Palladium-Catalyzed Oxidative Silylation of Simple Olefins To Give Allylsilanes Using Hexamethyldisilane and Molecular Oxygen as the Sole Oxidant

Article abstract of DOI:10.1021/acs.joc.5b01216

A Pd-catalyzed oxidative silylation of simple olefins with hexamethyldisilane to give allylsilanes has been achieved using molecular oxygen as the sole oxidant. The reaction provides a useful protocol to access synthetically useful allylsilanes from easil

Full text of DOI:10.1021/acs.joc.5b01216

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Note
Palladium-Catalyzed Oxidative Silylation of Simple
Olefins to give Allylsilanes Using Hexamethyldisilane
and Molecular Oxygen as the Sole Oxidant
Syunji Nakai, Masaki Matsui, Yosuke Shimizu, Yurina Adachi, and Yasushi Obora
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.5b01216 • Publication Date (Web): 18 Jun 2015
Downloaded from http://pubs.acs.org on June 23, 2015
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Palladium-Catalyzed Oxidative Silylation of Simple Olefins to give Allylsilanes Using
Hexamethyldisilane and Molecular Oxygen as the Sole Oxidant
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Syunji Nakai, Masaki Matsui, Yosuke Shimizu, Yurina Adachi, and Yasushi Obora*
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Department of Chemistry and Materials Engineering, Faculty of Chemistry, Materials and Bioengineering, Kansai University,
Suita, Osaka 564-8680, Japan
obora@kansai-u.ac.jp
A Pd-catalyzed oxidative silylation of simple olefins with hexamethyldisilane to give allylsilanes has been achieved
using molecular oxygen as the sole oxidant. The reaction provides a useful protocol to access synthetically useful allylsilanes
from easily accessible simple olefins and hexamethyldisilane without using any oxidants other than O2.
Allylsilanes are regarded as important motifs because of their inherent reactivity, stability, and low toxicity.
Therefore, allylsilanes have been used as building blocks for a range of organic transformations.1 One well known
example is the allylation of electrophilic carbonyl compounds; the Hosomi–Sakurai reaction.2
The synthetic utility of allylsilanes has been developed over many decades. The conventional methods for the
synthesis of allylsilanes include the reaction of allylmetal (Mg, Al, Cu, Sm) reagents3 and hydrosilylation of 1,3-
dienes.4 Reagents containing silicon-metal bonds (e.g. Si-Cu, Si-Li, Si-Al, and Si-Mn bonds) have also been used for
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synthesizing allylsilanes.5 Recently, allylsilanes have been prepared by Pd-catalyzed silyl-Heck reaction of olefins with
Me3SiI,6 Co-catalyzed dehydrogenative silylation of olefins with hydrosilanes,7 and Ni-catalyzed dealkoxylative cross
coupling from enol ethers.8 In addition, Cu-catalyzed enantioselective synthesis of allylsilanes has also been
developed.9
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The formation of allylsilanes by allylic silylation of simple olefins via the formation of a -allyl palladium
intermediate is especially intriguing.10 In general, allyl halides, allyl ethers and allyl esters have been used as allyl
sources.11
Hexamethyldisilane (Me3SiSiMe3) is a stable, commercially available organosilicon compound which has been
widely employed as a silyl source in organosilicon chemistry.12,13 Tsuji and co-workers reported allylic silylation of
allylic acetates with Me3SiSiMe3 to form allylsilanes.14 In this work allylic trifluoroacetates gave the best yields.
Furthermore, Lipshutz and co-workers reported silylation of allylic ethers and disilane in the presence of a Pd
catalyst.15 Quite recently, Szabó and co-workers reported the Pd-catalyzed allylic silylation of disilanes using allylic
alcohols as allylation agents.16
Another topic of current interest is catalytic C-H functionalization by oxidative coupling as an environmentally-
friendly C-H functionalization methodology.17 Recently, our group reported Pd(II)-catalyzed intermolecular oxidative
amination of olefins with amines using molecular oxygen as the oxidant.18
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In light of recent developments in oxidative C-H functionalization chemistry, silylation by C-H activation would be
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highly beneficial as a synthetic process with minimal byproducts. To date, transition-metal catalyzed aryl and alkyl C-
H silylations have been reported.19
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With regard to oxidative olefinic C-H silylation, Szabó and co-workers reported palladium-catalyzed synthesis of
allylic silanes from olefins and disilane in the presence of a strong oxidant such as hypervalent iodines.20 Being able to
carry out this transformation using simple olefins and milder oxidants would be highly desirable.
