Monodisperse NiPd alloy nanoparticles decorated on mesoporous graphitic carbon nitride as a catalyst for the highly efficient chemoselective reduction of α,β-unsaturated ketone compounds

Article abstract of DOI:10.1039/d0nj03104f

Herein, the study reported extraordinary chemoselective reduction with selectivity (>99%) by the catalytic transfer hydrogenation of various α,β-unsaturated ketones with a catalyst of NiPd alloy nanoparticles decorated on mesoporous graphitic carbon nitride (NiPd/mpg-C3N4) under mild conditions in a water/methanol medium. NiPd alloy NPs were synthesized by the reduction of metal salts in oleylamine (OAm) solution with the help of borane-tert-butylamine and then decorated on mpg-C3N4via a liquid phase self-assembly method. The NiPd/mpg-C3N4 nanocatalyst was characterized by TEM, XRD and ICP-MS. The NiPd/mpg-C3N4 nanocatalyst is a highly active catalyst for the chemoselective reduction of α,β-unsaturated ketones and all organic compounds were converted with high yield and 99% selectivity. In addition, the catalyst can be reused five times without an important loss in reaction yield. This journal is

Full text of DOI:10.1039/d0nj03104f

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Page 1 of 12
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DOI: 10.1039/D0NJ03104F
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Monodisperse NiPd Alloy Nanoparticles Decorated on Mesoporous Graphitic
Carbon Nitride as Catalyst for the Highly Efficient Chemoselective Reduction
of α, β-Unsaturated Ketone Compounds
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Çetin Bayrak,*a,b Abdullah Menzeka and Melike Sevim*a
Abstract: Herein, the study reported extraordinary chemoselective reduction with selectivity (>99%) by the catalytic transfer hydrogenation of
various α,β- unsaturated ketones with NiPd alloy nanoparticles decorated on mesoporous graphitic carbon nitride ( NiPd/mpg-C3N4) catalyst
under mild conditions in a water/methanol medium. NiPd alloy NPs were synthesized by the reduction of metal salts in oleylamine (OAm) solution
with the help of borane-tert-butylamine and then decorated on mpg-C3N4 via liquid phase self-assembly method. NiPd/mpg-C3N4 nanocatalyst
was characterized by TEM, XRD and ICP-MS. NiPd/mpg-C3N4 nanocatalyst is a highly active catalyst for the chemoselective reduction of α,β-
unsaturated ketones and all organic compounds were converted with high yield and 99% selectivity. In addition, the catalyst can be reused for
five times without important loss in reaction yield.
1. Introduction
The Pd/C-catalyzed hydrogenation reaction is known as a classical and efficient method for the reduction of the double bond in
the organic compounds and Pd/C is also a catalyst which is commercial and highly active heterogeneous. The Pd/C could catalyze
reducible functional groups of alkynes, alkenes and nitro groups.1 Therefore, it is not used for chemoselective conversions.2
Because the chemoselective transformations are too difficult to achieve with high yields in these reactions. In addition, the
chemoselective transformations of functional groups in organic compounds have a great attention in both industrial and synthetic
chemistry. These selective organic transformations can be carried out by different palladium catalysts.2-5 The design of new
catalysts for chemoselectivity can achieve the reduction of specific reducible functional groups.5 A great number of
heterogeneous catalysts based on different metals have been designed for selective catalytic transformations.6-8Among these
metals, Pd is the most utilized and investigated.2 However, catalysts which contain only palladium is not economical for the
industrial applications. According to the industrial requirements, researchers aim to improve more economical catalysts and we
have developed new and cheap catalyst for the selective reduction of the α, β-unsaturated carbonyl compounds which is very
important in organic chemistry. The reduced products are used as intermediates for the synthesis of chemicals, pharmaceuticals
and material chemistry.9-13 Moreover, the compounds are valuable substructures for a great number of pharmaceutical drugs
(Scheme 1).8, 14-18
O
OMe O
O
R
O
R
OH
HO
MeO
OMe
N
H
OH
(R)-Propafenone
R = H, Uvangoletin
R = CH3 Myriggalone H
R = H, Loureirin A
R = OMe Loureirin B
Fig 1: The pharmaceutical active reduced chalcone compounds.

