Chemoselective Hydrogenation of α,β-Unsaturated Carbonyls Catalyzed by Biomass-Derived Cobalt Nanoparticles in Water

Article abstract of DOI:10.1002/cctc.201801987

Herein, we report highly chemoselective hydrogenation of α,β-unsaturated carbonyls to saturated carbonyls catalyzed by cobalt nanoparticles supported on the biomass-derived carbon from bamboo shoots with molecular hydrogen in water, which is the first prototype using a heterogeneous non-noble metal catalyst for such organic transformation as far as we know. The optimal cobalt nanocatalyst, CoO_x@NC-800, manifested remarkable activity and selectivity for hydrogenation of C=C in α,β-unsaturated carbonyls under mild conditions. A broad set of α,β-aromatic and aliphatic unsaturated carbonyls were selectively reduced to their corresponding saturated carbonyls in up to 99 % yields with good tolerance of various functional groups. Meanwhile, a new straightforward one-pot cascade synthesis of saturated carbonyls was realized with high activity and selectivity via the cross-aldol condensation of ketones with aldehydes followed by selective hydrogenation. More importantly, this one-pot strategy is applicable for the expedient synthesis of Loureirin A, a versatile bioactive and medicinal molecule, from readily available starting materials, further highlighting the practical utility of the catalyst. In addition, the catalyst can be easily separated for successive reuses without significant loss in both activity and selectivity.

Full text of DOI:10.1002/cctc.201801987

Accepted Article
Title: Chemoselective Hydrogenation of α,β-Unsaturated Carbonyls
Catalyzed by Biomass-Derived Cobalt Nanoparticles in Water
Authors: Yong Yang, Tao Song, and Zhiming Ma
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ChemCatChem
10.1002/cctc.201801987
FULL PAPER
Chemoselective Hydrogenation of α,β-Unsaturated Carbonyls
Catalyzed by Biomass-Derived Cobalt Nanoparticles in Water
Tao Song, Zhiming Ma, and Yong Yang[a]*
[
a]
[a,b]
Dedication ((optional))
[
4]
[5]
[6]
[7]
Abstract: Herein, we report highly chemoselective hydrogenation of
α,β-unsaturated carbonyls to saturated carbonyls catalyzed by cobalt
nanoparticles supported on the biomass-derived carbon from bamboo
shoots with molecular hydrogen in water, which is the first prototype
using a heterogeneous non-noble metal catalyst for such organic
transformation as far as we know. The optimal cobalt nanocatalyst,
Pd , Ru , Rh , Ir , with assistance of sophisticated and
expensive
diisopropylphenyl)imidazol-2-ylidene,
dichlorotris(trisphenylphosphine),[
diphenylethylenediamine,[6c] and so on, for the homogeneous
catalysts, while with high expense of supports for the
heterogeneous catalysts (Scheme 2a).
organic
ligands,
such
as
N,N-bis(2,6-
[
4f]
Pincer-ligands,[4j]
5e]
N-(p-toluenesulfonyl)-1,2-
x
CoO @NC-800, manifested remarkable activity and selectivity for
hydrogenation of C=C in α,β-unsaturated carbonyls under mild
conditions. A broad set of α,β-aromatic and aliphatic unsaturated
carbonyls were selectively reduced to their corresponding saturated
carbonyls in up to 99% yields with good tolerance of various functional
groups. Meanwhile, a new straightforward one-pot cascade synthesis
of saturated carbonyls was realized with high activity and selectivity
via the cross-aldol condensation of ketones with aldehydes followed
by selective hydrogenation. More importantly, this one-pot strategy is
applicable for the expedient synthesis of Loureirin A, a versatile
bioactive and medicinal molecule, from readily available starting
materials, further highlighting the practical utility of the catalyst. In
addition, the catalyst can be easily separated for successive reuses
without significant loss in both activity and selectivity.
Scheme 1. Selected pharmaceutically active molecules contained the 1,4-diaryl
ketone skeletons.
Under the increasing pressure of the energy crisis and
economic constraints, the replacement of noble metals by
inexpensive and earth-abundant non-noble metals would be
preferable in sustainable catalysis and synthesis, especially for
more widespread and industrial applications. Despite recent
sporadic reports regarding ligand-enabled non-noble metal
catalyzed selective hydrogenation of the C=C bond of α,β-
unsaturated carbonyls,[8] a heterogeneous catalyst with high
chemoselectivity remains elusive.[9] As a consequence, from both
economic and environmental viewpoints, there is a strong
incentive to develop a reusable heterogeneous non-noble-metal
catalyst for highly efficient and selective hydrogenation of the C=C
bond of α,β-unsaturated carbonyls.
