity
of the hydrosilylation of 2b. In that case, again the application of Pt2(dvs)3 (I), [Pt(PPh3)4](II) and
r.t. were necessary to obtain isomer 3bb with a 93% yield (Table 2, entry 6, 8). When a higher
temperature and catalysts I or III were used, both isomers were obtained in different ratios.
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-2
Moreover, 4x10 mol of Pt had to be used to provide the total conversion of 1b. Because of the
steric hindrance of silane 1b and 2,2,7,7-tetramethyl-3,5-octadiyne (2c) in the hydrosilylation
reaction the only monoadduct 3bc was formed, even when the ratio 2c/1b = 1:2 was used. The
crystal structure of compound 3bc was measured, showing that the β-E-isomer was obtained in
the syn-addition of 1b to the C≡C bond of 2c (the molueclar structure of 3bc is presented in SI).
Hydrosilylation of another bulky diyne 2d required an extension of the reaction time to 72 h for
more steric 1b, compared to an analog reaction with 1a. In this particular case, the synthesis of
bisadduct was not achieved.
Hydrosilylation of 2e with 1b occurred selectively with the application of I. In order to reach
total conversion during the monohydrosilylation reaction, reagents and a catalyst were used with
-3
the following ratio: I:1b:2e = 4x10 :1:1 (Table 2, entry 13). A lower concentration of the catalyst
was insufficient for obtaining a high yield of the desired product. The formation of bisadduct 4be
with a 2-fold excess of 1b did not occur (Table 2, entry 14). Compound 3be was the only product.
The isolated yields of the mono- and bishydrosilylation products obtained under optimized
reaction conditions (Tables 1 and 2) are presented in Figure 1.
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Et3Si
H
Et3Si
H
H
H3COOC(H2C)8
H
SiEt3
H
H3C
Et3Si
Et3Si
(CH2)8COOCH3
CH3
SiEt3
CH3
H3COOC(H2C)8
H3C
H
(CH2)8COOCH3
3aa
91%
4aa
84%
3ab
82%
4ab
87%
H
Et3Si
H
Et3Si
Et3Si
H
H
SiEt3
Ph
Ph
Et3Si
Ph
OSiMe3
9
Ph
H
Me3SiO
Ph3Si
3ac
92%
3ad
92%
3ae
98%
4ae
93%
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Ph3Si
H
H
Ph3Si
H
Ph3Si
H
Ph3Si
H
CH3
H3COOC(H2C)8
(CH2)8COOCH3
Ph
OSiMe3
Ph
H3C
Me3SiO
3bd
91%
3ba
89%
3bb
85%
3bc
90%
3be
90%
Figure 1. The isolated yields of mono- and bishydrosilylation products.
We have clearly demonstrated that the application of commercially available catalysts and the
appropriate choice of reaction conditions and reagents made it possible to obtain the desired mono-
or bisilylated products in the hydrosilylation of 1,3-diynes with high yields and selectivities. The
reactions occurred via syn-addition of tertiary silane to the C-C triple bond with the formation of
the internal alkenyl silane. Pt-Karstedt’s catalyst was used for the synthesis of bisadducts, while
PtO2 and Pt(PPh3)4 because of their lower activity were more sufficient for the selective formation
of monosilylated enynes. For the first time, applying optimized reaction conditions, it was possible
to obtain the desired product using equimolar quantities of reagents, which due to the atom-
economy reaction simplifies the separation procedure and reduces the cost of the process.
Experimental Section
General information.
Fourier Transform-Infrared (FT-IR) spectra were recorded on a Bruker Tensor 27 Fourier
transform spectrophotometer equipped with a SPECAC Golden Gate, diamond ATR unit, with
−1
ensuring a resolution of 2cm .
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NMR spectra were recorded at 25°C on a Bruker Ultra Shield 300 MHz or Bruker Ascend 400
MHz NANOBAY spectrometers. CDCl3 was used as a solvent and for internal deuterium lock.
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13
Chemical shifts were reported in ppm with reference to the residual solvent peaks for H and C
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NMR and to TMS for Si NMR. The multiplicities were reported as follows: singlet (s), doublet
(d), a doublet of triplets (dt), multiplet (m), triplet (t) and broad resonances (br).
