Copper ferrite nanoparticles catalyzed formation of β-Ketophosphonates via oxyphosphorylation of styrenes with H-phosphonates: A DFT study on UV–vis absorption spectra

Article abstract of DOI:10.1016/j.catcom.2020.106015

Typical copper ferrite nanoparticles (CuFe₂O₄) were used as a catalyst for one-pot synthesis of β-ketophosphonates via the reaction of alkenes with H-phosphonates under conventional heating conditions. The catalyst was prepared by using the coprecipitation method and was analyzed by physiochemical techniques. By using this catalyst system, several types of useful and new β-ketophosphonate products were obtained in very good to excellent yields under optimized reaction conditions in a novel way. Furthermore, the catalyst is recyclable and reusable from the reaction.

Full text of DOI:10.1016/j.catcom.2020.106015

Journal Pre-proof
Copper ferrite nanoparticles catalyzed formation of β-
Ketophosphonates via oxyphosphorylation of styrenes with H-
phosphonates: A DFT study on UV–vis absorption spectra
Firouz Matloubi Moghaddam, Maryam Daneshfar, Reza Azaryan,
Jean-Luc Pirat
PII:
S1566-7367(20)30091-1
DOI:
https://doi.org/10.1016/j.catcom.2020.106015
CATCOM 106015
Reference:
To appear in:
Catalysis Communications
Received date:
Revised date:
Accepted date:
22 February 2020
9 April 2020
10 April 2020
Please cite this article as: F.M. Moghaddam, M. Daneshfar, R. Azaryan, et al., Copper
ferrite nanoparticles catalyzed formation of β-Ketophosphonates via oxyphosphorylation
of styrenes with H-phosphonates: A DFT study on UV–vis absorption spectra, Catalysis
Communications (2020), https://doi.org/10.1016/j.catcom.2020.106015
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Copper Ferrite Nanoparticles Catalyzed Formation of
β-Ketophosphonates via Oxyphosphorylation of Styrenes with
H‑ Phosphonates: A DFT study on UV-Vis absorption spectra
a
b
Firouz Matloubi Moghaddam*a, Maryam Daneshfara, Reza Azaryan , Jean-Luc Pirat
aLaboratory of Organic Synthesis and Natural Products, Department of Chemistry,
Sharif University of Technology, Azadi Street, PO Box 111559516 Tehran, Iran
*E-mail Address: matloubi@sharif.edu
bAM2N, UMR 5253, ICGM, ENSCM, 8 Rue de L'Ecole Normale, 34296
Montpellier Cedex 5, France.
Abstract: Typical copper ferrite nanoparticles (CuFe2O4) were used as a catalyst for one-pot
synthesis of β-ketophosphonates via the reaction of alkenes with H-phosphonates under
conventional heating conditions. The catalyst was prepared by using the coprecipitation method
and was analyzed by physiochemical techniques. By using this catalyst system, several types of
useful and new β-ketophosphonate products were obtained in very good to excellent yields under
optimized reaction conditions in a novel way. Furthermore, the catalyst is recyclable and
reusable from the reaction.
Keywords: oxyphosphorylation, CuFe2O4, styrenes, β-ketophosphonates, heterogeneous catalyst, DFT,
UV–visible spectroscopy
1. Introduction
The construction of a C–P bond is highly important in organic synthesis, since organophosphorus
compounds are important intermediates for the synthesis of many biological active compounds
and natural products [1-6].
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Dialkyl H-phosphonates are an important class of building blocks for the synthesis of
organophosphorus compounds, which have been applied for the synthesis of β -
Ketophosphonates,
-hydroxy
phosphonates,
bisphosphonates,
alkynylphosphonates,
phosphoramides, -aminophosphonates, etc [7].
Between them, β-ketophosphonates are an enormously useful class of phosphorus-containing
organic compounds, due to their bioactivity and applications in synthetic chemistry [8-10].
Because of their importance, extensive research has been performed in the development of new
protocols for their preparation [11, 12].
In 2011, Ji’s group found a new way to synthesize β-ketophosphonates by reacting alkenes with
dioxygen and H-phosphonates in the presence of copper/iron cocatalysts (Scheme 1a) [13].
Recently, Tan Jian Gu and Chun Cai reported homogeneous catalyst for the synthesis of β-
ketophosphonates. Copper/iron catalyzed phosphorylation of styrenes with the aid of DTBP (di-
tert-butyl peroxide) as the oxidant (Scheme 1b) [14].
