Copper-Impregnated Magnesium-Lanthanum Mixed Oxide: A Reusable Heterogeneous Catalyst for Allylation of Aldehydes and Ketones

Article abstract of DOI:10.1002/adsc.201901133

Copper-impregnated magnesium-lanthanum mixed oxide [Cu(II)/Mg?La] was used as catalyst in synthesis of homoallylic alcohols from aldehydes and ketones using allyltributylstannane as the allylating source. The present protocol provides a great application

Full text of DOI:10.1002/adsc.201901133

Title: Copper-Impregnated Magnesium-Lanthanum Mixed Oxide: A
Reusable Heterogeneous Catalyst for Allylation of Aldehydes and
Ketones
Authors: Pogula Jaya, SOUMI LAHA, Bojja Sreedhar, and Pravin
Likhar
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10.1002/adsc.201901133
Advanced Synthesis & Catalysis
FULL PAPER
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
Copper-Impregnated Magnesium-Lanthanum Mixed Oxide: A Reusable
Heterogeneous Catalyst for Allylation of Aldehydes and Ketones
Jaya Pogula,a, b Soumi Laha,b B. Sreedhar,c and Pravin R. Likhar* b
aAcademy of Scientific and Innovative Research (AcSIR), New Delhi, India.
bCatalysis and Fine Chemicals Department, CSIR-Indian Institute of Chemical Technology,
Hyderabad, India.
cAnalytical Department, CSIR-Indian Institute of Chemical Technology, Hyderabad, India.
Fax: +91-40-2716-0921; Tel: +91-40-2719-3510 (+91)-40-2719-1667.
Email: plikhar@iict.res.in
Received: ((will be filled in by the editorial staff))
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######.((Please
delete if not appropriate))
Abstract:
Copper-impregnated
magnesium-lanthanum
Importantly, the heterogeneous catalyst could be recovered
from the reaction mixture by centrifugation and used up to
three cycles.
mixed oxide [Cu(II)/Mg-La] was used as catalyst in
synthesis of homoallylic alcohols from aldehydes and
ketones using allyltributylstannane as the allylating source.
The present protocol provides a great application potential
for the synthesis of corresponding allyl alcohols with
excellent yields and selectivity. The catalyst exhibits broad
functional group compatibility with a variety of substituted
aldehydes and ketones to furnish the desired products in high
yields under heterogeneous conditions.
Keywords: aldehydes; ketones; allylation; copper;
magnesium-lanthanum mixed oxide; homoallylic alcohols;
heterogeneous catalysis; reusability.
magnesium metal. Different transition metal
catalyzed Barbier reactions in aqueous medium are
well documented in the literature.[9-18] From non-
aqueous perspective, heterogeneous catalytic
process has advantages over homogeneous in view
of its ease of handling, simple work-up and
recoverability.[19] Now a days most of these
methods are used even on an industrial scale as the
methods offer good yield and selectivity. The main
disadvantage of the homogeneous catalysis is
contamination of the metal in the product, which is
unacceptable e.g. in pharmaceutical syntheses. This
induces a considerable research effort to develop
new heterogeneous catalytic systems. Unfortunately,
in these reactions, the use of zero-valent metals
causes metal oxide or hydroxide precipitation on
the surface of the metal which leads to termination
or increased duration of the reaction. Furthermore,
some zero-valent metals are too reactive and
Introduction
Allylation of carbonyl compounds is an important
synthetic organic transformation since in this
reaction, a new carbon-carbon bond is formed along
with the introduction of hydroxyl functionality.[1]
Moreover, the double bond of the allylic moiety can
further undergo a number of synthetically useful
transformations such as hydrogenation, ozonolysis,
hydroboration,
cycloaddition,
epoxidation,
dihydroxylation, hydroformylation, hydration, etc.[2]
The general practice for the preparation of
homoallylic alcohols involves nucleophilic addition
of an allylic metal reagent to carbonyl
compounds.[3-7] However, the Barbier reaction[8] is
an alternative method for the synthesis of
homoallylic alcohols, the reaction of a carbonyl
compound with an organic halide in the presence of
1
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10.1002/adsc.201901133
Advanced Synthesis & Catalysis
significant amount of by-products such as pinacol
are produced. Roy et al. reported the first example
of carbonyl allylation in heterogeneous media
involving SnO and catalytic Cu2O[20] while Kantam
and co-workers had reported the Cu-exchanged
fluorapatite catalyst for the allylation of aldehydes
with allyltributylstannane or allyltrimethylsilane.[21]
Recently, magnesium-lanthanum mixed oxide (Mg-
La mixed oxide) has found extensive applications
as a heterogeneous catalyst for various organic
transformations. Figueras and co-workers examined
the direct condensation of alcohols[22] and Michael
addition reactions[23] over highly basic Mg-La
mixed oxide catalyst. The catalytic activity of the
Mg-La mixed oxide was demonstrated in the
condensation of aldehydes and imines with ethyl
diazoacetate using water as a solvent.[24] Different
transition-metals impregnated Mg–La mixed oxide
catalysts have also been developed and used as
effective heterogeneous catalysts in various organic
as described in the literature.[25a] Cu(II)/Mg-La
mixed oxide was prepared by impregnation method.