GC-MS analyses were performed on a Bruker 450-GC with a 30 m Varian DB-5 0.25 mm capillary
column and a Scion SQ-MS detector. Two temperature programs were used a) 80°C (3 min),
10°C/min, 250 °C (30 min), b) 150°C (3 min), 10°C/min, 280°C (44.5 min).
GC analyses were performed on a Bruker Scion 435-GC equipped with a 30 m Varian DB-5 0.25
mm capillary column. Two temperature programs were used a) 80°C (3 min), 10°C/min, 250°C
(30 min), b) 150°C (3 min), 10°C/min, 280 °C (44.5 min).
Elemental analyses were carried out on Vario EL III Analyser. The content of hydrogen and carbon
was obtained as data in percentage.
Diffraction data were collected by the ω-scan technique at room temperature (1) or at 100(1) K
(2) on Rigaku XCalibur four-circle diffractometer with EOS CCD detector and graphite-
monochromated MoKα radiation (λ=0.71073 Å). The data were corrected for Lorentz-polarization
40
as well as for absorption effects. Precise unit-cell parameters were determined by a least-squares
fit of 5900 (1) and 5637 (3) reflections of the highest intensity, chosen from the whole experiment.
41
The structures were solved with SHELXT-2013 and refined with the full-matrix least-squares
2
42
procedure on F by SHELXL-2013. All non-hydrogen atoms were refined anisotropically,
hydrogen atoms were placed in idealized positions and refined as ‘riding model’ with isotropic
displacement parameters set at 1.2 (1.5 for CH3) times Ueq of appropriate carrier atoms.
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Crystallographic data for the structural analysis has been deposited with the Cambridge
Crystallographic Data Centre, Nos. CCDC-1873913 (3ba) and CCDC-1873914 (3bc). Copies of
this information may be obtained free of charge from: The Director, CCDC, 12 Union Road,
Cambridge, CB2 1EZ, UK; e-mail: deposit@ccdc.cam.ac.uk, or www: www.ccdc.cam.ac.uk.
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To prove the regioselectivity of the process, cis-addition of silane (1a) to diyne (2a or 2c), and
formation of products 4aa and 3ac, for which we did not obtain any crystal structures, we have
carried out additional 1H-13C HSQC and NOESY 2D NMR experiments. Theses analysis clearly
showed the assumed process selectivity (for details see SI).
Melting Point analyses were carried out using Melting Point M-565 Buchi apparatus equipped
with a CD Demo MeltingPoint Monitor. The compound was placed in the capillary and heated
with the temperature gradients 2.5°C/min, 5°C/min and 10°C/min. The melting point was detected
automatically and by the visual inspections through the lens. Each analysis was repeated three
times.
General procedure for hydrosilylation of 1,3-diynes (2a–e) with triethylsilane (1a) and
triphenylsilane (1b) – a synthesis of monosilylsubsituted 1,3-enyes (3).
To a solution of silane (1a-b) (1.0 mmol) and an appropriate 1,3-diyne (2a-e) (1.0 mmol) in 2mL
−4
-2
of toluene or xylene Pt catalyst was added in the [Pt]:[1b] of [4x10 –10 ]:[1] ratio depending on
the experiment and the catalyst (for detailed ratio please see Tables 1 and 2 in the manuscript).
Subsequently, the reaction mixture was heated to 40-140°C (oil bath) or kept at room temperature
and stirred until the full conversion of Si–H was detected. The reaction time for hydrosilylation of
1
each 1,3-diyne was determined by GC-MS, H NMR and for products with a mass above 600 g/mol
1
was determined only by H NMR. Then the solvent was evaporated under vacuum. The crude
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product was dissolved in n-hexane and filtered through silica gel. After evaporation products were
characterized by NMR, GC-MS, IR and elemental analysis. Reactions, which were carried out at
140°C were performed in a Schlenk flask with a Rotaflo® stopcock.
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General procedure for hydrosilylation of 1,3-diynes (2a–e) with triethylsilane (1a) and
triphenylsilane (1b) – a synthesis of bisilylsubsituted 1,3-dienes (4).