In this paper, we report the Pd-catalyzed oxidative allylic silylation reaction of simple olefins and
hexamethyldisilane using atmospheric oxygen as the sole oxidant.
Initially we investigated various conditions to determine the optimal conditions for this reaction (Table 1). When 1-
decene (1a) was reacted with hexamethyldisilane (2) in the presence of Pd(OCOCF3)2 under an oxygen atmosphere (1
atm, balloon), (E)-2-decenyltrimethylsilane (3a) was obtained in 49% yield (Table 1, entry 1). The reaction proceeded
in a highly regio- and stereoselective manner, and afforded the (E)--adduct exclusively. In the reaction, addition of
acetylacetone (acacH) as an additive increases the yield of 3a (63%, entry 2). We found that high yields were achieved
when 2 was added portionwise to an excess of 1a. The yield of 3a was increased to 86% when 2 was added in three
portions, one portion every 24 h over 72 h (entry 3). The best yields were obtained when Pd(OCOCF3)2 was used as the
catalyst. The use of other selected Pd complexes showed low or no catalytic activity (entries 4–7). This suggests that
the initial -hydrogen abstraction by the trifluoroacetate ligand forming a -allylpalladium intermediate is a key step in
the reaction (vide infra). Various other additives were examined (entries 8–10). The use of dibenzylideneacetone (dba)
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similarly gave the product in good yield (entry 8). However, when DMSO and PPh3 were used as additives, the
catalytic activity considerably deteriorated (entries 9–10) compared with the reaction carried out in absence of additive
(entry 1). The reaction effectively proceeded by using olefin (1-decene) as both solvent and substrate. The use of
solvents such as DMF, DMA, and decane resulted in lower yields (entries 11–16). The excess 1-decene can be
recovered in 84% yield after the reaction and no isomerization of 1-decene was observed by GC analysis.
The reaction required molecular oxygen as oxidant and low or no coupling product was obtained when the reaction
was carried out under an atmosphere of air or Ar (entries 17–18). The reaction at room temperature (entry 19), and the
reaction at 60 °C only afforded the product in moderate yield (entry 20).
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The choice of hexamethyldisilane as a silyl source is crucial for an efficient reaction. We found that using other
disilanes such as PhMe2SiSiMe2Ph and PhMe2SiSiMe3 led no reaction at all.
Next we investigated a range of olefins under the optimized conditions (Table 2). A variety of olefins including,
simple -olefins and allylbenzene can be used in the reaction, and afford the corresponding (E)--allylsilanes (3a-3i)
in good to excellent yields with high selectivity (entries 1–6). Allylbenzene (1g), allylcyclohexane (1h), and 4-phenyl-
1-butene (1i) are tolerated in the reaction to afford corresponding allylsilanes (3g-i) in good yields (entries 7–9). When
the reaction was performed with 1,10-decadiene (1j) as a -diene, selective mono-allylic silylation took place on
one side of the -diene and afforded allylsilane (3j) in good yield with high selectivity (entry 10). The reactivity of
internal olefins was sluggish in the allylic silylation with 2. The reaction with cycloheptene (1k) gave the product in
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15% yield (entry 11). Unfortunately, the use of functionalized olefins such as allyl butylether, allyl phenylether and
allyl phenylacetate did not afford any allylsilane at all.
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Table 1. Pd-catalyzed oxidative silylation of 1-decene (1a) with hexamethyldisilane (2)a
cat. Pd (5 mol %)
additive (0.1 mmol)
+
Me3SiSiMe3
n-C7H15
SiMe3
n-C7H15
1a
40 oC, 24 h
under O2 (1atm)
3a
2
yield
(%)b
entry
Pd-catalyst
additive
Solvent
1
Pd(TFA)2
Pd(TFA)2
Pd(TFA)2
Pd(OAc)2
Pd(dba)2
Pd(acac)2
PdCl2
none
none
49
2
3c
acacH
acacH
acacH
acacH
acacH
acacH
dba
none
63
none
86 (80)
3
4
none
5
none
n.d.
n.d.
n.d.