The BET surface area was measured by N2
adsorption at 77 K and revealed values of 35.9 m2g-
1
for Mg-La mixed oxide and 29.0 m2g-1 for Cu-
loaded Mg-La mixed oxide. Copper content of the
catalyst was determined by ICP-OES analysis and
found to be 6.1 wt%.
The X-ray photoelectron spectroscopic analysis
(XPS) of freshly prepared Cu(II)/Mg-La catalyst
was carried out to evaluate the oxidation state of
copper on Cu(II)/Mg-La catalyst (Fig. 1). The
binding energies of Cu(II)/Mg-La were observed at
934.48 and 954.69 eV that correspond to Cu 2p3/2
and Cu 2p1/2 binding energy peaks due to copper in
+2 oxidation state.
transformations.[25] In search for
a
suitable
heterogeneous catalyst for allylation of carbonyl
compounds, we envisaged that copper impregnated
magnesium-lanthanide mixed oxide, Cu(II)/Mg–La
could exhibit interesting catalytic activities.
Herein, we disclose efficient allylation of aldehydes
and ketones enabled by Cu(II)/Mg-La mixed oxide
catalyst without the need of expensive ancillary
ligands or additives, demonstrating the versatility of
the reaction (Scheme 1) with the following
advantages: high yields, shorter reaction time, low
costs, and simplicity in process. The fresh and used
Cu(II)/Mg-La mixed oxide catalysts were
characterized by XPS and XRD analysis and a
plausible reaction mechanism is discussed.
Fig. 1: XPS of A) fresh and B) used Cu(II)/Mg-La
catalyst.
XRD patterns of the fresh and used Cu(II)/Mg-La
mixed oxide catalysts revealed the presence of both
La2O2(CO3)2 and CuO phases (Fig. 2).
Scheme 1. Allylation of aldehydes and ketones
using Cu(II)/Mg-La mixed oxide catalyst.
Results and Discussion
Fig. 2: XRD of (A) fresh and (B) used Cu(II)/Mg-
La catalyst.
Characterization
The Mg-La mixed oxide was synthesized by co-
precipitation of magnesium and lanthanum nitrate
2
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10.1002/adsc.201901133
Advanced Synthesis & Catalysis
1
Diffraction peaks at 2θ= 13.1, 22.8, 29.5o are
attributed to the lanthanum oxide carbonate
phase[25h] and that at 2θ= 32.48, 35.5, 38.7, 46.2,
48.8, 53.5, 58.3, 61.5, 66.2, 68.2o are due to copper
in oxide form.[25i]
The structure of the product was confirmed by H
NMR and Mass spectroscopic analysis (detailed
characterization of the products are provided in
supporting information).