To a solution of silane (1a-b) (2.0 mmol) and an appropriate 1,3-diyne (2a-e) (1.0 mmol) in 2mL
−4
-2
of toluene or xylene Pt catalyst was added in the [Pt]:[1b] of [4x10 –10 ]:[1] ratio depending on
the experiment and the catalyst (for detailed information concerning reagents ratios please see
Tables 1 and 2 in the manuscript). Subsequently, the reaction mixture was heated to 40-140 °C (oil
bath) or kept at room temperature and stirred until the full conversion of Si–H was detected. The
1
reaction time for hydrosilylation of each 1,3-diyne was determined by GC-MS, H NMR and for
1
products with a mass above 600 g/mol was determined only by H NMR. Then the solvent was
evaporated
under
vacuum.
The
crude
product
was
dissolved
in
n-hexane and filtered through silica gel. After evaporation products were characterized by NMR,
GC-MS, IR and elemental analysis. Reactions, which were carried out at 140°C were performed
in a Schlenk flask with a Rotaflo® stopcock.
Analytical data for obtained products.
(2E)-3-Triethylsilyl-hex-2-en-4-yne (3aa).
1
H NMR (300 MHz, CDCl3, δ, ppm): 0.63 (m, 6H, CH2CH3, JH,H= 7.6 Hz), 0.94 (t,
Et3Si
H
CH3
9H, CH2CH3, JH,H= 7.8 Hz), 1.94 (d, 3H, =C(H)CH3), 2.02 (s, 3H, ≡CCH3), 6.09 (m,
3aa
H3C
13
1
1H, =CH, JH,H= 6.4 Hz). C { H}NMR (75 MHz, CDCl3, δ, ppm): 3.0 (C≡CCH3), 4.8 (CH2CH3), 7.4
(CH2CH3), 18.2 (=C(H)CH3), 79.0 (C≡CCH3), 93.4 (C≡CCH3), 123.0 (=C(Si(CH2CH3)3), 145.6
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(=C(H)CH3). Si NMR (79 MHz, CDCl3, δ, ppm): 2.2 (SiCH2CH3). GC-MS (EI, 70 eV) m/z (rel.
5
6
7
8
+
-1
int., %): 194.2 (M , 20), 166.3 (23), 165.3 (60), 125.1 (100). FT-IR (ATR, cm ): 3054, 2957, 2924,
2872, 1705, 1590, 1435, 1376, 1312, 1260, 1189, 1164, 1119, 1095, 1072, 1026, 801, 750, 720,
693, 537. Elemental Anal. Calc. for C12H22Si: C, 74,14; H, 11.41; found: C, 74.03; H, 11.38. Isolated
yield = 179 mg (91 %) from 197 mg (1 mmol), transparent liquid.
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(2E, 4E)- 2,4-Bis(triethylsilyl)hexa-2,4-diene (4aa).
1
H NMR (300 MHz, CDCl3, δ, ppm): 0.59 (m, 12H, SiCH2CH3), 0.94 (t, 18H,
H
SiEt3
H3C
CH3
SiCH2CH3, JH,H= 7.9 Hz), 1.54 (d, 6H, =CHCH3) 5.77 (m, 2H, =CHCH3, JH,H= 6.4
Et3Si
4aa
H
13 1
Hz). C { H} NMR (75 MHz, CDCl3, δ, ppm): 4.1 (CH2CH3), 7.7 (CH2CH3), 16.3
29
(=CHCH3), 133.5 (=CHCH3), 141.9 (C=CHCH3). Si NMR (79 MHz, CDCl3, δ, ppm): -1.29
+
(SiCH2CH3). GC-MS (EI, 70 eV) m/z (rel. int., %): 310.3 (M , 10), 253.3 (25), 166.2 (13), 115.1
-1
(100). FT-IR (ATR, cm ): 2952, 2909, 2874, 1716, 1458, 1416, 1376, 1236, 1005, 969, 799, 714,
586, 529. Elemental Anal. Calc. for C18H38Si2: C, 69.59; H, 12.33; found: C, 69.38; H, 12.21 Isolated
yield = 264 mg (84 %) from 314 mg (1 mmol), pale yellow liquid.
Dimethyl (E)-11-(triethylsilyl)docos-10-en-12-ynedioate (3ab).
