Dehydrogenative Silylation of Alcohols Under Pd-Nanoparticle Catalysis

Article abstract of DOI:10.1002/chem.201803989

Pd-nanoparticle-catalyzed dehydrogenative coupling between various hydrosilanes and alcohols was shown to provide silyl ethers in good and reproducible yields. The synthetic methodology is effective for a wide range of simple and bulky silanes and secondary alcohols, while keeping various other functional groups intact. The procedure also exhibits high selectivity for the silylation of primary versus secondary alcohols in 1,2-diols, and allows the successive silylation of alkynols and hydrogenation of the triple bond to afford Z-alkenols in good yields.

Full text of DOI:10.1002/chem.201803989

A Journal of
Accepted Article
Title: Dehydrogenative Silylation of Alcohols Under Pd-nanoparticles
Catalysis
Authors: Yannick Landais, Suman Pramanik, Virignie Liautard,
Anthony Fernandes, Frédéric Robert, and Mathieu Pucheault
This manuscript has been accepted after peer review and appears as an
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content of this Accepted Article.
To be cited as: Chem. Eur. J. 10.1002/chem.201803989
Link to VoR: http://dx.doi.org/10.1002/chem.201803989
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10.1002/chem.201803989
Chemistry - A European Journal
COMMUNICATION
Dehydrogenative Silylation of Alcohols Under Pd-nanoparticles
Catalysis.
Suman Pramanik,[a] Anthony Fernandes,[a] Virginie Liautard,[a] Mathieu Pucheault,[a] Frederic Robert*[a]
and Yannick Landais*[a]
Abstract: Pd-nanoparticles catalyzed dehydrogenative coupling
between various hydrosilanes and alcohols was shown to provide silyl
ethers in good and reproducible yields. The synthetic methodology is
effective for a wide range of simple and bulky silanes and secondary
alcohols, while keeping various other functional groups intact. The
procedure also exhibits high selectivity for the silylation of primary
versus secondary alcohols in 1,2-diols, and allows the successive
silylation of alkynols and hydrogenation of the triple bond to afford Z-
alkenols in good yields.
catalysts used in these reactions are incompatible for both
sterically hindered silanes and alcohols in many instances. The
rate of B(C6F5)3-catalyzed dehydrogenative coupling is for
instance controlled by the steric factor of the hydrosilane.[9]
Reported dehydrogenative silylation reactions either involve bulky
silane or secondary alcohols as coupling partners.[8,10] The
development of new methods for dehydrogenative silylation,
irrespective of the nature of the silane and the alcohol, is in
demand,[11,12] with applications in diverse fields including material
science,[13] functional polymers,[14] and organocatalysis.[15]
During the past two decades, Pd nanoparticle (Pd-NP) catalysts
have attracted significant attention due to their wide applicability
in the field of coupling reactions forming C-C bond,[16] alkene
hydrogenation,[17] reduction of aromatic nitro compounds,[18] and
-allylic substitution reactions.[19] Transformation of hydrosilanes
into silanols in the presence of water has been reported using
carbon-supported or aluminium oxy-hydroxide-supported Pd-NP
catalysts (Scheme 1).[20] Dehydrocoupling of hydrosilanes with
methanol or ethanol has been developed by utilizing dealloyed
nanoporous Pd catalysts.[21] The exploration of new catalytic
methods based on supported nanoporous Pd-catalysts continues
to be beneficial in addressing remaining challenges in
dehydrogenative coupling reactions.