Introduction
The chemoselective hydrogenation of α,β-unsaturated
carbonyls is a pivotal tactics both in the academic research and
industry applications due to its extensive applications in the
synthesis of fine chemicals, pharmaceuticals and functional
materials.[1] In general, three types of product can be obtained
from the hydrogenation of α,β-unsaturated carbonyls via either
the selective reduction of the C=C or the C=O bond, or non-
selective reduction of both bonds. The highly chemoselective
reduction of one of the C=C and C=O bonds in the α,β-
unsaturated carbonyls is still demanding yet can be challenging
in some situations. Particularly, the selective hydrogenation of the
C=C bond of α,β-unsaturated carbonyls with the C=O bond intact
is one important synthetic transformation because the
corresponding reduced products are valuable substructures for
[
2]
many pharmaceutically active molecules (Scheme 1) .
Over the past decades, great efforts have been made to
contribute to the selective reduction of the C=C bond of α,β-
unsaturated carbonyls to saturated carbonyls with various
2
hydrogen donors, such as H , formic acid, alcohols, hydrosilanes,
borohydrides, (para)formaldehyde, and other ones. However, in
[
3]
most cases, they generally employ noble metals, e.g., as Pt ,
aDr. T. Song, Mr. Z. Ma, Prof. Dr. Y. Yang
Qingdao Institute of Bioenergy and Bioprocess Technology,
Chinese Academy of Sciences, Qingdao 266101, China
b
University of Chinese Academy of Sciences, Beijing 100049, China.
*
E-mail: yangyong@qibebt.ac.cn
Scheme 2. The strategies for chemoselective hydrogenation C=C bond of α,β-
Supporting information for this article is given via a link at the end of the
document.((Please delete this text if not appropriate))
unsaturated carbonyls.
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ChemCatChem
10.1002/cctc.201801987
FULL PAPER
Results and Discussion
significantly beneficial to the improvement of conversion. Among
2
all investigated solvents, H O, as a green and sustainable solvent,
In our continuation to develop green catalysis for sustainable
organic synthesis, we very recently developed an efficient and
recyclable inexpensive cobalt nanocomposites on N-doped
hierarchical carbon derived from biomass for chemoselective
hydrogenation of functionalized nitroarenes.[10] Inspired by the
impressive results, we are eager to extend the application of this
catalyst for the selective hydrogenation of α,β-unsaturated
carbonyls. Herein, we report that this cobalt nanocomposites
catalyst is capable of catalysing chemoselective hydrogenation of
the C=C bond of α,β-unsaturated carbonyls in water (Scheme 2c).
The present catalytic system shows outstanding catalytic activity
with exclusive selectivity to C=C bond reduction and broad
substrate scope for various α,β-unsaturated carbonyl compounds
with good tolerance of functional groups. In addition, the cobalt
nanocomposites catalyst also shows high activity for one-pot
direct synthesis of saturated carbonyls from ketones and
aldehydes as starting materials via a sequential cross-aldol
condensation and selective hydrogenation (Scheme 2d). More
importantly, this new straightforward one-pot cascade method is
applicable for expedient synthesis of pharmaceutically active
Loureirin A in a simple and green manner.
showed superior catalytic efficiency with complete conversion and
exclusive selectivity to 2a.
Interestingly, the pressure of H can be reduced from 5 to 2
2
MPa with maintaining the equal activity and selectivity upon
addition of an equivalent of tetrabutylammmonium iodide (TBAI)
(with respect to 1a) into the reaction mixture under otherwise
identical conditions. This result indicates that TBAI might act as a
surfactant to improve the solubility of organic substrate and
dispersion of the catalyst in water, and the interfacial contact
between the catalyst and substrate as well. To confirm this, the
hydrogenation of 1a in the absence of TBAI or the presence of 0.5
equivalent of TBAI was performed.