57
6
none
7
none
8
Pd(TFA)2
Pd(TFA)2
Pd(TFA)2
Pd(TFA)2
Pd(TFA)2
Pd(TFA)2
Pd(TFA)2
Pd(TFA)2
Pd(TFA)2
Pd(TFA)2
Pd(TFA)2
Pd(TFA)2
Pd(TFA)2
none
9
DMSO
PPh3
none
28
10
11
12
13
14d
15d
16e
17f
18g
19h
20i
none
3
acacH
acacH
acacH
acacH
acacH
acacH
acacH
acacH
acacH
acacH
PhCF3
toluene
nesitylene
DMF
DMA
decane
none
69
62
48
6
2
n.d.
25
none
n.d.
49
none
none
30
a Reaction conditions: 1a (20 mmol) was reacted with 2 (0.5 mmol) in the presence of a Pd catalyst (0.05 mmol) and additive (0.10 mmol) at 40 °C for 24 h
under an atmosphere of oxygen. TFA= trifluoroacetate, acacH = acetylacetone, dba = dibenzylideneacetone. b GC yields based on 2 except the values in the
parenthesis. The selectivity of the (E)--adduct is >95%. c 2 was added in three portions (0.2, 0.2, and 0.1 mmol, respectively) every 24 h over the 72 h. d
g
Solvent (1 mL) was used. e Reaction was performed by using 1a (0.5 mmol), 2 (0.5 mmol), and solvent (20 mmol). f Reaction performed under air.
Reaction performed under Ar. h Reaction temperature was room temperature. i Reaction temperature was 60 °C.
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Table 2. Pd-catalyzed oxidative silylation of various olefins (1) with 2. a
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entry
1c
Olefin
Product
yield (%)
80
n-C7H15
SiMe3
n-C7H15
3a
1a
2
63
n-C4H9
n-C5H11
n-C6H13
n-C9H17
SiMe3
SiMe3
SiMe3
SiMe3
n-C4H9
1b
n-C5H11
1c
3b
3c
3d
3e
3
4
5
6
7
84
53
73
83
76
n-C6H13
1d
n-C9H17
1e
n-C11H21
n-C11H21
SiMe3
1f
3f
SiMe3
1g
1h
1i
3g
3h
8
9
57
58
SiMe3
SiMe3
3i
3j
10
76
15
( )5
SiMe3
( )5
1j
11b
Me3Si
1k
3k
a
Reaction conditions: 1a (20 mmol) was reacted with 2 (0.5 mmol) in the presence of Pd(TFA)2 (0.05 mmol) and acetylacetone (0.10 mmol) at 40 °C
under an atmosphere of oxygen and 2 was added in three portions (0.2, 0.2, and 0.1 mmol, respectively) every 24 h over the 72 h. b Reaction time was 24 h.
It is reported that the reaction of olefins with Pd(II) generates an 3-allyl palladium intermediate by means of
allylic C-H bond activation.21,22 Therefore, (3-cinnamyl)palladium trifluoroacetate dimer (4) and (3-
cinnamyl)palladium acetate dimer (5) were prepared independently and the stoichiometric reaction with 2 was carried
out (Scheme 1).18a,23 This study showed that the reaction of 4 with 2 gave corresponding allylsilane 3g in 23% yield,
but the reaction with 5 was sluggish and gave 3g in only 9% along with hexamethydisiloxane as byproduct. This
implies that the transformation of the 3-allyl palladium intermediate with disilane is the key rate-determining step in
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this reaction. In addition, the use of 4 as catalyst under the conditions as shown in entry 2, Table 1 afforded 3a in 7%
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yield.
Scheme 1. Stoichiometric reaction of 3-allyl palladium acetate dimers (4 and 5) with 2.
acacH (0.1 mmol)
Ph
2
Me3Si
Ph
+
40 oC, 24 h
under O2 (1 atm)
Pd
3g
R
23% (from 4)
9% (from 5)
2
R = OCOCF3 (4)
R = OCOCH3 (5)
A plausible reaction mechanism for the transformation is shown in Figure 1. Initially, Pd(II) reacts with olefin 1 to
form 3-allyl palladium intermediate (A) through allylic hydrogen abstraction.18a,22,23 Then the A is subjected
transmetallation with Me3SiSiMe3 (2) to form silyl(3-allyl)palladium intermediate B, followed by the production of
allylsilane 3 with Pd(0). Then, Pd(0) is reoxidized by dioxygen to generate Pd(II).24 The key to achieving high yields is
the portionwise addition of hexamethyldisilane due to the formation of hexamethyldisiloxane (Me3SiOSiMe3) under
the oxygen atmosphere. The formation of hexamethyldisiloxane (7.87 ppm)25 and Me3SiOCOCF3 (33.11 ppm)26 was
observed when the reaction mixture was monitored by 29Si NMR. In addition, it is difficult to rationalize the role of
acetylacetone as efficient additive in the reaction. However, the positive effect of the acacH additive in the direct C-H
activation has been reported.27
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Figure 1. Plausible reaction mechanism for the oxidative allylsilylation of disilane with olefins.