1
H NMR (300 MHz, CDCl3, δ, ppm): 0.62 (m, 6H, SiCH2CH3, JH,H= 7.8
Et3Si
H
(CH2)8COOCH3
Hz), 0.93 (t, 9H, SiCH2CH3, JH,H= 7.9 Hz), 1.29-2.37 (m, 32H,
H3COOC(H2C)8
3ab
13
1
CH3OOC(CH2)8), 3.66 (s, 6H, CH3OOC), 5.97 (t, 1H, CH=C, JH,H= 6.9 Hz). C { H} NMR (75 MHz,
CDCl3, δ, ppm): 2.6 (SiCH2CH3), 7.7 (SiCH2CH3), 19.3-34.2 (CH3OOC(CH2)8), 51.5 (CH3OOC),
65.4 (C≡C-C≡C), 80.1 (C≡C-CSi), 97.5 (C≡C-CSi), 122.0 (CH=CSi), 151.2 (CH=CSi), 174.4
29
(CH3OOC). Si NMR (79 MHz, CDCl3, δ, ppm): -2.16 (SiCH2CH3). GC-MS (EI, 70 eV) m/z (rel.
+
int., %): 506.6 (M , 19), 117.0 (95), 115.1 (49), 87.2 (100). FT-IR (ATR, cm ): 2955, 2936, 2912,
-1
2876, 1376, 1358, 1249, 1158, 1034, 850, 751. Elemental Anal. Calc. for C30H54O4Si: C, 71.09; H,
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10.74; found: C, 71.16; H, 10.82. Isolated yield = 427 mg (82 %) from 529 mg (1 mmol), yellow
5
6
oil
7
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Methyl (10E,12E)-21-(methylperoxy)-11,12-bis(triethylsilyl)docosa-10,12,21-trienoate (4ab).
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1
H
H NMR (300 MHz, CDCl3, δ, ppm): 0.56 (m, 12H, SiCH2CH3, JH,H= 7.9
SiEt3
H3COOC(H2C)8
(CH2)8COOCH3
Et3Si
Hz), 0.93 (t, 18H, SiCH2CH3, JH,H= 7.8 Hz), 1.26 (m, 20H,
H
4ab
CH3OOCCH2CH2(CH2)5CH2), 1.60 (m, 4H, CH3OOCCH2CH2(CH2)5CH2), 1.90 (m, 4H,
CH3OOCCH2CH2(CH2)5CH2), 2.29 (t, 4H, CH3OOCCH2CH2(CH2)5CH2, JH,H= 7.5 Hz), 3.65 (s, 6H,
13 1
CH3OOC), 5.58 (t, 2H, CH=C, JH,H= 6.5 Hz). C { H} NMR (75 MHz, CDCl3, δ, ppm): 4.1
(SiCH2CH3), 7.7 (SiCH2CH3), 25.1, 29.3, 29.4, 29.6, 29.8, 31.0. 34.2 (CH3OOC(CH2)8), 51.6
29
(CH3OOC), 139.7 (CH=CSi), 140.4 (CH=CSi), 174.7 (CH3OOC). Si NMR (79 MHz, CDCl3, δ,
ppm): -1.54 (SiCH2CH3). GC MS (EI, 70 eV) m/z (rel. int., %): 622.8 (M+, 44), 117.0 (27), 115.1
-1
(46), 87.2 (100). FT-IR (ATR, cm ): 2948, 2921, 2873, 2853, 1750, 1458, 1236, 1169, 1012, 716.
Elemental Anal. Calc. for C36H70O4Si2: C, 69.49; H, 11.32; found: C, 69.19; H, 11.44. Isolated yield
= 555mg (87 %) from 638 mg (1 mmol), transparent liquid.
(E)-4-Triethylsilyl-2,2,7,7-tetramethyloct-3-en-5-yn (3ac).
1
H NMR (300 MHz, CDCl3, δ, ppm): 0.62 (m, 6H, CH2CH3, JH,H= 7.8 Hz), 0.95 (t, 9H,
Et3Si
H
CH2CH3, JH,H= 7.8 Hz), 1.19 (s, 9H, (CH3)3), 1.24 (s, 9H, (CH3)3), 5.85 (s, 1H,
3ac
13
=CH(C(CH3)3). C { H} NMR (75 MHz, CDCl3, δ, ppm): 3.1 (SiCH2CH3),
1
7.5(SiCH2CH3), 28.6 (≡C-C(CH3)3), 29.9 (=C-C(CH3)3), 31.0 (≡C-C(CH3)3), 35.8 (=C-C(CH3)3),
29
79.0 (≡C-C(CH3)3), 108.4 (C≡C-C(CH3)3), 118.9 (=C-C(CH3)3), 158.9 (C=C-C(CH3)3). Si NMR
(79 MHz, CDCl3, δ, ppm): 3.16 (SiCH2CH3). GC MS (EI, 70 eV) m/z (rel. int., %): 278.3 (M+, 17),
-1
139.1 (56), 115.0 (61), 87.1 (100). FT-IR (ATR, cm ): 2990, 2909, 2874, 1578, 1476, 1306, 1246,
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1004, 718, 696. Elemental Anal. Calc. for C18H34Si: C, 77,61; H, 12.30; found: C, 77.54; H, 12.33.