Chen and co-workers reported the synthesis of β-ketophosphonates via homogeneous catalyst
CuSO4·5H2O in CH3CN under open air conditions. In a sharp contrast to Song’s method, the
most prominent advantage of this reaction is using common and inexpensive CuSO4·5H2O,
instead of expensive CuOTf as catalyst. The advantages also include a base free condition and
extensive reaction scope (Scheme 1c) [15, 16].
Exploration of new substrates for β-ketophosphonates with alkynes or alkynyl carboxylic acids
under different conditions were employed [16]. Transition metal catalysts were used for the
direct phosphorylation of alkynes. Zhao group reported the synthesis of β-ketophosphonates
directly from alkynes and H-phosphonates in the presence of AgNO3/CuSO4 and K2S2O8.
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Over the past few years, the use of both α,β-alkynyl carboxylic acids and α,β-alkenyl carboxylic
acids as terminal alkyne and alkene equivalents, began to be developed in the literature [17].
Some advantages of α,β-alkynyl carboxylic acids and α,β-alkenyl carboxylic acids are no
unpleasant smell, and easy handling and storage due to their states as solid compounds [15].
However, almost all of these methods have limitations such as recycling and reuse of the
catalyst, tedious procedures, relatively harsh reaction conditions, or losing a large amount of
catalyst during work-up of the reaction.
Therefore, the development of mild, convenient, efficient, and environmentally benign methods
to access β-ketophosphonates is still highly desirable in synthetic chemistry.
We report the application of a highly active recyclable heterogeneous nanocopper ferrite catalyst
for the oxyphosphorylation reaction of various styrenes under conventional heating conditions.
Compared to previous homogenous unrecyclable catalysts, this is a low cost catalyst and
prepared in a few steps from available starting materials (Scheme 1d).
On the other hand, because of its ferromagnetic nature, this catalyst completely and easily
removed from the reaction, and it was possible to reuse it in consequent runs. This is a very
important advantage because any remaining metal-based catalyst in the product is dangerous,
particularly in cases where the end product is directly related to human life such as in
pharmaceutical synthesis. Further, in comparison to ferromagnetic catalysts reported
elsewhere,[18, 19] the rate of precipitation of the nanocopper ferrite catalyst on application of an
external magnetic field is faster.
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Scheme 1: Comparison of previous methods with this work.
2. Experimental
2.1 Materials and Characterization Methods
All materials used are commercially available and were purchased from Merck and used without
1
any additional purification. H NMR and 31P NMR spectra were recorded on a Bruker
1
AVANCE DRX 500 MHz NMR spectrometer at RT. H NMR spectra were recorded in CDCl3
with tetramethylsilane (TMS) as the internal standard and 31P NMR spectra were obtained in
H3PO4 as the internal standard. The XRF analysis was performed with a SPECTRO XEPOS
spectrometer. The samples were characterized by crystallographic phase identification carried
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out with a Sradi P diffractometer using CuKa radiation and equipped with a graphite
monochromator in the diffracted beam and an oscillation counter. FT-IR spectra of samples were
obtained using an ABB Bomem MB-100 FT-IR spectrophotometer. Field emission scanning
electron microscopy (MIRA3 TESCAN-RMRC) and transmission electron microscope
(TECNAI F20) were used to characterize the morphologies and the particle size distribution of
the nanoparticles. Magnetic measurements were performed at RT using an AGFM
magnetometer.
2.2 Synthesis of Nickel/ Copper/ Cobalt Ferrite nanoparticles
The solutions of iron chloride (FeCl3.6H2O) (100 mL, 0.2 M) and nickel/ copper/ cobalt chloride
(NiCl2.6H2O)/ (CuCl2.2H2O)/ (CoCl2.2H2O) (100 mL, 0.1 M) were prepared separately and
mixed together. For pH to reach 13, a solution of NaOH (3M) was added slowly to the flask.
Finally, oleic acid (3drops) was added to the solution as surfactant to prevent the aggregation and
agglomeration of the nanoparticles. Then, the suspension was vigorously stirred using a magnetic
stirring bar at 60 °C for 2 h. After complete precipitation, the residue was washed with double-
distilled water (3× 25ml) and dried in an oven at 90 °C overnight. It was then calcinated at 500
°C for 3 h.