In conclusion, we have demonstrated the Pd(OCOCF3)2-catalyzed oxidative silylation of simple olefins with hexa-
methyldisilane, using atmospheric oxygen as the sole oxidant.
Experimental Section
General
GC analysis was performed with a flame ionization detector using a 0.22 mm × 25 m capillary column (BP-5). 1H
and 13C NMR were measured at 400 MHz, respectively, in CDCl3 with Me4Si as the internal standard.
Compounds except for 3a,6b 3b,28a 3c,28a 3d,28a 3e,28b 3f,28b 3g,15 3h,28c 3i,4 3k28e were reported previously.
Experimental Procedure
Typical procedure for the preparation of 3a (entry 3, Table 1): To a mixture of Pd (OCOCF3)2 (17 mg, 0.05
mmol), and acetylacetone (10 mg, 0.1 mmol) was added 1a (2.8 g, 20 mmol) and 2 (73 mg, 0.5 mmol) under O2 in a 30
mL round-bottomed flask. The reaction mixture was stirred at 40 °C for 72 h. Compound 2 was added in three batches,
one every 24 h over a period of 72 h. (first time 0.2 mmol (29 mg), second time 0.2 mmol (29 mg), third time 0.1 mmol
(15 mg)) The product (3a) was isolated by column chromatography (silica gel, n-hexane) in 80% yield (85 mg).
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Procedure for the preparation of 3a (entry 1, Table 1): To a mixture of Pd (OCOCF3)2 (17 mg, 0.05 mmol) was
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added 1a (2.8 g, 20 mmol) and 2 (73 mg, 0.5 mmol) under O2 in a 30 mL round-bottomed flask. The reaction mixture
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o
was stirred at 40 C for 24 h. The yield of product was estimated from peak areas based on an internal standard
(tridecane) using GC and the product (3a) was obtained in 49% yield.
Reaction of 4/5 with 2 (Scheme 1): A mixture of 4/5 (0.05 mmol) and acetyllacetone (10 mg, 0.1 mmol) was added
o
2 (73 mg, 0.5 mmol) under O2 in a 30 mL round-bottomed flask. The reaction mixture was stirred at 40 C for 24 h.
The yields of products were estimated from peak areas based on an internal standard (tridecane) using GC and the
product 3g was obtained in 23% and 9% yield, respectively.
1
3j: Yield 76% (80 mg), colorless liquid, H NMR (CDCl3, 400 MHz):  5.88-5.78 (m, 1H), 5.42-5.21 (m, 2H), 5.04-
4.93 (m, 2H), 2.08-1.96 (m, 4H), 1.42-1.28 (m, 8H) 0.00 (s, 9H); 13C{1H}NMR (CDCl3, 400 MHz): 139.2 (CH),
128.9 (CH), 126.0 (CH), 114.1 (CH2), 33.8 (CH2), 32.7 (CH2), 29.8 (CH2), 28.8 (CH2), 28.6 (CH2), 22.6 (CH2), -2.00
(CH3), IR (neat, cm-1) : 3005, 2954, 2926, 2854, 1641, 1248, 1155, 964, 910, 850, 696; GC-MS (EI) m/z (relative
intensity) 210 (1) [M +], 139(3), 136(4), 114(2), 99(2), 73(100), 59(5), 45(6); HRMS(EI-TOF) m/z calcd for C13H26Si
[M+] 210.1804, found 210.1803.
ACKNOWLEDGMENT
This work was supported by the "Development of Innovative Catalytic Processes for Organosilicon Functional
Materials" project (PL: K. Sato, AIST) from the New Energy and Industrial Technology Development Organization
(NEDO).
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Supporting Information Available: Original NMR spectra for products 3. This material is available free of charge via
the Internet at http://pubs.acs.org
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