Silyl ether compounds have attracted much attention in material
science.[1] Protection of alcohols through silylation is well-known
in organic synthesis and is frequently used in the preparation of
synthetic materials[2] and in total synthesis of natural products.[3]
Hydrolytic silylation is an invaluable tool for the production of
functionalized mesoporous silica nanospheres through grafting or
co-condensation processes.[4] The protection of alcohols and
phenols with silyl groups significantly changes their thermal
stability and polarity. Additionally, trimethylsilyl derivatives are
thus often prepared from free alcohols for GC analysis purposes,
due to a lower polarity and a higher volatility than the parent
alcohols.[5] The high demand for silyl ethers thus continuously
attracts interest among organic chemists for their synthesis.[6-8]
The silylation of alcohols is commonly performed by the use of
silyl chlorides in the presence of base, producing equimolar
amount of hydrochloride salts.[6] To circumvent the frequent lack
of efficiency for the protection of sterically hindered or less
reactive alcohols, silyl triflate reagents are generally required.[7]
However, the latter suffer from moisture sensitivity and high costs.
Recently, considerable attention has been paid to the
construction of Si-O bond through catalytic dehydrogenative
silylation of alcohols.[8] This alternative method is based on the
use of hydrosilanes under neutral conditions, producing H2 as the
sole by-product (Scheme 1). Although this atom economical
approach has considerable importance, the coupling process
using non-toxic and hydrolytically more stable silicon reagents,
Catalytic dehydrocoupling
R2
R2
R1 Si
R3
Either the silane or alcoholis sterically crowded
catalyst/additives
R1 Si OR
+
H2
H
+
ROH
R3
Pd-nanoparticle (Pd-NP) catalyzed dehydrogenative silylation
C or AlO(OH) supported
R2
R1 Si OR
R3
R2
R1 Si
R3
Pd-NP catalyst
+
ROH
+
H2
H
(R = H, Me, Et)
H2O, MeOH or EtOH as the couplingpartner
This Work
C supported
Pd-NP catalyst
R2
R2
R1 Si
R3
R1 Si OR
R3
+
H2
+
ROH
H
[a]
Dr. S. Pramanik, A. Fernandes, Dr. V. Liautard, Dr. M. Pucheault,
Dr. F. Robert, Prof. Dr. Y. Landais
Both hydrosilaneand alcohol may be sterically crowded
University of Bordeaux, Institute of Molecular Sciences, UMR-CNRS
5255
351, Cours de la libération, 33405 Talence cedex, France.
E-mail: yannick.landais@u-bordeaux.fr
Scheme 1. Catalytic dehydrogenative silylation.
E-mail: frederic.robert@u-bordeaux.fr
Supporting information for this article can be found under
https://doi.org/xx.xxxx/chem.2018xxxxx.
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10.1002/chem.201803989
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COMMUNICATION
During our continuous studies on the reactivity of organosilicon
compounds and derivatives,[22] we experienced some difficulties
for the synthesis of sterically crowded silyl ethers using reported
literature procedures. Therefore, we were looking for a catalytic
system which would be tolerant to steric hindrance, allowing for
the dehydrogenative silylation of bulky secondary alcohols with
various silanes. Recent studies by one of us on the use of
montmorillonite, Layer Double Hydroxides (LDH), oxides or
carbon as solid supports, showed these catalysts to be highly
reactive in a wide range of transformations, indicating that they
might suit our purpose.[23] Herein, we report the development of a
convenient dehydrocoupling reaction between hydrosilanes and
alcohols with various steric demands, leading to the
corresponding silyl ethers, using Pd-NP. Yields are generally
good, the procedure allowing various substituents on the silicon
center. The procedure has good functional group tolerance,
including Lewis basic moieties and exhibits excellent selectivity in
1,2-diol monoprotection.