A considerable lower
conversion was observed in each case, especially for the reaction
without TBAI (entries 1 and 3), demonstrating the importance of
TBAI for the enhanced reaction efficiency. Other common
surfactants, such as tetrabutylammonium bromide (TBAB),
tetrabutylammonium fluoride (TBAF), sodium dodecyl sulfate
(SDS), hexadecyl trimethyl ammonium bromide (CTAB), were
also employed for the reaction (Table 1, entries 7-10). All showed
a pronounced improvement in activity under identical conditions,
while TBAI gave the maximum. Reducing the reaction
temperature or the dosage of catalyst resulted in lower conversion
under otherwise identical conditions (Table 1, entries 4-6). In line
with our previous findings, the catalyst CoO
x
@NC-800 also gave
o
the best result compared with that pyrolyzed at 700 or 900 C
(
Table 1, entries 11 and 12). In sharp contrast, the catalyst
CoO @C-800, which was prepared form pyrolysis of the mixture
x
of cobalt salt and the commercially available activated carbon
without N-dopant, only achieved half of the reaction efficiency to
that of CoO
3), indicating the critical role of N-dopant in the carbon
framework for the reaction. Other control experiments showed
that CoCl , pure Co , pure nano Co (100 nm) as catalyst or
x
@NC-800 under identical conditions (Table 1, entry
1
2
3
O
4
3 4
O
in the absence of the catalyst led to considerably lower activity or
even no reactivity (Table 1, entry 14-18), further reflecting the
x
Figure 1. Schematic illustration of the preparation of CoO @NC.
The cobalt nanoparticles (NPs) comprising of metallic cobalt as
core covered with cobalt oxide as shell on N-doped hierarchical
porous carbon derived from naturally renewable biomass,
essential role of the catalyst CoO
Therefore, upon rapid investigation of reaction factors, the optimal
reaction conditions involve 10 mol% of CoO @NC-800 as the
x
@NC-800 in catalysis.
x
denoted as CoO
x
@NC-T (where
T
represents pyrolysis
catalyst, an equivalent of TBAI as the surfactant, H
2
O as solvent,
o
temperature), were synthesized by a facile tandem hydrothermal-
pyrolysis process as reported in our earlier work[10] (Figure 1, see
details in the Supporting Information). Our previous work
regarding the hydrogenation of nitro compounds catalyzed by the
at 110 C reaction temperature, under 2 MPa of H
1, entry 2).
2
pressure (Table
Table 1. Optimization of reaction conditions.[a]
x
catalyst CoO @NC-T demonstrated that the synergistic effect
between Co NPs and N,O atoms incorporated in the carbon
framework dramatically improved the catalytic performance and
the catalyst CoO
decided to perform the hydrogeantion of 1,3-diphenylprop-2-en-
-one (chalcone, 1a) as a model substrate to assess whether the
catalyst CoO @NC-800 could enable selective hydrogenation of
x
@NC-800 gave the best outcome. We then
Entry
Cat.
Additive
Conv.(%)[b]
Selec.(%)[b]
1
2
3
CoO
x
@NC-800
TBAI(0.5 eq.)
TBAI(1 eq.)
Blank
86
100
34
88
76
62
95
>99
>99
>99
>99
>99
>99
>99
1
x
CoO
x
@NC-800
@NC-800
@NC-800
@NC-800
@NC-800
@NC-800
C=C or C=O bond with molecular hydrogen under similar
conditions. To our delight, the reaction proceeded smoothly to
convert 1a to 1,3-diphenylpropan-1-one (2a) with 52% conversion
CoO
CoO
CoO
CoO
CoO
x
4[c]
TBAI(1 eq.)
TBAI(1 eq.)
TBAI(1 eq.)
TBAB(1 eq.)
x
x
x
x
and 100% selectivity using CH
3
CN as solvent under 5 MPa of H
2
5[d]
after 24 h (Table S5, entry 4). Rapid screening of the solvents
showed that the reaction efficiency had a profound dependence
on the polarity of the solvent (Table S5 in the Supporting
Information) and increasing the polarity of the solvents was
6[e]
7
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ChemCatChem
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FULL PAPER
8
9
1
1
1
1
1
1
1
1
1
CoO
CoO
CoO
CoO
CoO
x
x
x
x
x
@NC-800
@NC-800
@NC-800
@NC-700
@NC-900
TBAF (1 eq.)
SDS(1 eq.)
CTAB (1eq.)
TBAI(1 eq.)
TBAI(1 eq.)
TBAI(1 eq.)
TBAI(1 eq.)
TBAI(1 eq.)
TBAI(1 eq.)
TBAI(1 eq.)
Blank
69
86
82
76
83
50
10
13
11
0
>99
>99
>99
>99
>99
>99
>99
>99
>99
0
dehalogenated products. The two conjugated C=C bonds in
diphenylpenta-1,4-dien-3-one (1l) were both selectively reduced.
Heteroaromatic chacone-type derivatives (1m-1o) were also
compatible with the present conditions and gave the
corresponding saturated ketones in 61% to 84% yields,
respectively. Moreover, a set of α,β-unsaturated aldehyde (1p),
ketone (1q), ester (1r), acid (1s), nitrile (1p), and amide (1u) were
also successful for the selective reduction of C=C bonds, giving
the desired products in excellent yields under identical conditions.
