Hydrosilylation of ketones: From metal-organic frameworks to simple base catalysts

Article abstract of DOI:10.1002/asia.201000427

A convenient base-catalyzed hydrosilylation of aromatic ketones using inexpensive bases, such as 1M sodium hydroxide in methanol or sodium/potassium tert-butoxide, has been developed. Mild reaction conditions (room temperature, 1 h) successfully promote the hydrosilylation of a variety of ketones.

Full text of DOI:10.1002/asia.201000427

DOI: 10.1002/asia.201000427
Hydrosilylation of Ketones: From Metal–Organic Frameworks to Simple
Base Catalysts
[
a]
[a]
[a]
[a]
[a, b]
Daniele Addis, Shaolin Zhou, Shoubhik Das, Kathrin Junge, Hendrik Kosslick,
[
b]
[a, b]
[a, b]
[a]
Jçrg Harloff, Henrik Lund,
Axel Schulz,*
and Matthias Beller*
The catalytic reduction of carbonÀheteroatom multiple
bonds under mild conditions constitutes an important trans-
formation in organic synthesis and the pharmaceutical as
catalysts continues to attract academic and industrial inter-
est.
Based on the recent work of groups including ourselves
[1]
[17,18]
well as agrochemical industry. Obviously, high selectivity
and broad tolerance towards functional groups are key fac-
tors for the acceptance and application of novel methodolo-
gies. In addition to molecular hydrogen and hydrogen trans-
on iron-, zinc-, and copper-catalyzed reductions,
we
started a joint program to explore the catalytic performance
of heterogeneous catalysts for the hydrosilylation of ke-
[19]
tones. In particular, we were attracted by the use of so-
called metal–organic frameworks (MOFs), an important
[2]
fer reagents, hydrosilanes are commonly used as reducing
[3]
[20]
agents.
class of porous crystalline materials. Because of their high
[4]
Since the early reports three decades ago, the asymmet-
ric and non-asymmetric hydrosilylations of prochiral ketones
relied mainly on precious-metal-based catalysts, such as rho-
porosity and surface area, these materials may also find ap-
[21]
plications in catalysis.
At the starting point of our investigations, we used the
[
5]
[6]
[7]
dium, ruthenium, and iridium. However, less-expensive
known {Cu
material (Figure 1)
A
H
U
G
R
N
U
G
3
2
[22]
[8]
[9]
[10]
metals, such as titanium, tin, and copper
plored, too. More recently, efforts have been devoted to
the development of more-benign and available bio-relevant
metal catalysts based on iron and zinc complexes.
Notably, silanes have also been used as reducing reagents
in the presence of acid, fluoride ions, or base,
were ex-
[11]
none. To the best of our knowledge, this and similar MOFs
[23]
have not been applied in such reductions.
[12]
[13]
In exploratory experiments, the variation of the reaction
temperature and solvent were performed in the presence of
different silanes. To determine product yields conveniently
by GC, NaOH (1m) in methanol was added after 16 hours
to hydrolyze the corresponding silyl ether to 1-phenyletha-
nol. Selected catalytic results are shown in Table 1. Whilst
[14]
[15]
[14a,15b,16]
although in many cases harsh reaction conditions and large
amounts of salt or base were required. Clearly, each of these
procedures has its merits as well as limitations. Either the
cost of the metal catalyst, toxicity of the residual metal in
the product, operational difficulties (such as low tempera-
ture À50 to À708C), or the use of complex ligand systems
limit their applications. Hence, the development of novel
[
a] D. Addis, S. Zhou, S. Das, Dr. K. Junge, Dr. H. Kosslick, H. Lund,
Prof. Dr. A. Schulz, Prof. Dr. M. Beller
Leibniz-Institut fꢀr Katalyse e.V. an der Universitꢁt Rostock
Albert-Einstein-Straße 29a
D-18059 Rostock (Germany)
Fax : (+49)381-1281-5000
E-mail: matthias.beller@catalysis.de
[
b] Dr. H. Kosslick, Dr. J. Harloff, H. Lund, Prof. Dr. A. Schulz
Institut fꢀr Chemie, Universitꢁt Rostock
Albert-Einstein-Straße 3
D-18059 Rostock (Germany)
Fax : (+49)381-1281-5000
E-mail: axel.schulz@uni-rostock.de
3 2
Figure 1. Structure of the {Cu ACHTUNRTGENNGNU( BTC) } pore.
Chem. Asian J. 2010, 5, 2341 – 2345
ꢂ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2341