(-)-Menthol 1a and sterically hindered carbazole substituted
hydrosilane 2a were chosen as model substrates for
dehydrogenative coupling reaction, illustrating notably a relatively
high steric hindrance around silicon. All standard methods to
access 3a proceeding through the silyl chloride or triflate
analogues of 2a failed before. Several Pd-NP based catalysts
were used in our study.[24] The Pd-NP were formed by borane
reduction of palladium(II) chloride in the presence of the solid
support, namely Kunipia MMT, K10 MMT or DARCO® Charcoal:
Pd-NP1 was thus obtained through reduction of PdCl2 using
NaBH4 in the presence of Kunipia MMT, Pd-NP2 using
diisopropylamine-borane (DIPAB) complex and Kunipia MMT,
Pd-NP3 using NaBH4 and K10 MMT, and Pd-NP4 using NaBH4
and DARCO® carbon (See supporting information, SI). We began
our investigations with Pd-NP1 catalyst in n-dibutylether as a
solvent. The dehydrocoupled product 3a was obtained in an
encouraging 50% yield as a 1:1 mixture of two diastereomers
(Table 1, entry 1). It is worth noticing that (-)-menthol is not altered
by the Pd-catalyst (e.g. through an hydrogenation-
dehydrogenation process), as shown by the formation of only two
sets of peaks in the 1H NMR (300 MHz) of 3a in the presence of
chiral shift reagent [Eu(hfc)3] (SI). The survey of catalyst
screening showed that Pd-nanoparticle catalysts Pd-NP2 and Pd-
NP3 gave respectively moderate to low yield of the desired
product (entry 2 and 3, Table 1). Carbon-supported Pd catalyst
Pd-NP4 showed similar catalytic activity than MMT-supported Pd
catalyst Pd-NP1, affording the desired dehydrocoupled product in
53% yield. As the carbon-based catalyst was easier to remove by
filtration, it was designated as the catalyst of choice for further
studies (entry 4). X-ray Photoelectron Spectroscopy (XPS)
analysis showed that most of the palladium was under the form of
Pd(0) (70%), the remaining being PdO (30%), probably as a result
of the oxidation of Pd(0) by air during the XPS analysis. The metal
loading was found to average between 0.3 to 0.35% depending
on sample. ICP analysis showed that Pd-NP4 contains 92 mg of
Pd(0) per gram of catalyst or 0.864 mmol/g. We further tested
various solvents including THF, t-butyl methylether, n-hexane and
n-heptane (entry 5 to 8) and found that n-dibutylether was the
most suitable for the reaction. When the reaction was heated for
24 h at 70 °C in the presence of Pd-NP4 catalyst, the yield was
improved to 56% (entry 9), which corresponds to a TON of 662.
Although yield is still moderate, it is noteworthy that all standard
methods to access 3a failed. When commercial Pd-C was used
(entry 10), very low yield of 3a was obtained, showing the unique
efficiency of Pd-nanoparticles in this process.
Table 1. Optimization of the dehydrogenative silylation of menthol.
N
Pd-NP, Solvent
70 C, 16 h
Me
Si
Ph
N
Me
Si
+
H
OH
O
Ph
1a
2a
3a
Entry[a]
Catalyst[b]
Solvent
Yield [%][c]
1
2
3
4
5
Pd-NP1
Pd-NP2
Pd-NP3
Pd-NP4
Pd-NP4
Pd-NP4
Pd-NP4
Pd-NP4
Pd-NP4
Pd-C (10%)
nBu2O
nBu2O
50
44
12
53
8
17
21
23
nBu2O
nBu2O
THF
MTBE
6
7
n-hexane
n-heptane
nBu2O
8
9[d]
10
56 (54)[e]
3
nBu2O
[a] Reaction Conditions: 1a (0.5 mmol), 2a (1.5 equiv., 0.75 mmol), Pd-catalyst
(15 mg) in solvent (2 mL) at 70 °C for 16 h. [b] Pd-NP1: PdCl2/NaBH4/MMT
Kunipia; Pd-NP2: PdCl2/iPr2NH-BH3/MMT Kunipia; Pd-NP3: PdCl2/NaBH4/K10
MMT; Pd-NP4: PdCl2/NaBH4/DARCO® carbon. Reduction of PdCl2 (1 mmol) is
performed over 1 g of solid support (MMT or Charcoal) in MeOH. [c] Yield was
calculated from the 1H NMR of the reaction mixture using mesitylene as internal
standard. [d] 2.5 equiv. of silane was used and the reaction heated for 24 h. [e]
Isolated yield after column chromatography.