In addition, the aliphatic unsaturated aldehydes including terminal
alkenyl (1x), disubstituted alkenyl (1y), and trisubstituted alkenyl
0
1
2
3
4
5
6
7
8
CoO
CoCl
Co
Nano Co
x
@C-800
2
3 4
O
(
1z) were all exclusively reduced to the their respective saturated
3 4
O
aldehydes in 61-82% yields. Other aliphatic unsaturated
carbonyls, like ketones (1v, 1w, 1ac), ester (1aa), or carboxylic
acid (1ab) were also smoothly converted to the saturated
carbonyls.
Blank
Blank
0
0
[
a] Reaction conditions: chalcone 1a (0.2 mmol), catalyst (20 mg, 10 mol% of
Meanwhile, natural and/or biologically active compounds,
such as Davidigenin, Rheosmin, Menthone, and Testosterone,
could also be efficiently and chemoselectively synthesized from
their respective α,β-unsaturated carbonyls in good to high yields
under the standard reaction conditions. Remarkably,
Testosterone was synthesized with exclusive diastereoselectivity,
affording cis-isomer as the sole product in the present catalysis
system. Note that the trisubstituted unsaturated ketone was
hydrogenated as effectively and efficiently as the disubstituted
ones, exemplified as synthesis of Menthone (Scheme 3).
o
Co), H
2
O (5 mL), H
2
(2 MPa), 110 C, 24 h. [b] Determined by GC and GC-MS
using dodecane as an internal standard sample and confirmed with their
o
o
corresponding authentic samples. [c] 100 C. [d] 90 C. [e] 10 mg of catalyst was
used.
To explore the general applicability of this protocol, various α,β-
unsaturated carbonyls were subjected to the optimized reaction
conditions (Table 2). Both electron-donating and -withdrawing
aromatic substituted α,β-enones (1a-1h) were reduced efficiently
to provide the corresponding desired products in good to excellent
yields. The steric effects have
Table 2. Substrate scope [a]
.
Scheme 3. Synthesis of natural and/or bioactive compounds under the standard
conditions.
The impressive results for the direct hydrogenation of α,β-
unsaturated carbonyls as demonstrated above clearly suggest
x
that the catalyst CoO @NC is inactive for reduction of the C=O
bond. It is well-known that the α,β-unsaturated carbonyls are
usually synthesized via the cross-aldol (or Claisen-Schmidt)
condensation between ketones and aldehydes in the presence of
base or acid[11]. The unique selectivity of this catalyst inspired us
to develop one-pot cascade synthesis of saturated carbonyls by
the cross-aldol condensation of ketones with aldehydes and
sequential selective hydrogenation. We then chose benzaldehyde
and acetonphenone as the model substrates to perform the one-
pot cascade reaction for the synthesis of saturated carbonyls. To
our delight, the 1,3-diphenylpropan-1-one (2a) could be obtained
with nearly quantitative yield under slightly modified optimal
x
conditions catalysed by the catalyst CoO @NC-800 upon addition
of NaOH as a base (Table S6). Subsequently, various typical
aldehydes and ketones were employed as the substrates to
proceed the reaction. We found that this protocol is suitable for
both electron-donating and -withdrawing aromatic substituted
benzaldehydes and acetonphenones to deliver the desired
saturated ketones in good to excellent yields. Furthermore, the
aliphatic acetone was also applicable for the synthesis of 4-
phenylbutan-2-one (2q) with 63% isolated yield (Table 3).
[
x
a] Reaction conditions: substrates (0.2 mmol), CoO @NC-800 (20 mg, 10mol%
o
of Co), TBAI (73.8 mg, 0.2 mmol), H
of isolated products are given.
2 2
O (5 mL), H (2 MPa), 110 C, 24 h. Yields
Table 3. One-pot synthesis of saturated ketones from various aldehydes and
negligible effect on reactivity, especially for the ortho-substituted
α,β-enones with either -OH or -Me group(1c, 1e, and 1h).
Halogen-substituted chalcones (1h-1k) gave the corresponding
saturated carbonyls in high isolated yields without detection of
ketones [
a]
.
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Conversion/%
Selectivity/%
100
80
60
40
20
0
0
1
2
3
4
5
Number of recycle
[
x
a] Reaction conditions: aldehyde (0.2 mmol), ketone (0.4 mmol), CoO @NC-
x
Figure 2. Recyclability of the catalyst CoO @NC-800 for the selective
o
8
2 2
00 (20 mg, 10 mol% of Co), NaOH (0.2 mmol), H O (5 mL), H (2 MPa), 110 C,
hydrogenation of α,β-unsaturated carbonyls under the standard conditions.