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In recent years, some methods have been introduced for the selective reductions of α, β-unsaturated carbonyl compounds.9,
19-21 ln these reactions, molecular hydrogen is generally used as a reducing reagent. But, there are some disadvantages of these
reactions: (a) H2 gas which is highly flammable can cause explosive when mixed with air; (b) The high amounts of H2 gas results
in the reduction of all reducible functional groups. Therefore, methods have been introduced for the catalytic transfer
hydrogenation by using various hydrogen donors.22-27 At this point, ammonia-borane (AB, NH3BH3) is the best well-known
candidate for the transfer of hydrogen reaction. The NH3BH3 has some characteristics specialities that have a high hydrogen
capacity, fast hydrogen transfer reaction and no poisoning.28, 29 NH3BH3 has recently been used as hydrogen source in the
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reduction of organic compounds using different nanoparticles as catalysts.30-32 Antonietti et al. reported a Pd@C3N4 catalyst
for the hydrogenation of phenol and derivatives by using hydrogen from another source. The innovator part of this study is the
production and transference of the hydrogen via ammonia-borane. In this way, the first step is to produce hydrogen and the
second step is to transfer the hydrogen in one vessel. Chen et al. used formic acid as a hydrogen carrier in the presence of Pd /
C3N4 catalyst for the reduction of styrene and its derivatives.34 Metin et al. used AgPd/C3N4 catalyst for the reductive amination
of aldehydes via using formic acid as a hydrogen source.35
In the reduction of functional organic groups, researchers have used different material to support colloidal nanoparticles.36,
37 mpg-C3N4 has been used as support material in many fields35, 38, 39 and it has been used for the reduction of nitro compounds,
phenol and derivatives hydrogenation.40 In this study, we used mesoporous graphitic carbon nitride material for its unique
characteristics. Morphological analysis showed that high surface area (182m2g-1)41 and porous structure of mpg-C3N4 allows to
decorate our nanoparticles.
In this study, we synthesized Ni30Pd70 alloy nanoparticles and decorated on the surface of mpg-C3N4. At this reaction, our
motivation was to build-up cheap and active catalyst via transfer hydrogenation method. Because only Pd is an expensive catalyst
for these reactions. Therefore, AB was used as a hydrogen source instead of commercial hydrogen gas. In this way, we developed
cheap catalyst as an alternative for Pd, and hydrogen gas emerged during the reaction for the reduction of functional organic
groups. This is the first example of Ni30Pd70/mpg-C3N4 nanocatalyst used for the chemoselective reduction of α, β- unsaturated
ketones.
2. Results and Discussion
2.1. Chemistry
Monodisperse NiPd alloy NPs were synthesized by using our established protocol which was reduction of Ni(ac)2 and Pd(acac)2 in
a mixture of OAm and ODE mixture with the help of strong reducing agent BTB. Fig. 1A and B shows the representative TEM
images of the NiPd/mpg-C3N4 nanocatalysts at different magnifications. As clearly seen from the TEM images, the NiPd/mpg-C3N4
has monodisperse particle size distribution 3.7 nm which is taken ethanol dispersion. The cloudy structure belongs to the mpg-
C3N4 structure. There is no agglomeration in the nanoparticles structure and it provides the high catalytic activity in organic
reactions. The NiPd content of Ni30Pd70/mpg-C3N4 catalysts was determined to be 14.6% wt by ICP-MS analyses.

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Fig 2. The representative TEM images of A) colloidal Ni30Pd70 NPs B) Ni30Pd70/mpg-C3N4 nanocatalyst.
Fig 3. shows the XRD patterns of the Ni30Pd70/mpg-C3N4 nanocatalyst. The broad peak observed at 2θ=40.1 belongs to (111) plane
of fcc-NiPd (JCPDS: 65-5788). And this specific peak shows the alloy formation. The peak observed at 2θ=27.4 belongs to the mpg-
C3N4 structure.
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Fig 3. XRD patterns of the NiPd/C3N4 catalyst.
In the present study, we have investigated chemoselective reduction of α, β-unsaturated carbonyl compounds with
Ni30Pd70/mpg-C3N4 by using NH3BH3 as a hydrogen source at room temperature. With this purpose, we have chosen of chalcone
compounds as starting material and all of the α, β-unsaturated carbonyl compounds have electron donating groups such as Me
and OMe. These α, β-unsaturated carbonyl compounds were obtained from condensation reactions of substituted acetophenone
with substituted benzaldehyde derivatives (Scheme 1-2). The known chalcone compounds were synthesized according to
literature.42 But, Compound 17 has not yet been synthesized.