COMMUNICATION
poly(methylhydrosiloxane) (PMHS), (EtO) MeSiH, and
tion reaction with acetophenone was performed with the fil-
trate of a {Cu3(BTC) }-catalyzed reaction. To our surprise,
2
Ph SiH did not lead to the desired 1-phenylethanol, the re-
ACHTUNGTRENNUNG
2
2
2
action proceeded smoothly when the more reactive phenyl-
silane was used (Table 1, entries 4–6). Even in the presence
we again obtained near-complete conversion (98%) and
94% yield of 1-phenylethanol, apparently thus demonstrat-
ing significant catalyst leaching.
Moreover, we looked for the activity of any acidic or
basic impurities present in the reaction. To our surprise,
smooth reduction of acetophenone took place in the pres-
ence of base in methanol at room temperature. Whilst it is
known that phenylsilane undergoes alcoholysis with alcohol
Table 1. Hydrosilylation of acetophenone with {Cu
silanes and solvents.
3 2
ACHTUNGTNERNUG( BTC) }: variation of
[24]
and base, there have been no reports on the reduction of
ketones under such conditions. In the presence of 5 mol%
of tBuONa or an inexpensive 1m solution of NaOH in meth-
anol, the starting material disappeared quickly, leading to
the formation of the corresponding silyl ether in good to
quantitative yield (Table 2). Interestingly, apart from
PhSiH , other less expensive silanes, such as (EtO) MeSiH
[
a]
Entry
Cu
3
A
C
H
T
U
N
G
T
R
E
N
N
U
N
G
(BTC)
2
[mg]
Silane
(EtO) MeSiH
Ph SiH
PMHS
Solvent T [8C] Yield [%]
1
2
3
4
5
6
7
8
9
1
1
7.5
7.5
7.5
7.5
1
1
1
1
1
A
H
U
G
R
N
U
G
2
THF
65
<1
6
2
2
toluene
toluene
toluene
toluene
toluene
AcOEt
RT
RT
RT
RT
RT
RT
RT
RT
RT
RT
<1
>99
99
PhSiH
PhSiH
PhSiH
PhSiH
PhSiH
PhSiH
PhSiH
PhSiH
3
3
3
3
3
3
3
3
[
[
[
[
b]
b]
b]
b]
99
74
3
2
and Ph SiH worked well in this benchmark reduction.
2
2
CH
Et
2
Cl
O
2
40
94
2
[
[
b]
0
1
1
1
THF
n-hexane
81
38
[a]
Table 2. Base-catalyzed hydrosilylation of acetophenone.
b]
[
a] Reaction conditions: MOF (0.0125 mmol), acetophenone (0.5 mmol),
toluene (2 mL), then addition of the silane (1.3 equiv (EtO) MeSiH;
equiv Ph SiH ; 3 equiv PMHS; 2 equiv PhSiH ). After 16 h, NaOH in
2
2
2
2
3
methanol (2 mL, 1m) was added to the solution at 08C and the mixture
was left to stir for 2 h at RT. Yield was determined by GC analysis (50 m
Lipodex E, 95–2008C) with diglyme as an internal standard; [b] Reaction
time: 1 h. THF=tetrahydrofuran, Ac=acetyl.
[
a]
Entry
Base [5 mol%]
Silane [2 equiv]
(EtO) MeSiH
PhSiH
Ph SiH
(EtO) MeSiH
Conv. [%]
Yield [%]
1
2
3
4
5
tBuOK
tBuOK
tBuOK
tBuONa
tBuONa
NaOH
A
H
U
G
R
N
U
G
2
>99
>99
>99
>99
99
98
98
96
95
96
60
3
2
2
A
H
U
T
E
N
N
2
PhSiH
PhSiH
3
of only 1 mg of {Cu
A
H
U
G
E
N
N
(BTC) }, which corresponds to around
[b]
3
2
6
3
60
1
mol% of copper, we obtained >99% yield of 1-phenyl-
[
(
a] Reaction conditions: acetophenone (0.5 mmol), toluene (2 mL), silane
2 equiv). After 1 h, NaOH (2m) was added to the solution at 08C and
ACHTUNGTRENNUNGe thanol within 1 hour. With respect to the solvent, the best
results were observed in toluene and diethyl ether. Other
solvents, such as ethyl acetate, dichloromethane, and n-
hexane also worked, but gave significantly lower yields.
Noteworthy, in toluene and diethyl ether the blue color of
the mixture was stirred for 2 h at RT. Yield was determined by GC analy-
sis (50 m Lipodex E, 95–2008C) with diglyme as an internal standard.
[
b] 1 mmol acetophenone, addition of the silane (2 equiv). After 0.5 h,
NaOH in methanol (2 mL, 1m) was added to the solution at 08C and the
mixture was left to stir for 2 h at RT.
{
Cu ACHTUNGTRENNUNG( BTC) } did not change during the reaction. However,
3 2
in the other solvents the reaction solution turned black a
few minutes after the addition of silane. Apparently, in the
latter cases, leaching of copper ions and formation of
copper(0) took place. This effect proceeded within minutes
in n-hexane, whilst in toluene it was only observed after
The performance of these simple bases was quite unex-
pected, considering the reaction of ketones and aldehydes
with stoichiometric amounts of pentacoordinated hydrosi-
[25]
[26]
lanes or with more complex lithium amino-alkoxides.
2
days. It is important to note that not only the solvent
In order to demonstrate the general applicability of these
convenient procedures, we investigated the hydrosilylation
of different ketones in the presence of: A) a 2m solution of
NaOH in methanol and B) catalytic amounts (5 mol%) of
tBuOK. Under the latter conditions, complete formation of
the corresponding silyl ether was obtained within a few mi-
nutes. The two procedures are compared in Table 3. In gen-
eral, the reactions catalyzed by potassium tert-butoxide gave
somewhat higher yields compared to NaOH. However, in
the case of 4-phenylbut-3-en-2-one, NaOH gave the allylic
alcohol in 76% yield, whilst tBuOK gave only 46% yield
(Table 3, entry 10). Acetophenones containing electron-
withdrawing substituents (Cl, Br, F, CF -, CN, NO ), in the
played a crucial role in preventing the formation of elemen-
tal copper, because reduction to copper(0) could also be ob-
served in toluene after 20 minutes, if no ketone was added.
Based on these initial promising results, we tested 15 dif-
ferent MOF-based materials in the standard reaction under
the optimized conditions (2 equivalents of PhSiH , toluene,
3
room temperature). In addition to various copper-based
MOFs, different zinc-, iron-, and one chromium-containing
metal-organic framework were considered and gave product
yields in the range 30–80%. However, there was no clear
trend observed with respect to the size of the pores or the
coordinating metal. Hence, we wanted to investigate in
more detail what was happening in the reaction media. In
order to confirm any leaching effect, a second hydrosilyla-
[23]
3
2
ortho-, meta-, or para-positions provided their corresponding
benzyl alcohols in moderate to good yields (48–92%) in the
2342
www.chemasianj.org
ꢂ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Asian J. 2010, 5, 2341 – 2345