.
2
4 h Yields of isolated products are given.
To gain insight into the exclusive selectivity to C=C bond in the
hydrogenation of unsaturated carbonyls, control experiments
were performed (Scheme 5). When 1,3-diphenylpropan-1-one (2a)
was subjected to the optimized conditions, only 17% conversion
of 2a was reduced to its respective alcohol after 24 h, clearly
indicating the significantly preferable selectivity to C=C bond
(Scheme 5b). In contrast, full conversion of styrene to
ethylbenzene with completely recovery of 2a was observed, when
the reaction of the mixture of 2a and styrene (1:1 molar ratio) was
conducted under the optimized conditions, further confirming the
outstanding selectivity to C=C bond of the catalyst (Scheme 5c).
Based on our previous works and other reported results, N,O-
doped hierarchically structured porous materials could modify the
selective adsorption properties of catalyst for the C=C bond and
C=O bond,[17] and also provide large surface areas for reaction,
interfacial transport, or dispersion of active sites at different length
scales of pores[2b]. The comprehensive effects might be decisive
for the outstanding selectivity and activity.
To demonstrate the practical applicability of the one-pot
cascade protocol, we extended it for the direct synthesis of
Loureirin A, an important bioactive and medicinal molecule, from
readily available starting materials (Scheme 4).[12] Under the
slightly modified conditions, 68% of isolated yield of Loureirin A
was achieved. Compared with the traditional synthetic method,[13]
(
de)protection of free hydroxyl group, separation and purification
of the intermediate are no need, making this protocol more time-
saving and cost-effective. Therefore, it provides an alternative
and attractive synthetic method for preparation of Loureirin A and
other important bioactive saturated carbonyls, further highlighting
its practical importance and utility.
Scheme 4. Synthesis of Loureirin A by one-pot cascade strategy.
Durability and recyclability of a catalyst is critical for practical
applications. The catalyst CoO @NC-800 was recollected by
x
centrifugation, washed, and dried after completion of a selective
hydrogenation experiment for subsequent cycles. As shown in
Figure 2, the selectivity remained with negligible changes after
five recycling experiments, demonstrating the high durability of
the catalyst because of that the N atoms in carbon structure can
act as basic coordination sites for stabilizing highly dispersed Co
NPs.[8,14-16]A slight decrease in reaction efficiency is most likely
due to the loss of catalyst during the recycle process.
Scheme 5. Control experiments under the standard conditions
A plausible reaction pathway is proposed as shown in Scheme
6
. Initially, the H
further generates the activated hydrogen species, such as cobalt
hydride species [Co-H ]. Meanwhile, the substrate interacts with
2 x
is dissociated on the surface of CoO @NC-800,
2
the heterogeneous catalyst preferentially via the selective
adsorption of the C=C bond other than C=O bond of α,β-
unsaturated carbonyls by the catalyst surface. Subsequently, the
C=C bond is chemoselectively hydrogenated by the activated
hydrogen atoms. The formed saturated ketone desorbs from the
surface of catalyst, thereby completing the entire catalytic cycle.
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FULL PAPER
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heterogeneous cobalt nanostructured catalyst. A broad set of α,β-
aromatic and aliphatic unsaturated carbonyl compounds was
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high yields with good functional groups tolerance. Meanwhile, the
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x
optimal catalyst CoO @NC-800 is also applicable for one-pot
direct synthesis of saturated ketones starting from readily
available aldehydes and ketones, including an important bioactive
and medicinal Loureirin A, in a cost-effective and green manner.
To the best of our knowledge, this is the first example using a
heterogeneous non-noble metal catalyst for the chemoselcetive
hydrogenation of C=C bond of α,β-unsaturated carbonyls.
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We gratefully acknowledge the start-up financial support from
Qingdao Institute of Bioenergy and Bioprocess Technology
(
QIBEBT), Chinese Academy of Sciences (Grant No.
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Entry for the Table of Contents
COMMUNICATION
Tao Song, Zhiming Ma,[a,b] and Yong
[
a]
[
a]
Yang *
Page No. – Page No.
Chemoselective Hydrogenation of
α,β-Unsaturated Carbonyls Catalyzed
by Biomass-Derived Cobalt
Text for Table of Contents
Nanoparticles in Water
A heterogeneous and reusable biomass-derived non-noble cobalt nanoparticles has been firstly developed for efficient and selective
hydrogenation of α,β-unsaturated carbonyls to saturated carbonyls, and the direct one-pot synthesis of saturated ketones including
important bioactive and medical Loureirin A starting from aldehydes and ketones have also been realized in a sequential, cost-effective,
and green manner.
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