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O
R1
R4
R4
R3
O
R2
R3
O
10% NaOH
R1
EtOH-rt
R
R2
R
1)
4)
4)
4)
4)
2)
5)
3)
6)
8)
R = OMe
R1 = R2 = R4 = H, R3 = OMe
R1 = R2 = R4 = H, R3 = OMe
R1 = R2 = R4 = H, R3 = CH3
R1 = R2 = OMe, R3 = R4 = H
R2 = R3 = R4 = OMe, R1 = H
R = R3= OMe, R1 = R2 = R4 = H
R = CH3, R3 = OMe, R1 = R2 = R4 = H
R = R3 = CH3, R1 = R2 = R4 = H
R = CH3, R1 = R2 = OMe, R3 = R4 = H
R = CH3, R2 = R3 = R4 = OMe, R1 = H
R = CH3
R = CH3
R = CH3
R = CH3
7)
9)
11)
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10)
12)
Scheme 1. Synthesis of α, β-unsaturated carbonyl compounds (3, 6, 8, 10 and 12).
OMe O
R1
R4
R3
OMe O
R2
R3
O
10% NaOH
EtOH-rt
R1
MeO
R2
MeO
13)
R4
2)
7)
9)
11)
14)
15)
R1 = R2 = R4 = H, R3 = OMe
R1 = R2 = R4 = H, R3 = CH3
R1 = R2 = OMe, R3 = R4 = H
R2 = R3 = R4 = OMe, R1 = H
R1 = R3 = OMe, R2 = R4 = H
R1 = R2 = R4 = H, R3 = OMe
R1 = R2 = R4 = H, R3 = CH3
R1 = R2 = OMe, R3 = R4 = H
R2 = R3 = R4 = OMe, R1 = H
R1 = R3 = OMe, R2 = R4 = H
13)
13)
13)
13)
6)
1
17)
18)
19)
Scheme 2. Synthesis of α, β-unsaturated carbonyl compounds (15-19).
Reaction conversions and selectivity including the catalyst amount, reaction times, amount of hydrogen source were
discovered and the results are shown in Table 1. For the reduction reactions of α, β-unsaturated carbonyl compounds by
hydrogenation, optimization conditions of the reaction belonging to the compound 10 were firstly investigated. ln the first test
reaction, it was converted into compound 20 with 30% conversion and 99% selectivity after 0.5 h (Table 1, entry 1). We have
observed the effects of several factors such as reaction time to determine the optimum reaction conditions. When the compound
10 reacted with NH3BH3 (0.5 equiv.), it was determined that the compound 20 occurred by 50% conversion and 99% selectivity
after 1 h (Table 1, entry 2). When the reaction time (total 2h) was extended to increase the reaction yield, eventually the yield
was also determined as 80%, (Table 1, entry 3). As a result, we have defined the conditions in entry 4 of Table 1 as optimized
conditions. It was observed that the compound 20 along with a product without carbonyl group (PWCG) occurred when the
amount of NH3BH3 and reaction time were increased (Table 1, entry 5-7). We have not observed that a mixture of 10 and PWCG
or a mixture of 10, 20 and PWCG occurred in these reaction. Therefore, the compound 20 may be obtained as alone from the
reduction of the compound 10.