Hydrosilylation of Ketones
Table 3. Hydrosilylation of different ketones in the presence of base:
substrate scope.
presence of 5 mol% tBuOK (Table 3, entries 2–4, 8, 9, 11,
2). Notable is the chemoselective reduction of the carbonyl
1
Entry
Ketone
Yield
NaOH (A) [%]
Yield
tBuOK (B) [%]
group in the presence of halides, nitro, and cyano substitu-
ents. 4-Methoxyacetophenone bearing an electron-donating
substituent on the phenyl ring showed a decreased reactivity
yielding the corresponding alcohol in 58% yield (Table 3,
entry 7). In addition to substituted acetophenones, tetralone
reacted well both in the presence of NaOH and tBuOK
[
a]
[b]
1
60
70
99
77
(
Table 3, entry 5). Whilst diaryl ketones did not react in the
2
presence of NaOH, hydrosilylation took place smoothly
with the more reactive alkoxide (Table 3, entry 6). Finally,
we demonstrated that aldehydes were also easily reduced
under these conditions to give high yields of the correspond-
ing alcohols (Table 3, entries 13 and 14).
In summary, we report a convenient and general hydrosi-
lylation of aromatic ketones and two aldehydes. Based on
the exploration of the catalytic potential of MOFs in the re-
duction of acetophenone, we discovered that simple and in-
expensive bases, such as NaOH (2m) in methanol or catalyt-
ic amounts of tBuOK, promote this reaction. This procedure
works well with 12 different aromatic ketones and two alde-
hydes under mild conditions (room temperature, air) toler-
ating other sensitive functional groups.
3
4
5
6
7
10
38
58
67
60
66
58
50
<1
30
Experimental Section
A
H
U
G
R
N
U
G
3 2
ACHTUNGTNERNUG( BTC) }-catalyzed hydrosilylation of ketones: A 10 mL oven-dried
3
A
H
U
G
R
N
U
G
2
8
9
15
<1
76
73
48
46
90
92
3
(
action mixture was further stirred for 30 min at RT, then cooled to 08C
followed by the sequential addition of diglyme (80 mL) as a GC standard
in case of analysis by GC), and 1m NaOH in methanol (2 mL) with vigo-
rous stirring (caution: The reaction mixture bubbled briefly but vigorous-
ly upon the addition of the base). The reaction mixture was further
stirred for an hour (or until the organic layer became colorless/pale
yellow) at room temperature and was extracted with diethyl ether (3ꢃ
0 mL). The combined organic layers were washed with brine, dried over
anhydrous Na SO , filtered (an aliquot was removed for GC analysis),
and concentrated under vacuum. The residue was purified by column
chromatography on silica gel using an ethyl acetate/n-hexane mixture (20
to 40%) to afford the desired product.
(
1
1
1
0
1
2
1
2
4
52
Reduction of ketones with base in methanol: A 10 mL oven-dried
Schlenk tube containing a stirrer bar was purged with argon (argon/
vacuum three cycles), anhydrous toluene (2 mL) followed by ketone
48
(
3
1 mmol) and PhSiH (0.18 mL, 2 equivalents) were added using a syringe
under argon. The reaction mixture was further stirred for 30 min at RT,
then cooled to 08C followed by the sequential addition of diglyme
1
1
3
4
75
97
91
99
(
80 mL) as a GC standard (in case of analysis by GC), and 1m NaOH in
methanol (2 mL) with vigorous stirring (caution: The reaction mixture
bubbled briefly but vigorously upon the addition of the base). The reac-
tion mixture was further stirred for an hour (or until the organic layer
became colorless/pale yellow) at room temperature and was extracted
with diethyl ether (3ꢃ10 mL). The combined organic layers were washed
[
3
a] Ketone or aldehyde (1 mmol), silane (2 equiv PhSiH ). After 0.5 h,
NaOH in methanol (2 mL, 1m) was added to the solution at 08C and the
mixture was left to stir for 2 h at RT; [b] tBuOK (5.6 mg), acetophenone
2 4
with brine, dried over anhydrous Na SO , filtered (an aliquot was re-
moved for GC analysis), and concentrated under vacuum. The residue
was purified by column chromatography on silica gel using an ethyl ace-
tate/n-hexane mixture (20 to 40%) to afford the desired product.
(
3
1 mmol), silane (2 equiv PhSiH ). After 0.5 h, NaOH in water (2m) was
added to the solution at 08C and the mixture was left to stir for 2 h at
RT.
tBuOK-catalyzed hydrosilylation of ketones:
A 10 mL oven-dried
Schlenk tube containing a stirrer bar, was charged with tBuOK (5.6 mg,
Chem. Asian J. 2010, 5, 2341 – 2345
ꢂ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemasianj.org
2343