With these optimized reaction conditions in hand, the
methodology was extended to a variety of hydrosilanes using Pd-
NP4 as the catalyst (Table 2). Hydrosilanes showing various
substitutions patterns, including aryl and alkyl groups are well
tolerated (Table 2, entry 2-3). The silylation of (-)-menthol with
triphenylsilane afforded the corresponding silyl ether 3d in high
yield (entry 4). The reaction proceeded at 100 °C in the presence
of tert-butyl substituted hydrosilanes 2e and 2f which are bulkier
than arylsilanes (entry 5 and 6), affording moderate yields of silyl
ethers. The reaction leading to 3c could be performed with low
catalyst loading (1 mg), albeit at the expense of the yield (32%
and a TON of 11428) (entry 3, [c]). It is noteworthy that Pd-NP4
catalyst could be reused without alteration of its activity. For
instance, when reaction in Table 2 (entry 3) was repeated three
times with the same Pd-NP4 (recovered through a simple
filtration), 3c was isolated in 97%, 96% and 91% yields and TON
of 1147, 1123 and 1076 respectively. Cyclohexyldimethylsilane
(2g) reacted smoothly to furnish the desired silyl ether in high yield
(entry 7). In reactions where yields are moderate (Table 2, entries
1, 5, 6), menthol was recovered, while the starting silane was
converted into silanol or siloxane. Our Pd-NP catalytic method
thus leads to dehydrogenative silylation of (-)-menthol with
various hydrosilanes in moderate to excellent yields depending
on the steric hindrance of the starting silane.
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10.1002/chem.201803989
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2d
Ph3SiH ( , 2.5 equiv.)
Table 2. Scope of hydrosilanes for dehydrocoupling.
Pd-NP4 (30 mg/mmol)
ROH
RO-SiPh3
nBu2O, 70°C
3
1
1
2 3
2
R R R SiH ( , 2.5 equiv.)
R1
Si
R3
Pd-NP4 (cat.)
Ph3SiO
Ph
OSiPh3
Me
OSiPh3
Ph
R2
OH
nBu2O, 70 C, Time
O
Me
a
3i, 22 h, 91%
3j
, 20 h, 94%
3h
, 44 h, 52%
1a
3
tBu
O
Entry[a] Silane
R1
R2
R3
Time
(h)
Yield
[%][b]
OSiPh3
OSiPh3
EtO
Ph3SiO
1
2
3
4
5
6
7
2a
2b
2c
2d
2e
2f
Carbazole
Ph
Me
Et
Ph
tBu
Me
Me
Me
Me
Et
Ph
Me
Me
Me
46
16
20
20
46
42
21
3a 54[c] (d.r. 1:1)
3b, 85
3m
3l
, 18 h, 97%
3k
, 20 h, 87%
, 24 h, 95%
Ph
Et
Ph
3c, 97[d]
3d, 81
Ph
3e 43[c] (d.r 1:1)
OSiPh3
tBu
3f, 47[c]
2g
Cyclohexyl
3g, 93
Cl
3n
OSiPh3
, 18 h, 93%
Cl
Ph3SiO
[a] Reaction Conditions: 1a (0.5 mmol), 2 (2.5 equiv., 1.25 mmol), Pd-catalyst
(15 mg, 0.0135 mmol of Pd(0)), in nBu2O (2 mL) at 70 °C. [b] Isolated yield after
column chromatography. [c] 30 mg of catalyst was used instead of 15 mg and
heated at 100 °C instead of 70 °C. [d] Reaction was also performed with 1 mg
of Pd-catalyst leading to 3c in 32% yield (TON: 11428).
3p
, 12 h, 94%
3o, 26 h, 58%
[a] Reaction at 100 °C using 60 mg/mmol catalyst.