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Table 1
Optimization of the reaction conditions in the H2O/MeOH.
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7
O
OMe
O
OMe
x(mg)
Ni30Pd70/ C3N4
OMe
OMe
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9
NH3BH3 (y eqiuv.)
Solvent, rt, z (h)
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Entry
x(mg)
y (eqiuv.)
oC
z (h)
solvent
conversionb (%)
Selectivityb (%)
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3
H2O/MeOH (3:7)
H2O/MeOH (3:7)
H2O/MeOH (3:7)
H2O/MeOH (3:7)
H2O/MeOH (3:7)
H2O/MeOH (3:7)
H2O/MeOH (3:7)
30
50
80
100
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100
100
> 99
> 99
> 99
> 99
> 95
60-75
50-62
24
a
Reaction conditions: Chalcone (1 eqiuv, 0,25 mol), NH3BH3 (y eqiuv.), rt, z (h), bConversions were calculated by 1H NMR of the compound 10 as standard
Table 1: Optimization of the reaction conditions.
We have extended the reduction reaction of substituted α, β-unsaturated ketone compounds. Compounds 6, 8, 10, 12 and 16
have OMe and Me groups. According to optimized conditions, these compounds were converted into corresponding saturated
ketones 21, 22, 20, 23 and 25 with high yields, respectively. Similarly, compounds 3, 15, 17, 18 and 19 have only two and more
OMe groups. Compounds 24, 26, 27, 28 and 29 with high yield were also obtained from the reduction reactions of these
compounds.

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Table 2
O
O
5
6
7
8
(5 mg)
Ni30Pd70/ C3N4
R1
R2
R1
R2
NH3BH3 (1 eqiuv.)
MeOH / H2O (7:3), rt, 3h
3, 6, 8,10,12 and 15-19
20-29
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O
O
O
O
OMe
OMe
OMe
OMe
OMe
22 (> 99 %)
23 (> 99 %)
OMe O
( 98 %)
21 95 %)
20
OMe
OMe
O
OMe O
OMe O
OMe
MeO
OMe
MeO
MeO
MeO
OMe MeO
OMe
( 98 %)
26
27 ( 96 %)
25 ( 96 %)
(> 99 %)
24
OMe O
OMe O
OMe
MeO
OMe
OMe
OMe
( 97 %)
( 98 %)
29
28
Reaction conditions: Chalcone (1 eqiuv, 0,25 mol), NH3BH3 (1 eqiuv.), rt, 3h, MeOH / H2O (7:3)
Table 2: The reduction reactions of α, β-unsaturated carbonyl compounds.
2.2. Reusability of catalyst
To test the reusability of the catalyst, the chalcone compounds were conducted with the same reaction conditions. But the
catalyst was reused. In accordance with this purpose, a number of reduction reactions of compound 10 were performed. Here,
Ni30Pd70/C3N4 catalyst was used for five times in the optimized reaction to test reusability of the catalyst. The first experiment
was performed with 20 mg catalyst and after the reaction, catalyst was centrifuged and recover. After five runs, the reaction yield
was over 97%. Fig 4b. shows the morphological structure of the catalyst after 5 runs. The results showed that this catalyst is a
reusable and significantly efficient catalyst for the dehydrogenation of AB and chemoselective hydrogenation of C=C bond of α,
β-unsaturated carbonyls.
(A)
100
99
97
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99
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80
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40
20
0
1
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Cycle
Fig 4. The reusability of NiPd/C3N4 catalyst in the tandem dehydrogenation of AB and chemoselective hydrogenation of C=C
bond of α, β-unsaturated carbonyls.