A. Schulz, M. Beller et al.
COMMUNICATION
5
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drous toluene (2 mL) followed by ketone (1 mmol). The PhSiH
3
(
(
0.18 mL, 2 equivalents) was slowly added using a syringe under argon
fast gas evolution was observed). The reaction mixture was further
stirred for 30 min at RT, then cooled to 08C followed by the sequential
addition of diglyme (80 mL) as a GC standard (in case of analysis by
GC), and 2m NaOH in water (2 mL) with vigorous stirring (caution: The
reaction mixture bubbled briefly but vigorously upon the addition of the
base). The reaction mixture was further stirred for an hour (or until the
organic layer became colorless/pale yellow) at room temperature and
was extracted with diethyl ether (3ꢃ10 mL). The combined organic
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layers were washed with brine, dried over anhydrous Na SO , filtered (an
aliquot was removed for GC analysis) and concentrated under vacuum.
The residue was purified by column chromatography on silica gel using
an ethyl acetate/n-hexane mixture (20 to 40%) to afford the desired
product.
2
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(Yield=59%); 2D Cu-MOF: {Cu(1,4-BDC)} (Yield=79%);
{Cu(1,2,4,5-BTC)0.5DMF} (Yield=76%); [Cu(4,4’-BPDC)0.5
(Yield=64%); MOF-177: Zn (BTB) (DEF)15(H O) (Yield=
33%); [Cr (H O) O(1,3,5-BTC) ]·H O (Yield=21%); Cu [(o-Br-
(CO (Yield=23%).
A
H
U
G
R
N
U
G
A
H
U
G
R
N
U
G
n
(Yield=58%); [Cu(4,4’-
3
A
C
H
T
U
N
G
T
R
E
N
N
U
N
G
(BTB)
2 n
}
[
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·
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N
U
G
A
T
N
T
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N
N
2
3
3
F
) ]
2 2 2
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2
3
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A
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N
T
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23] MOF-2: {Zn
BDC)
A
C
H
T
U
N
G
T
R
E
N
N
U
N
G
(1,4-BDC)}
n
4
(Yield=75%); MOF-5: {Zn OACHTUNGTRENUGNN
3
}
n
(Yield=85%); IRMOF-3 (Yield=41%); CuCl
2
2
+
2+
(
(
Yield=26%); IRMOF-10 (Cu 50%): Cu
Yield=82%); IRMOF-10 (Fe
A
H
U
T
E
N
N
4
O
O
A
H
U
G
R
N
U
3
3
}
}
n
n
Received: June 12, 2010
Published online: October 4, 2010
3
+
3+
50%): Fe
A
H
U
T
E
N
N
4
A
H
U
G
E
N
N
Chem. Asian J. 2010, 5, 2341 – 2345
ꢂ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemasianj.org
2345