A variety of commercially available copper salts
such as CuI, Cu2O, CuCl, CuCl2.2H2O, CuO,
Cu(acac)2.H2O and Cu-bronze were screened in
allylation reaction using acetonitrile as a solvent at
65 ºC to compare the catalytic activity with
Cu(II)/Mg–La mixed oxide catalyst (Table 2,
entries 1, 2, 3, 4, 5, 6 and 7). Though moderate to
good yields of the desired products were obtained, a
longer reaction duration was needed (24 to 30
hours). The activity of synthesized catalysts such as
Optimization of reaction conditions:
Optimization of reaction conditions was performed
using 4-nitrobenzaldehyde as a model substrate. 20
mg of Cu(II)/Mg–La mixed oxide catalyst (6.1 wt%
Cu),
1
mmol of 4-nitrobenzaldehyde and
allyltributyltin (1.2 mmol). Initially, the effects of
different solvents on the product yields were
examined. The reaction was performed in different
solvents such as dichloromethane (DCM), THF,
methanol, acetonitrile, toluene, water, DMSO and
DMF (Table 1). In DCM solvent, the yield of the
desired product, 1-(4-nitrophenyl)but-3-en-1-ol was
low (Table 1, entry 1), polar solvents such as THF,
methanol, acetonitrile, DMSO and DMF furnished
moderate to good yields of the product (Table 1,
entries 2, 3, 4, 8 and 9). In an effort to further
improve the yield, the reaction was carried out at
65oC in acetonitrile. Gratifyingly, the product was
obtained in excellent yields of 94% with shorter
reaction duration (Table 1, entry 5). Moreover,
moderate product yields were obtained using water
as a solvent (Table 1, entry 7).
Cu(II)/Al2O3,
Cu(0)/Al2O3,
Cu(II)/Fe3O4,
Cu(0)/Fe3O4 were also compared in this reaction
(Table 2, entries 8, 9, 10, 11) and moderate to good
yields of the desired product were observed.
Table 2. Screening of different catalysts.[a]
Entry
Catalyst
Time (h)
Yield
(%)(b)
62
1
2
3
4
5
6
7
8
9
10
11
12
13
14
CuI
Cu2O
CuCl
CuCl2.2H2O
CuO
Cu(acac)2.H2O
Cu-Bronze
Cu(II)/Al2O3
Cu(0)/Al2O3
Cu(II)/Fe3O4
Cu(0)/Fe3O4
Mg-La
28
28
24
26
26
30
26
24
24
24
24
24
5
84
75
83
82
72
88
78
85
60
66
50
94
Table 1. Screening of reaction parameters.[a]
Entry
Solvent
DCM
Temp ( ºC) Time (h) Yield (%)[b]
1
2
3
4
5
6
7
8
9
40
24
24
24
24
05
24
24
24
24
20
82
68
48
94
85
60
65
70
THF
65
Methanol
Acetonitrile
Acetonitrile
Toluene
Water
60
Cu(II)/Mg-La
None
RT
65
24
0
[a]Reaction conditions: 4-Nitrobenzaldehyde (1 mmol),
allyltributylstannane (1.2 mmol), catalyst, acetonitrile (3
mL) at 65 ºC. [b]Isolated yields.
100
100
80
DMSO
DMF
Significantly, lower yield of the product was
obtained when only Mg-La mixed oxide was used
as a catalyst (Table 2, entry 12) while Cu(II)/Mg–
La furnished excellent yields with short reaction
time (Table 2, entry 13). It is important to note that
100
[a]Reaction conditions: 4-Nitrobenzaldehyde (1 mmol),
allyltributylstannane (1.2 mmol), Cu(II)/Mg-La (20 mg,
1.9 mmol% of Cu), solvent (3 mL). [b]Isolated yields.
3
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10.1002/adsc.201901133
Advanced Synthesis & Catalysis
in the absence of any catalyst, the reaction failed to
produce any product (Table 2, entry 14).
excellent yields without reduction of the nitro group
(Table 4, entries 3b-d).
Table 4: Study of substrate scope in the
allylation of aldehydes catalyzed by Cu(II)/Mg-
La mixed oxide.[a]
The activities of different allylating reagents were
also tested and the results are summarized in (Table
3). It can be seen from table 3, the rate of the
reaction is highly dependent on the choice of the
allylating agent. Both tetraallyltin and allyl
tributylstannane afforded excellent yields in short
period of time (Table 3, entry 1& 2). However,
allylsilanes such as allyltrimethylsilane and
tetraallylsilane furnished low yields of the product
(Table 3, entries 3 and 4). Allyltributylstannane was
further used in the allylation reaction taking into
account the lower price and safety aspect of the
reagent.