2.3 General Procedure for Synthesis of β-ketophosphonates from alkenes and H-
phosphonates
A mixture of alkenes (0.5 mmol), H-phosphonates (1.5 mmol), CuFe2O4 (10 mol%), DTBP (1.0
mmol), and Et3N (0.5 mmol) in CH3CN (1.0 mL) was stirred at 85 °C for 6 h. The reaction was
monitored by TLC plate and, after the completion of the reaction, the mixture was cooled to
room temperature. The magnetic nanoparticles of the catalyst were collected with the help of a
magnet. Then, 10 mL of water was added to the mixture and the product was extracted with ethyl
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acetate (4 × 10 mL). The organic layer was separated, washed with brine, and dried over Na2SO4.
The volatiles were removed under vacuum to afford the crude product. The crude product was
purified by column chromatography on silica gel and eluted with petroleum ether/ethyl acetate
(1:1) to afford the desired phosphonate as a yellow oil.
3. Results and discussion
Copper ferrite nanoparticles were synthesized using the coprecipitation method described in the
Experimental Section. The activity of the copper ferrite nanoparticles in the β-ketophosphonates
synthesis was investigated under conventional heating conditions.
The structures of catalysts were characterized using various physicochemical techniques
including FT-IR, EDS, XRD, VSM, FE SEM, and TEM analysis.
Figure S1. shows the FT-IR spectrum of copper ferrite nanoparticles, in the range of
-1
-1
450-4,000 cm . The spectrum presents characteristic bands at 3434, 540, and 470 cm . The
-1
-1
broad band at 3,434 cm can be assigned to the absorbed water. The peaks at 470 and 540 cm
are assigned to the vibration of Fe-O and Cu-O bond, respectively, which confirm the structure
of copper ferrite nanoparticles.
The XRD patterns of the copper ferrite nanoparticles are shown in Figure S2. The XRD patterns
of catalyst indicating a particle size of 47.7 nm are calculated by the broadening of the most
intense peak at 2θ= 35.75 using the Debye-Scherrer equation, which is in agreement with the
average particle size obtained from TEM (Figure S3).
The magnetic properties of the nanoparticles were investigated at room temperature. According
to the magnetization curve of the sample shown in Figure S4, CuFe2O4 nanoparticles have a
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superparamagnetic behavior with a small coercivity and can be easily attracted by a small
external magnet.
The energy dispersive spectrum (EDS) shows the presence of Cu, Fe, and O in the catalyst
structure (Figure S5).
To optimize the reaction conditions, various types of solvents and bases at different temperatures
in the presence of various amounts of catalyst were surveyed in the reaction between the model
substrates styrene and diethyl phosphite. The results are summarized in Table 1.
First, we performed an oxidant screening (entries 1-6). Oxidants such as O2, K2S2O8, DTBP, and
H2O2 were examined. The result showed that the metal catalyst and DTBP were crucial for the
reaction. As the next optimization step, a variety of ferrite nanoparticles were investigated, with
the finding that copper ferrite nanoparticles were the optimal choice for the reaction (entries 7-8).
In fact, the presence of copper was critical to the success of this oxyphosphorylation reaction and
no product was detected when nickel ferrite was used as catalyst (entry 8).
Furthermore, to improve the efficiency of the reaction, different bases were investigated under
the same reaction conditions (entries 9-12). According to the results obtained, Et3N shows the
best reactivity and was chosen as the optimal base for this reaction.
Then, the effects of various polar and nonpolar solvents in this reaction were studied (entries 13–
22). No product was detected when the reaction was performed in water and ethanol as green
solvents (entries 18 and 20). Therefore, CH3CN as a polar aprotic solvent was selected for
performing the reaction.
Finally, the influence of temperature on the reaction was also investigated (entries 3, 23-24). The
reaction efficiency was affected by the temperature, and 85 °C was found to be the optimal
temperature for this reaction with higher conversion (entry 3).