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3. Experimental
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3.1. Materials and Methods
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Solvents were purified and dried with known methods. For all compounds, values as well as Mp, H and 13C NMR spectra and
chemical shift were performed as explained previously.18, 43 PLC (preparative thick-layer chromatography) was used as 1 mm of
silica gel 60 PF (Merck, Darmstadt, Germany) on glass plates. Palladium (II) acetylacetonate (Pd (acac)2, 99%), nickel (II) acetate
(Ni(ac)2, 97%), borane tert-butyl- amine (BTB, 95%), Oleylamine (OAm) (>70%), 1-octadecene (ODE, 90%), ammonia-borane (AB,
97%), Ludox® HS-40 and the solvents (hexanes, ethanol and acetone) used for the nanoparticles synthesis were purchased from
Sigma-Aldrich and Ammonium hydrogen difloride (NH4HF2, 98.5%) was purchased from Fluka. Guanidine hydrochloride (GndCI,
98%) was purchased from Alfa-Aesar.
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3.1.1. Instrumentation
All transmission electron microscope (TEM) images were obtained by FEI Technai G2 Spirit BiO (TWIN) at 120 kV. Elemental
analysis measurements were performed an Agilent Technologies 7700 inductively coupled with plasma-mass spectroscopy
(ICP-MS). X-ray diffraction (XRD) patterns were performed on a Panalytical Empyrean diffractometer with Cu-Kα radiation (40 kV,
15 mA, 1.54051 A°) over a 2θ range from 10°- 90° at room temperature.
3.2. Synthesis of monodispersed mpg-C3N4
mpg-C3N4 was synthesized with a silica-templating method containing the polycondensation of guanidine hydrochloride (GndCl)
with the help of Ludox®HS-40 colloidal silica NPs.44 In general procedure, 4.0 g of GndCl was dissolved in 4 mL water in a glass vial
and 10 g of Ludox®HS-40 colloidal silica was added into the mixture and this solution was stirred overnight at 50 oC. The white
product was placed in a quartz crucible for the heat treatment process. The crucible was heated to 550 oC with a ramp rate of 4-
5 oC min-1 under Argon gas flow and continued at this temperature for 2 h. The product then reacted with 4 M of 200 mL NH4F2
solution for 2 days. At the end of this procedure, the silica particles were taken out and porous structure was obtained. Finally,
the resulting product was washed with water several times with ethanol and dried under vacuum to remove impurities
3.3. Synthesis of NiPd NPs and supported on mpg-C3N4
Monodisperse NiPd alloy NPs were synthesized by using our established protocol.45 In a recipe for the synthesis of Ni30Pd70 NPs;
In a glass vial, 0.2 mmol of palladium (II) acetylacetonate, 0.2 mmol Nickel(II) acetate tetrahydrate and were dissolved in 3 mL
of OAm at room temperature. In a four neckled glass reactor, 200 mg of BTB was dissolved in a mixture of 3 mL OAm and 7 ml
OAc and then heated to 100 °C under nitrogen gas flow. The temperature was increased to 100 °C and the first mixture which
includes the metal precursors was injected to the reaction mixture and was maintained at this temperature for one hour. Finally,
the last product was separated from the reaction mixture by adding acetone/isopropanol (1:1) mixture by centrifugation at 9000
rpm, 10 min. The resultant NPs was collected by dispersing them into hexane. The composition of the yielded NPs was determined
via ICP-MS analysis and Ni30Pd70 was found. In a typical procedure, 100 mg of mpg-C3N4 was well-dispersed in 50 mL of ethanol
via ultrasonic bath half an hour. 50 mg of monodisperse Ni30Pd70 NPs were dissolved in 25 mL of hexane at room temperature