Isolated yield = 260 mg (92%) from 283 mg (1 mmol), transparent liquid.
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Product 3ac has been previously obtained.
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(E)-4-Triethylsilyl-2,7-dimethyl-2,7-trimethylsiloxy-octa-3-en-5-yne (3ad).
1
H NMR (300 MHz, CDCl3, δ, ppm): 0.13 (s, 9H, OSi(CH3)3), 0.17 (s, 9H,
Et3Si
H
OSiMe3
OSi(CH3)3), 0.68 (m, 6H, CH2CH3), 0.95 (t, 9H, CH2CH3, JH,H= 7.8 Hz), 1.51 (s,
3ad
Me3SiO
6H, =CHC(CH3)2-OSi(CH3)3), 1.54 (s, 6H, C≡CC(CH3)2OSi(CH3)3), 6.24 (s, 1H,
13
1
=CHC(CH3)2OSi(CH3)3). C { H} NMR (75 MHz, CDCl3, δ, ppm): 2.1 (C≡CC(CH3)2OSi(CH3)3), 2.7
(=CHC(CH3)2OSi(CH3)3), 2.9 (CH2CH3), 7.4 (CH2CH3), 30.0 (=CH-C(CH3)2OSi(CH3)3), 33.2
(C≡CC(CH3)2OSi(CH3)3), 67.6 (C≡CC(CH3)2OSi(CH3)3), 76.8 (=CHC(CH3)2OSi(CH3)3), 81.8 (-
C≡CCCH3)2OSi(CH3)3), 104.8 (C≡CC(CH3)2OSi(CH3)3), 117.4 (C=CHC(CH3)2OSi(CH3)3), 160.6
29
(=CHC(CH3)2OSi(CH3)3). Si NMR (79 MHz, CDCl3, δ, ppm): 4.94 (SiCH2CH3), 9.34 (C=CH-
C(CH3)2OSi(CH3)3), 12.44 (C≡C-C(CH3)2OSi(CH3)3). GC MS (EI, 70 eV) m/z (rel. int., %): 426.4
-1
(M+, 20), 131.1 (100), 73.1 (34), 87.1 (18). FT-IR (ATR, cm ): 3424, 2954, 2912, 2875, 1742,
1459, 1416, 1360, 1282, 1239, 1168, 1050, 1003, 961, 842, 720, 700, 587. Elemental Anal. Calc.
for C22H46O2Si3: C, 61.90; H, 10.86; found: C, 61.79; H, 10.82. Isolated yield = 394 mg (92%) from
428 mg (1 mmol), transparent oil.
(E)-2-Triethylsilyl-1,4-diphenylbuta-1-en-3-yne (3ae)
1
H NMR (300 MHz, CDCl3, δ, ppm): 0.86 (m, 6H, CH2CH3, JH,H= 7.7 Hz), 1.09 (t,
Et3Si
H
13
9H, CH2CH3, JH,H= 7.8 Hz), 6.87 (s, 1H, =CH), 7.32 - 8.06 (m, 10H, C6H5). C { H}
1
3ae
NMR (75 MHz, CDCl3, δ, ppm): 3.2 (CH2CH3), 7.5 (CH2CH3), 91.0 (C≡CC6H5),
100.6 (≡CC6H5), 121.0 (=C(H)C6H5), 124.6, 128.0, 128.4, 128.5, 128.6, 129.0 (C6H5), 131.4
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(=CSi(CH2CH3)3), 132.7, 138.0 (C6H5), 145.0 (=CH). Si NMR (79 MHz, CDCl3, δ, ppm): 5.38
5
6
+
(SiCH2CH3). GC MS (EI, 70 eV) m/z (rel. int., %): 318.3 (M , 99), 131.0 (100), 87.1 (50), 59.1
7
8
-1
(60). FT-IR (ATR, cm ): 3085, 2967, 2925, 2863, 1567, 1462, 1428, 1360, 1109, 746, 707, 507.