Table 3. Allylation of 4-nitrobenzaldehyde
with different allylating reagent.[a]
[a]Reaction conditions: 4-Nitrobenzaldehyde (1 mmol),
allylating reagent (1.2 mmol), Cu(II)/Mg-La (20 mg, 1.9
º
mmol% of Cu), acetonitrile (3 mL) at 65 C. [b]Isolated
yields. NR= No reaction.
Next, the catalytic activity of Cu(II)/Mg-La mixed
oxide was tested in the allylation of different
structurally divergent aldehydes possessing a wide
range of functional groups to understand the scope
and the generality of the developed process. The
results are summarized in Table 4. Simple
benzaldehyde produced the corresponding product in
good yields (Table 4, entry 3a). Nitro substituted
benzaldehydes furnished the desired product in
4
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10.1002/adsc.201901133
Advanced Synthesis & Catalysis
Remarkably, other functional groups such as cyano
and methoxy were well tolerated and the
corresponding allylic alcohols were obtained in
satisfactory yields (Table 4, entries 3e–i).
Fluro-,
chloro-
and
bromo-
substituted
benzaldehydes smoothly underwent the allylation
reaction furnishing good yields of the product (Table
4, entries 3j-m). Importantly, in these reactions, no
dehalogenated homoallylic products were observed.
In general, electron-donating group products
(Table 4, entry 3n) on the aromatic ring furnished
lower yields of desired products compared to
electron-withdrawing groups. However, allylation
was slow with bulky substrates such as 1-
naphthaldehyde and 2-naphthaldehyde when
compared with other aromatic aldehydes (Table 4,
entries 3o-p).
Among the various aldehydes tested, hetero
aromatic
aldehydes
such
as
2-pyridine
carboxaldehyde, 3-pyridine carboxaldehyde and 4-
pyridine carboxaldehyde produced good yields
(Table 4, entries 3q-s). Notably, in the allylation of
α,
β-unsaturated
aldehydes
such
as
cinnamaldehyde good yield of the desired product
was obtained (Table 4, entry 3t). Significantly,
more challenging aliphatic aldehydes such as
hexanaldehyde gave satisfactory yields (Table 4,
entry 3u).
Encouraged by the results obtained from Table 4,
we planned to examine the catalytic activity of
Cu(II)/Mg-La mixed oxide in the allylation of more
challenging and difficult carbonyl substrates
ketones.
Initially, we performed the reaction of simple
ketone, such as acetophenone with allyl
tributylstannane (Table 5, entry 5a). Remarkably, a
moderate yield of the desired tertiary homoallylic
alcohol was obtained using Cu(II)/Mg-La (20 mg,
1.9 mmol
%
of Cu) as catalyst, allyl
tributylstannane as allylating reagent and
º
acetonitrile as solvent at 65 C. Moreover, chloro-,
nitro-, hydroxyl- and bromo- substituted
acetophenones (5b-d)provided the corresponding
desired products in moderate to good yields (Table
5). The allylation reaction was also attempted using
alkyl ketones, but it failed to furnish the desired
allylic product.
[a]Reaction
conditions:
Aldehyde
(1
mmol),
allyltributylstannane (1.2 mmol), 1.9 mmol% of Cu,
acetonitrile (3 mL) at 65 ºC. [b]Isolated yields.
5
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10.1002/adsc.201901133
Advanced Synthesis & Catalysis
Table 5: Study of substrate scope in the Scheme 2. Allylation of 4-nitrobenzaldehyde in
allylation of ketones catalyzed by Cu(II)/Mg- gram-scale reactions.
La mixed oxide.[a]
Recyclability of the catalyst
The recyclability of the catalyst was examined
using
4-nitrobenzaldehyde
with
allyl
tributylstannane at 65 ºC in acetonitrile and the
results are shown in Fig. 3. The activity graph
illustrates that the catalyst can be used for four
consecutive cycles. The observed decrease in the
conversion (%) from the cycles could be due to the
clogging of some of the catalytic active sites with
organic reagents during the course of the reaction
and not due to leaching of active metal from the
support (see Experimetal Section). In the
recyclability studies, catalyst was recovered by
centrifugation and washed with distilled water, air-
dried and reused directly for the next cycle without
any further purification. The ICP-OES analysis
showed that the Cu content in the fresh and in the
3rd cycle are 6.1% and 5.6 wt%, respectively.