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and added into the mpg-C3N4 mixture for the decoration of the NPs. The resultant ethanol/hexane mixture was sonicated for 2 h
to ensure complete adsorption of the Ni30Pd70 NPs onto mpg-C3N4. Next, the resultant mixture was centrifuged at 7500 rpm for
10 min and the separated nanocomposite was washed with ethanol at several times and dried.
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Fig 5. Schematic illustirations of experimental procedure.
3.4. General procedure for chemoselectivity reduction of α, β-unsaturated carbonyl compounds with Ni30Pd70/mpg-C3N4.
Ni30Pd70/mpg-C3N4 catalyst (5 mg) was suspended in water (3 mL) and MeOH (7 mL) mixture and it was sonicated for 5 min in a
glass pressure tube. Then, convenient chalcone derivatives (1 equiv.) and NH3BH3 (1 equiv.) were added to the reaction mixture,
respectively. The reaction mixture was stirred for 3 h at room temperature and the reaction was stopped. The catalyst was
removed by filtration and then the solvent was removed under vacuum. The crude product was extracted with CH2CI2 (2 X 15
mL). The combined extracts were dried over Na2SO4 and the solvent was removed under vacuum. Purification was performed
through thin-layer chromatography (TLC) using EtOAc/hexane eluent on silica gel.
3.5. Synthesis of 3-(2,3-dimethoxyphenyl)-1-(p-tolyl)propan-1-one (20):
Compound 20 (98 %) was obtained as a yellow liquid; Rf = 0.64 EtOAc/Hexane (2:8); 1H NMR (400 MHz, CDCl3): 7.88 (d, A part of
AB Systems, J = 8.2 Hz, 2H), 7.24 (d, B part of AB Systems, J = 8.2 Hz, 2H), 6.99 (t, J = 7.9 Hz, 1H), 6.84 – 6.79 (m, 2H), 3.87 (s, OMe,
3H), 3.85 (s, OMe, 3H), 3.36 – 3.18 (m, 2H), 3.09 – 2.90 (m, 2H), 2.40 (s, CH3, 3H). 13C NMR (100 MHz, CDCl3): 199.40 (CO), 152.81
(C), 147.27 (C), 143.78 (C), 135.24 (C), 134.38 (C), 129.29 (2 X CH), 128.37 (2 X CH), 124.03 (CH), 122.11 (CH), 110.59 (CH), 60.61
(OMe), 55.70 (OMe), 39.63 (CH2), 25.40, 21.63.
3.6. Synthesis of 1-(2,4-dimethoxyphenyl)-3-(p-tolyl)propan-1-one (25):
Compound 25 (96 %) was obtained as a yellow solid; Rf = 0.52 EtOAc/Hexane (2:8); M.p: 64-66 °C; 1H NMR (400 MHz, CDCl3): 7.81
(d, J = 8.6 Hz, 1H), 7.14 – 7.08 (m, 4H), 6.52 (dd, J = 8.7, 2.2 Hz, 1H), 6.45 (s, 1H), 3.86 (s, OMe, 3H), 3.84 (s, OMe, 3H), 3.32 – 3.19
(m, CH2, 2H), 3.04 – 2.91 (m, CH2, 2H), 2.31 (s, CH3, 3H). 13C NMR (100 MHz, CDCl3): 199.54 (CO), 164.38 (C), 160.77 (C), 138.99
(C), 135.25 (C), 132.78 (CH), 129.06 (2 X CH), 128.35 (2 X CH), 121.11 (C), 105.04 (CH), 98.42 (CH), 55.52 (OMe), 55.46 (OMe),
45.50 (CH2), 30.25, 21.00.