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Elemental Anal. Calc. for C22H26Si: C, 82.96; H, 8.23; found: C, 83.03; H, 8.30 Isolated yield = 317
mg (98%) from 323 mg (1 mmol), yellow oil.
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Product 3ae has been previously obtained.
(1E, 3E)-2,3-Bis(triethylsilyl)-1,4-diphenylbuta-1,3-diene (4ae).
1
H
H NMR (300 MHz, CDCl3, δ, ppm): 0.60 (m, 12H, -CH2CH3), 0.99 (t, 18H, -CH2CH3,
SiEt3
Ph
Ph
Et3Si
13
JH,H= 7.9 Hz), 6.83 (s, 2H, C=CH) 7.28-7.65 (m, 10H, C6H5). C { H} NMR (75 MHz,
1
H
4ae
CDCl3, δ, ppm): 4.4 (CH2CH3), 7.8 (CH2CH3), 127.2 (C=CHCH=CH-), 128.3
(C=CHCH=CH-), 129.0 (C=CHCH=CH-), 136.8 (C=CHCH=CH-), 139.8 (CH=CSi), 145.7
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(CH=CSi). Si NMR (79 MHz, CDCl3, δ, ppm): 1.73 (SiCH2CH3). GC MS (EI, 70 eV) m/z (rel.
+
-1
int., %): 434.5 (M , 34), 180.2 (48), 115.2 (100), 87.2 (97). FT-IR (ATR, cm ): 3058, 3022, 2952,
2909, 2873, 1598, 1491, 1457, 1414, 1376, 1237, 1074, 1005, 972, 919, 798, 751, 719, 690, 594.
Elemental Anal. Calcd for C28H42Si2: C, 77.35; H, 9.74; found: C, 77.41; H, 9.67. Isolated yield =
410 mg (93%) from 441 mg (1 mmol), yellow oil.
(2E)-3-Triphenylsilyl-hex-2-en-4-yne (3ba).
1
H NMR (300 MHz, CDCl3, δ, ppm): 1.96 (s, 3H, ≡CCH3), 2.01 (d, 3H, =CCH3),
Ph3Si
H
CH3
13
6.22 (m, 1H, =CH, JH,H= 6.5 Hz), 7.34 - 7.62 (m, 15H, C6H5). C { H} NMR (75 MHz,
1
3ba
H3C
CDCl3, δ, ppm): 4.9 (≡CCH3), 18.4 (=CCH3), 79.3 (C≡CCH3), 95.6 (≡CCH3), 120.7 (=CSi(C6H5)3),
29
127.8, 129.7, 134.0, 136.5 (C6H5), 151.3 (=CH). Si NMR (79 MHz, CDCl3, δ, ppm): -15.96
+
(SiC6H5). GC MS (EI, 70 eV) m/z (rel. int., %): 388.2 (M , 30), 260.2 (45), 259.2 (100), 181.1 (57).
-1
FT-IR (ATR, cm ): 3100, 2912, 2846, 1578, 1483, 1425, 1257, 1107, 737, 694, 504, 483.
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Elemental Anal. Calc. for C24H22Si: C, 85.15; H, 6.55; found: C, 85.24; H, 6.52. Isolated yield =
310 mg (89%) from 348 mg (1 mmol), white solid, mp = 116-122°C. Crystal data: C24H22Si,
Mr = 338.50, triclinic, P-1, a = 7.1974(5) Å, b = 8.1606(7) Å, c = 16.5692(10) Å, α = 82.517(6)°,
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-3
b = 83.519(5)º, γ = 77.911(7)°, V = 939.82(12) Å , Z = 2, F(000) = 360, dx = 1.196 g·cm ,
-1
μ = 0.128 mm . 14413 reflections collected up to 2Q = 27.0°, of which 3834 independent
2
(Rint = 0.023), 3290 with I>2σ(I). Final R(F) [I>2σ(I)] = 0.039, wR(F ) [I>2σ(I)] = 0.093, R(F) [all
2
-3
data] = 0.048, wR(F ) [all data] = 0.099, S = 1.05, max/min Dr = 0.36/−0.24 e×Å .