100
80
60
40
20
0
1
2
3
4
[a]Reaction
conditions:
Ketone
(1
mmol),
No of Cycles
allyltributylstannane (1.2 mmol), 1.9 mmol% of Cu,
acetonitrile (3 mL) at 65 ºC. [b]Isolated yields.
Fig. 3: Recyclability test over Cu(II)/Mg-La
catalyst.
Spurred with the success of allylation of aldehydes
and ketones with allyltributylstannane, a gram-scale
synthesis of 1-(4-nitrophenyl)but-3-en-1-ol was
carried out under the standard reaction conditions.
Pleasingly, homoallyl alcohol 3b was obtained in
satisfactory yield of 82 % when the reaction was
carried out at 20.0 mmol scale (Scheme 2).
Plausible reaction mechanism
In order to get insight into the mechanism of the
allylation reaction catalyzed by Cu(II)/Mg-La, we
first investigated the role of tin species in the
allylation of aldehydes. In a controlled experiment,
Cu(II)/Mg-La mixed oxide and allyltributylstannane
were refluxed in acetonitrile. The solid material
was filtered off, washed with THF and vacuum
dried to get surface transient organometallic (STO)
intermediate. Interestingly, on heating STO
intermediate
with
4-nitrobenzaldehyde
in
acetonitrile yielded the corresponding homoallylic
6
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10.1002/adsc.201901133
Advanced Synthesis & Catalysis
alcohol. But, our efforts to isolate the intermediate
along with aldehydes failed. At this juncture, we
speculate that the plausible mechanism of allylation
may be undergoing formation of copper (IV)
species from the oxidation of Cu(II)/Mg-La mixed
oxide by allyltributylstannane. However, we are not
sure whether the active catalytic species is copper
(IV) or not. In the recent reports, Kar and co-
workers have postulated Cu (IV) as a possible
intermediate in oxidation catalysis.[26] The authors
claim is based on the series of experimental
Further, the reaction of trapped intermediate with 4-
nitrobenzaldehyde yielded the corresponding
desired homoallylic alcohol. At this stage, we
assume that the reaction path may follow the Cu(II)
to Cu (IV) oxidation state. Further investigation in
this direction is in progress.
Supporting Information
1
13
Characterization of all compounds with H and C
NMR spectra are available in the Supporting
Information.
characterization
including
electrochemistry,
UV/Vis/NIR, EPR, XANES measurements, and
DFT calculations which indicates the existence of
+IVoxidation state of Cu.[25c] It is indeed true that
the observation of the oxidation state + IV is very
rare in copper chemistry.
Conclusion
We have developed a simple and efficient method
for the allylation of aldehydes and ketones using
copper(II)/magnesium-lanthanum mixed oxide as
heterogeneous and reusable catalyst. The catalyst
preparation involves simple synthetic steps and can
be scaled-up to a large scale. The simple allylation
methodology, easy recovery, and reusable catalytic
systems are expected to contribute to the
development of benign allylation processes for a
variety of aldehydes and ketones.
To investigate the oxidative addition step, the
mixture of copper(II)/magnesium-lanthanum mixed
oxide and allyltributylstannane was refluxed in
acetonitrile and solid material was filtered off,
washed with acetonitrile and vaccume dried. The
trapped intermediate was subjected to TGA-DTA-
MS analysis (Fig. 4). The observed m/z values of
the evolved gas fragments are 26, 41 and 43 a.m.u.
corresponding to C2H2, C3H5, and C3H7,
respectively. The m/z value corresponding to allyl
tributylstannane was not detected, which suggests
that the mass fragmentation occurred during
pyrolysis of intermediate.
Experimental Section
Preparation of catalyst
The Mg-La mixed oxide was obtained by co-
precipitation of magnesium nitrate [Mg(NO3)2·6H2O]
and lanthanum nitrate [La(NO3)3·6H2O] (0.39 mol and
0.13 mol respectively, in 0.5 L water for an atomic ratio
Mg/La=3) at a constant pH 10.0 using a mixture of KOH
(1 mol) and K2CO3 (0.26 mol) in 0.52 L of distilled
water. The gel was washed until the pH reached neutral
º
followed by oven dried at 120 C subsequently calcined
in static air at 650 ºC/5 h at a ramping rate of 10 ºC min-1.