Scheme 2. Scope of the dehydrogenative silylation of alcohols
After successful synthesis of silyl ethers from (-)-menthol, the
scope of the transformation was further investigated, varying the
nature of the alcohol partner 1 using Ph3SiH (Scheme 2).
Sterically crowded (-)-borneol was shown to afford the silyl ether
3h when reacting with triphenylsilane over a longer period of time,
albeit in moderate yield. Unreacted (-)-borneol and
triphenylsilanol were also isolated. Small and medium-sized
secondary aryl alcohols were amenable to the Pd-nanoparticle
catalyzed dehydrocoupling reactions to give the silyl ethers 3i and
3j in excellent yields. It is noticeable that Pd-catalyzed
debenzylation did not occur with benzylic alcohols and ethers (i.e.
3i). Cyclic secondary and tertiary alcohols were also tested, 4-
tertbutylcyclohexanol and 1-adamantanol being found equally
effective, providing the corresponding dehydrocoupled product
3k-l. Selective coupling with alcohols in the presence of fragile or
reducible ester and chloro functionalities also showed the
efficiency of the current protocol to furnish 3m-o. The feasibility of
our method was further manifested with naturally occuring
5α-cholestan-3β-ol that was silylated to give 3p under our reaction
conditions.
When the above procedure was applied to propargylic alcohols,
protection of the OH groups was observed, along with the
hydrogenation of the triple bond (Scheme 3). Catalytic access to
thermodynamically less stable Z-alkenols was thus achieved by
tandem dehydrogenative silylation/hydrogenation of propargyl
alcohols or homopropargyl alcohols. It provides an atom
economical process for both the dehydrocoupling and
hydrogenation reactions using in-situ generated H2. Aryl and alkyl
substituted allyl silyl ethers (3q and 3r respectively) were
synthesized directly from propargyl alcohols in good yields.
Homopropargyl alcohols also provided the homoallyl silyl ethers
in this reaction (3s). Selectivity in favour of the Z-alkene was not
influenced by the nature of the silyl protecting group. The length
of the carbon chain between the triple bond and the alcohol
function has no major influence on the process as shown by the
formation of alkoxysilane 3t.
R1R2R3SiH 2 (2.5 equiv.)
OH
SiR1R2R3
Pd-NP4
(cat.)
nBu2O, 70 C
O
n
n
R
R
3
1
OSiMe2Ph
OSiPh3
OSiEt3
nPr
Me
Ph
3q, 15 h, 69%
Me
, 16 h, 78%
3s
3r
, 24 h, 66%
OSiMe2Ph
nBu
3t, 15 h, 62%
Scheme 3. Tandem dehydrogenative silylation/hydrogenation of alkynols.
In addition, selectivity between primary and secondary alcohols
was examined (Scheme 4). Homochiral 1-phenylethane-1,2-diol
was reacted with 1.0 and 2.0 equivalents of dimethyltert-
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10.1002/chem.201803989
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butylsilane under standard reaction conditions. Although our
methodology is efficient for the silylation of secondary benzylic
alcohols (as mentioned in Scheme 2), an excellent selectivity was
observed towards primary alcohol even in the presence of excess
hydrosilane. Optical rotation of silyl ether 5a proved to be in
excellent agreement with that reported in the literature,[25]
indicating that the dehydrogenative silylation of benzylic 1,2-diols
is not only regioselective, but also occurs with no racemization at
the benzylic center. Competition between secondary and tertiary
alcohols in diol 4b, using a smaller hydrosilane, led to the sole
protection of the secondary hydroxy group (i.e. 5c), albeit
requiring an excess of the silane to obtain high yield.
uses readily available starting materials and Pd-nanoparticles
which are easily accessible. It is thus anticipated that this
approach should find applications in organic synthesis.
Experimental Section
General procedure for the dehydrogenative silylation
In a sealed tube equipped with a magnetic stir bar, was placed (-)-menthol (78
mg, 0.5 mmol). It was introduced into a glove box and 15 mg of Pd-nanoparticle
catalyst was added. The tube was capped and taken out from the glove box.