Dimethyl (E)-11-(triphenylsilyl)docos-10-en-12-ynedioate (3bb).
Ph3Si
H
(CH2)8COOCH3
1
H NMR (300 MHz, CDCl3, δ, ppm): 1.10-2.37 (m, 32H,
3bb
H3COOC(H2C)8
CH3OOC(CH2)8), 3.57 (s, 6H, CH3OOC), 6.04 (t, 1H, CH=C, JH,H= 7.0 Hz), 7.13-7.52 (m, 15H, C6H5).
13
1
C { H} NMR (75 MHz, CDCl3, δ, ppm): 19.9, 25.0, 28.7, 28.9, 29.0, 29.2, 32.5, 34.1
(CH3OOC(CH2)8), 51.5 (CH3OOC), 80.4 (C≡C-CSi), 99.7 (C≡C-CSi), 119.5 (CH=CSi), 127.7-
29
136.4 (C6H5), 156.5 (CH=CSi), 174.3 (CH3OOC). Si NMR (79 MHz, CDCl3, δ, ppm): -15.99
-1
(SiC6H5). FT-IR (ATR, cm ): 3069, 2928, 2855, 1736, 1429, 1363, 1171, 1109, 1028, 998, 866,
741, 698, 541, 507. Elemental Anal. Calc. for C42H54O4Si: C, 77.49; H, 8.36; found: C, 77.42; H,
8.40. Isolated yield = 570 mg (85%) from 671mg (1 mmol), white solid, mp = 116-122°C.
2,2,7,7-Tetramethyl-4-triphenylsilyl-oct-3-en-5-yne (3bc).
1
H NMR (300 MHz, CDCl3, δ, ppm): 1.13 (s, 9H, (CH3)3), 1.29 (s, 9H, (CH3)3), 6.15
Ph3Si
H
13
(s, 1H, =CH(C(CH3)3), 7.26-7.70 (m, 15H, C6H5). C { H} NMR (75 MHz, CDCl3, δ,
1
3bc
ppm): 28.5 (=C(H)C(CH3)3), 29.7 (≡CC(CH3)3), 30.6 (=C(H)C(CH3)3), 36.1
(≡CC(CH3)3), 79.7 (C≡CC(CH3)3), 110.7 (≡CC(CH3)3), 117.2 (=CSi(C6H5)3), 127.7, 129.5, 134.3,
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136.6 (C6H5), 164.2 (=CH). Si NMR (79 MHz, CDCl3, δ, ppm): -14.99 (Si(C6H5)3). GC MS (EI, 70
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8
9
-1
eV) m/z (rel. int., %): 422.4 (M+, 16), 260.3 (27), 259.2 (100), 181.1 (17). FT-IR (ATR, cm ):
3068, 2973, 2956, 2864, 1567, 1475, 1462, 1428, 1360, 1264, 1246, 1203, 1187, 1109, 1028, 997,
746, 707, 698, 620, 545, 525, 508, 497, 425. Elemental Anal. Calcd for C30H34Si: C, 85.25; H, 8.11;
found: C, 85.21; H, 8.14. Isolated yield = 391 mg (90%) from 434 mg (1 mmol), white solid, mp
= 99-102°C. Crystal data: C30H34Si, Mr = 422.66, orthorhombic, P212121, a = 8.4109(4) Å,
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-3
b = 10.9387(4) Å, c = 28.7518(13) Å, V = 2645.3(2) Å , Z = 4, F(000) = 912, dx = 1.061 g·cm ,
-1
μ = 0.102 mm . 14123 reflections collected up to 2Q = 27.1°, of which 5233 independent
2
(Rint = 0.021), 4608 with I>2σ(I). Final R(F) [I>2σ(I)] = 0.040, wR(F ) [I>2σ(I)] = 0.103, R(F) [all
2
-3
data] = 0.049, wR(F ) [all data] = 0.1107, S = 1.05, max/min Dr = 0.22/−0.14 e×Å .
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Product 3bc has been previously obtained.
2,7-Dimethyl-2,7-bis(trimethylsiloxy)-4-triphenylsilyl-oct-3-en-5-yne (3bd).