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3.7. Synthesis of 1-(2,4-dimethoxyphenyl)-3-(4-methoxyphenyl)propan-1-one (26):
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Compound 26 (98 %) was obtained as a yellow solid; Rf = 0.4 EtOAc/Hexane (2:8); M.p: 65-67 °C; 1H NMR (400 MHz, CDCl3): 7.81
(d, J = 8.8 Hz, 1H), 7.15 (d, A part AB systems, J = 8.6 Hz, 2H), 6.83 (d, B part AB systems, J = 8.6 Hz, 2H), 6.52 (dd, J = 8.8, 2.3 Hz,
1H), 6.45 (d, J = 2.3 Hz, 1H).3.86 (s, OMe, 3H), 3.85 (s, OMe, 3H), 3.78 (s, OMe, 3H), 3.29 – 3.18 (m, CH2, 2H), 3.02 – 2.88 (m, CH2,
2H). 13C NMR (100 MHz, CDCl3): 199.59 (CO), 164.37 (C), 160.75 (C), 157.78 (C), 134.07 (C), 132.92 (C), 129.36 (2 X CH), 121.20
(C), 113.79 (2 X CH), 105.10 (CH), 98.35 (CH), 55.52 (OMe), 55.47 (OMe), 55.26 (OMe), 45.66 (CH2), 29.70 (CH2).
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3.8. Synthesis of 3-(2,3-dimethoxyphenyl)-1-(2,4-dimethoxyphenyl)propan-1-one (27):
Compound 27 (96 %) was obtained as a white solid; Rf = 0.32 EtOAc/Hexane (2:8); M.p: 58-60 °C; 1H NMR (400 MHz, CDCl3): 7.83
(d, J = 8.7 Hz, 1H), 6.98 (t, J = 7.9 Hz, 1H), 6.86 – 6.75 (m, 2H), 6.52 (dd, J = 8.7, 2.3 Hz, 1H), 6.44 (d, J = 2.3 Hz, 1H), 3.86 (s, OMe,
3H), 3.85 (s, OMe, 3H), 3.84 (s, OMe, 3H), 3.83 (s, OMe, 3H), 3.28 – 3.21 (m, 2H), 3.04 – 2.97 (m, 2H). 13C NMR (100 MHz, CDCl3):
199.68 (CO), 164.32 (C), 160.84 (C), 152.77 (C), 147.31 (C), 135.87 (C), 132.79 (CH), 123.99 (CH), 122.07 (CH), 121.14 (C), 110.30
(CH), 105.04 (CH), 98.39 (CH), 60.57 (OMe), 55.67 (OMe), 55.50 (OMe), 55.44 (OMe), 44.44 (CH2), 25.16 (CH2).
3.9. Synthesis of 1,3-bis(2,4-dimethoxyphenyl)propan-1-one (28):
Compound 28 (97 %) was obtained as a yellow solid; Rf = 0.32 EtOAc/Hexane (2:8); M.p: 82-84 °C; 1H NMR (400 MHz, CDCl3): 7.80
(d, J = 8.7 Hz, 1H), 7.07 (d, J = 8.1 Hz, 1H), 6.52 (dd, J = 8.7, 2.2 Hz, 1H), 6.47 – 6.34 (m, 3H), 3.85 (s, 2 X OMe, 6H), 3.79 (s, 2 X OMe,
6H), 3.27 – 3.10 (m, 2H), 2.99 – 2.84 (m, 2H). 13C NMR (100 MHz, CDCl3): 200.31 (CO), 164.17 (C), 160.70 (C), 159.20 (C), 158.46
(C), 132.70 (CH), 130.17 (CH), 122.65 (C), 121.40 (C), 105.12 (CH), 103.75 (CH), 98.47 (CH), 98.35 (CH), 55.50 (OMe), 55.44 (OMe),
55.34 (OMe), 55.23 (OMe), 43.88 (CH2), 29.71 (CH2).
3.10. Synthesis of 1-(2,4-dimethoxyphenyl)-3-(3,4,5-trimethoxyphenyl)propan-1-one (29):
Compound 29 (98 %) was obtained as a brown liquid; Rf = 0.16 EtOAc/Hexane (2:8); 1H NMR (400 MHz, CDCl3): 7.81 (d, J = 8.7 Hz,
1H), 6.54 (dd, J = 8.7, 2.2 Hz, 1H), 6.45 (m, 3H), 3.88 (s, OMe, 3H), 3.86 (s, OMe, 3H), 3.84 (s, 2 X OMe, 6H), 3.82 (s, OMe, 3H), 3.31
– 3.22 (m, 2H), 2.95 (t, J = 7.7 Hz, 2H). 13C NMR (100 MHz, CDCl3): 199.42 (CO), 164.44 (C), 160.73 (C), 153.09 (CH), 137.84 (C),
136.10 (C), 132.75 (C), 121.09 (C), 105.40 (CH), 105.14 (CH), 98.38 (CH), 60.85 (OMe), 56.05 (2 X OMe), 55.54 (OMe), 55.50 (OMe),
45.39 (CH2), 31.06 (CH2).
4. Conclusions
In summary, we have determined extraordinary chemoselectivity in the hydrogenation of the C=C bond in α, β-unsaturated
compounds in the presence of reducible groups, such as carbonyl, at room temperature. To the best of our knowledge, this is the
first example using a heterogeneous Ni30Pd70/mpg-C3N4 catalyst for the chemoselective hydrogenation of C=C bond of α,
β-unsaturated carbonyls. In addition, the catalyst can be reused for five times without important loss in reaction yield.
Conflicts of interest
The authors declare no competing financial interest.

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Acknowledgements
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This work was realized in the Department of Chemistry at Ataturk University. The authors would like to thank the
Department of Chemistry at Ataturk University-FAD-2019-7025 for their support.
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Graphical Abstract
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