Anhydrous n-dibutylether (1.5 mL) (distilled over Na) was added via syringe
followed by the addition of a solution of triphenylsilane (2.5 equiv., 1.25 mmol)
in n-dibutylether (0.5 mL). The reaction mixture was heated to 70 °C until
starting material is consumed. After the reaction is completed, the crude mixture
was filtered through a short plug of silica to remove Pd-catalyst eluting with
dichloromethane. Following evaporation of the solvents under vacuum, flash
column chromatography was performed on silica gel using ethyl acetate in
petroleum ether to get the desired product (168 mg, 81% yield).
tBuMe2SiH
OSiMe2tBu
OH
OH
Pd-NP4 (cat.)
+
nBu2O, 70 °C, 20 h
OSiMe2tBu
OH
OSiMe2tBu
4a
5a
5b
tBuMe2SiH (1.0 equiv.)
tBuMe2SiH (2.0 equiv.)
85%
94%
not formed
traces
Acknowledgements
PhMe2SiH
SP thanks EU for a postdoctoral grant through H2020-MSCA-IF-
2015 program (N° 704870). The Agence Nationale de la
recherche is thanked for financial support (ANR-16-CE07-0018-
01). The University of Bordeaux and CNRS are gratefully
acknowledged for financial support.
OH
OH
OSiMe2Ph
Pd-NP4
(cat.)
+
HO
nBu2O, 70 °C, 20 h
PhMe2SiO
HO
4b
5c
5d
PhMe2SiH (1.0 equiv.)
PhMe2SiH (2.0 equiv.)
47%
73%
not formed
not formed
Keywords: dehydrogenative silylation
• hydrosilane • Pd
Scheme 4. Selectivity for the silylation between 1°, 2° and 3° alcohols.
nanoparticles • protecting group • hydrogenation
[1]
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Finally, silyl ethers may also be obtained through a tandem ring
opening-silylation of epoxides using our catalysts.[26] Silyl ether 7
was thus prepared in good yield through the epoxide ring opening
of styrene oxide 6 in the presence of Bu2SiH2, illustrating the
versatility of these readily available catalysts (Scheme 5).
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t
tBu2SiH2 (1.5 equiv.)
O
OSiHtBu2
[3]
[4]
Pd-NP4
(cat.)
nBu2O, 70 °C, 16 h
7
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74%
Scheme 5. Silylation of epoxides.
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In conclusion, we have developed a practical method for the
dehydrogenative coupling between various types of hydrosilanes
and alcohols. This Pd-nanoparticle catalyzed method offers
significant advantages over the previous protocols for the
synthesis of sterically hindered silyl ethers. It allows the reaction
to be performed under mild neutral conditions, without the
recourse to strong bases (tBuOK or KOH for instance), using
cheap and readily prepared catalysts. The method offers good
compatibility with various functional groups, such as chlorides,
esters and benzylic alcohols and ethers. Examples of synthesis
of allyl and homoallylsilyl ethers, from propargyl and
homopropargyl alcohols, in an atom economical tandem
silylation-hydrogenation process, were also provided to
demonstrate the utility of the process. This synthesis of silyl ethers
[7]
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10.1002/chem.201803989
Chemistry - A European Journal
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S. Pramanik, A. Fernandes, V. Liautard,
M. Pucheault, F. Robert* and Y.
Landais*
Page No. – Page No.
Dehydrogenative Silylation of
Alcohols Under Pd-nanoparticles
Catalysis.
Pd-nanoparticles-catalyzed dehydrogenative coupling between hydrosilanes and
alcohols to give silyl ethers is described. High selectivity for the silylation of primary
versus secondary and secondary versus tertiary alcohols in 1,2-diols is observed.
Tandem silylation/hydrogenation of the triple bond of alkynols to afford Z-alkenols
has also been achieved.
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