1
H NMR (300 MHz, CDCl3, δ, ppm): -0.04 (s, 9H, OSi(CH3)3), -0.02 (s, 9H,
Ph3Si
H
OSiMe3
OSi(CH3)3), 1.32 (s, 6H, =C(H)C(CH3)2OSi(CH3)3), 1.61 (s, 6H, C≡C-
3bd
Me3SiO
13
1
C(CH3)2OSi(CH3)3), 6.39 (s, 1H, =C(H)C(CH3)2OSi(CH3)3, 7.26-7.63 (m, 15H, C6H5). C { H} NMR
(75 MHz, CDCl3, δ, ppm): 1.8 (≡CC(CH3)2OSi(CH3)3), 2.4 (=C(H)C(CH3)2OSi(CH3)3), 29.9
(=C(H)C(CH3)2OSi(CH3)3), 32.8 (≡CC(CH3)2OSi(CH3)3), 67.4 (≡CC(CH3)2OSi(CH3)3), 77.0
(=C(H)C(CH3)2OSi(CH3)3), 82.2 (C≡CC(CH3)2OSi(CH3)3), 106.8 (≡CC(CH3)2OSi(CH3)3), 115.9
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(=CSiC6H5), 127.9, 129.8, 133.4, 136.6 (C6H5), 165.9 (=C(H)C(CH3)2OSi(CH3)3). Si NMR (79
MHz, CDCl3, δ, ppm): -14.21 (Si(C6H5)3), 9.70 (C=CH-C(CH3)2OSi(CH3)3), 12.76 (C≡C-
C(CH3)2OSi(CH3)3. GC MS (EI, 70 eV) m/z (rel. int., %): 570.4 (M+, 21), 259.2 (90), 131.1 (100),
-1
73.1 (73). FT-IR (ATR, cm ): 3070, 2978, 2955, 2930, 1428, 1376, 1250, 1159, 1110,1035, 804,
707, 509. Elemental Anal. Calcd for C34H46O2Si3: C, 71.52; H, 8.12; found: C, 71.47; H, 8.05.
Isolated yield = 526 mg (91 %) from 578 mg (1 mmol), light yellow liquid.
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(1E)-1,4-Diphenyl-2-triphenylsilyl-but-1-3-yne (3be).
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1
H
H NMR (300 MHz, CDCl3, δ, ppm): 7.10 (s, 1H, =CH), 7.33-8.12 (m, 25H, C6H5).
Ph3Si
7
8
9
13
1
C { H} NMR (75 MHz, CDCl3, δ, ppm): 91.5 (≡CC6H5), 102.2 (C≡CC6H5), 118.2
3be
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(=CSi(C6H5)3), 124.2, 128.0, 128.2, 128.2, 128.4, 129.1, 129.3, 129.9, 131.3, 133.4,
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136.6, 137.6 (C6H5), 149.7 (=CH). Si NMR (79 MHz, CDCl3, δ, ppm): -13.49 (SiC6H5). GC MS
+
(EI, 70 eV) m/z (rel. int., %): 462.3 (M , 66), 259.2 (100), 181.1 (57), 105.1 (32). FT-IR (ATR,
-1
cm ): 3066, 308, 1487, 1426, 1108, 1016, 774, 690, 508, 488, 472. Elemental Anal. Calcd for
C34H26Si: C, 88.27; H, 5.66; found: C, 88.36; H, 5.71. Isolated yield = 427 mg (90%) from 474 mg
(1 mmol), yellow solid, mp =114-120°C.
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Product 3be has been previously obtained.
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Acknowledgment
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The authors acknowledge the financial support from the National Centre for Research and
Development in Poland – Lider Programme no. LIDER/26/527/L-5/13NCBR/2014, and National
Science Centre in Poland – grant PRELUDIUM UMO-2017/27/N/ST5/00224. The authors are
grateful to Prof. Dr. Maciej Kubicki from the Faculty of Chemistry of Adam Mickiewicz
University in Poznan for analysis of the crystal structures.
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Supporting Information
Description of spectroscopic data for all new compounds, X-ray analysis and literature description
on previous methods on hydrosilylation of 1,3-diynes. (PDF)
Author Contributions
The manuscript was written through the contributions of all authors. All authors have given
approval to the final version of the manuscript.
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REFERENCES
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