The copper impregnated Mg-La mixed oxide catalyst
was synthesized by an impregnation method. Mg–La
mixed oxide (1.5 g) was suspended in 150 mL of
aqueous Cu(NO3)2·3H2O (0.362 g, 1.5 mmol) solution
and stirred at 25 ºC for 12 h under a nitrogen atmosphere.
The solid was filtered, washed with distilled water, dried
at 100 oC and calcined at 250 ºC for 5 h to obtain the grey
colored powder Cu (II)/Mg–La catalyst.
Typical procedure for the allylation of 4-
Fig. 4: TGA-DTA-MS thermogram of STO.
nitrobenzaldehyde
with
allyltributylstannane
7
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10.1002/adsc.201901133
Advanced Synthesis & Catalysis
A mixture of 4-nitrobenzaldehyde (1 mmol), allyl
tributylstannane (1.2 mmol) and Cu (II)/Mg-La (20 mg)
in 3 mL of acetonitrile was stirred at 65 C for 5 h. The
[2] a) A. Fujino, T. Sugai, Adv. Synth. Catal. 2008, 350,
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Angew. Chem. 2003, 115, 4880; Angew. Chem. Int. Ed.
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º
reaction was monitored by TLC (n-hexane–ethyl acetate,
9:1). After completion of the reaction as determined by
TLC, the reaction mixture was cooled to room
temperature, centrifuged to separate the solid catalyst
and the catalyst was washed 3 times with ethyl acetate
(3x10mL). The combined organic layer was treated with
saturated aqueous solution of NH4Cl. Next, distilled
water was added and the organic layer was separated.
The aqueous layer was back extracted with ethyl acetate
(15 mL). The combined organic layer was dried on
anhydrous Na2SO4. The solvent was evaporated under
reduced pressure and the residue was purified by column
chromatography on silica gel with hexane and ethyl
acetate (9:1) to produce the corresponding homoallylic
products.
[3] a) T. Akiyama, J. Iwai, Synlett. 1998, 273; b) S.
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1993, 115, 8467.
Recyclability experiments
The following experiment was conducted to investigate
the heterogeneous nature of Cu(II)/Mg–La catalyst. In a
mixture of 4-nitrobenzaldehyde (1 mmol, 151mg) and
allyltributylstannane (1.2 mmol, 0.37 mL), Cu (II)/Mg-
La (20 mg) in 3 mL of acetonitrile was added and stirred
at 65 ºC for 3 h. After 3 h, the catalyst was separated
from the hot reaction mixture by centrifugation and
analysed the product by GC (only 50% conversion was
observed). The same reaction mixture (in absence of
catalyst) was continued at 65 ºC and no increase in the
product conversion was observed even after 5 h.
[4] H. R. Kalita, A. J. Borah, P. Phukan, Tetrahedron
Lett. 2007, 48, 5047.
[5] N. S. Krishnaveni, K. Surendra, V. P. Kumar, B.
Srinivas, C. S. Reddy, K. R. Rao, Tetrahedron Lett.
2005, 46, 4299.
Inductively
coupled
plasma
optical
emission
spectroscopic (ICP-OES) analysis of the reaction mixture
demonstrated that the negligible amount of copper metal
(0.062 ppm) was leached into the solution, thus
suggesting that the present reaction proceeds
heterogeneously.
[6] J. Lu, S.-J. Ji, R. Qian, J. -P. Chen, Y. Liu, T. -P.
Loh, Synlett. 2004, 534.
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The authors wish to thank the CSIR and industry sponsored
project SSP-0670 for financial support and thanks to AcSIR
for all academic activities. S.L thanks DST, govt. of India for
financial support (WOS-A/CS-1103/2015G). The authors are
grateful to the Director, CSIR-IICT for providing the necessary
infrastructure.
(Manuscript
Communication
number:
IICT/Pubs./2019/26)
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Sommer, N. Deibel, F. Ehret, M. Bauer, B. Sarkar, S.
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