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Table 1. Optimization of thereaction conditionsa
Entry Catalyst
Oxidant
Solvent
T (°C)
Base
Yield b(%)
1
2
3
4
CuFe2O4
CuFe2O4
CuFe2O4
CuFe2O4
CuFe2O4
CuFe2O4
CoCuFe2O4
NiFe2O4
CuFe2O4
CuFe2O4
CuFe2O4
CuFe2O4
CuFe2O4
CuFe2O4
CuFe2O4
CuFe2O4
CuFe2O4
CuFe2O4
CuFe2O4
CuFe2O4
CuFe2O4
CuFe2O4
CuFe2O4
CuFe2O4
-
O2
DTBP
K2S2O8
H2O2
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
DMF
DMSO
Toluene
1,4-dioxane
DCE
H2O
THF
85
85
85
85
85
85
85
85
85
85
85
85
85
85
85
85
85
85
66
78
77
60
r.t
Et3N
Et3N
Et3N
Et3N
Et3N
Et3N
Et3N
Et3N
-
Et2NH
DABCO
DIPEA
Et3N
Et3N
Et3N
Et3N
Et3N
Et3N
Et3N
Et3N
Et3N
Et3N
Et3N
Et3N
45
55
80
59
56
81
77
NR
40
42
38
85
35
45
28
40
78
NR
65
NR
65
70
NR
30
5
6c
7
DTBP
DTBP
DTBP
DTBP
DTBP
DTBP
DTBP
DTBP
DTBP
DTBP
DTBP
DTBP
DTBP
DTBP
DTBP
DTBP
DTBP
DTBP
DTBP
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
EtOH
EtOAC
CHCl3
CH3CN
CH3CN
45
aReaction conditions: 1a (0.5 mmol), 2a (1.5 mmol), catalyst (10 mol%), base (0.5 mmol), solvent (1 mL),
oxidant (1 mmol), 6 h. bIsolated yield. cOxidant (2 mmol). NR = no reaction
Having these optimized reaction conditions in hand, we next examined the scope of the
phosphorylation of alkenes with H-phosphonates for the synthesis of β-ketophosphonates (Table
2).
As illustrated in Table 2, a variety of β-ketophosphonates can be conveniently and efficiently
obtained by these copper ferrite nanoparticles in the oxyphosphorylation reaction of alkenes. In
general, both electron-donating and electron-withdrawing substituents at the phenyl ring of
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styrene were suitable for this transformation and the corresponding oxidative coupling products
were obtained in very good to excellent yields (3a–3o).
The electronic effects of the substituents attached to phenyl rings had no noticeable effect on the
efficiency of oxyphosphorylation reactions. Bromo and chloro groups at the phenyl ring of
styrene are useful for further functionalization at a later stage using cross coupling reactions (3i–
3l). Fluorine has been recognized as an important element in materials science, and many
fluorine-containing biologically active agents are finding applications as pharmaceuticals and
agrochemicals (3g–3h). Additionally, stilbene was also a suitable substrate for this reaction,
which highlights the potential application of this method (3o).
Table 2. Scope of the oxyphosphorylation of alkenes with H-phosphonatesa
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aReaction conditions: 1a (0.5 mmol), 2a (1.5mmol), catalyst (10 mol%), base (0.5 mmol),
solvent (1 mL), oxidant (1 mmol), 6 h. ball Isolated yields
To determine if the oxyphosphorylation of alkynes and allylic compounds was feasible, we
extended our study to phenylacetylene and safrole under the optimized reaction conditions.
CuFe2O4 catalyzed oxyphosphorylation of phenylacetylene leading to β‑ ketophosphonates (3p-
3q) [Eq. (S2)]. Surprisingly, through the reaction between safrole and dialkyl H-phosphonates,
two unexpected products (3r-3s) were isolated which have not been reported to date [Eq. (S3)].
Further studies on mechanistic details and other substrates are currently underway in our group.
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To check the reusability of the catalyst, the oxyphosphorylation of styrene with diethyl phosphite
was performed under the optimized reaction conditions. First, catalyst was recovered from the
0
reaction mixture by a magnetic rod, washed twice with water, and dried in an oven at 100 C.
Then, recovered nanoparticles were employed in another run under the same reaction condition.
This process was repeated six times, and each time the isolated yield was measured exactly. The
results indicate that no considerable loss of activity was observed up to 6 cycles (Figure S6).
In order to study the surface morphology of the catalyst, FE SEM images were obtained (Figure
1). The FE SEM images of the catalysts before and after six runs of the reaction were obtained to
confirm that the size, morphology, and dispersity of the nanoparticles were not approximately
transformed during these runs. According to the images, it is obvious that the activity, efficiency,
and morphology of the catalyst remains constant.
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Figure 1. The FE SEM images of CuFe2O4 nanoparticles before employing as catalyst (left) and after six
times reuse (right).
In order to gain reasonable insight into the reaction mechanism, radical trapping experiments
were performed [Eq. (S1)]. By employing 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) or 2,6-
di-tert-butyl-4-methylphenol (BHT) as radical scavengers along with styrene and diethyl
phosphite under the standard conditions, the reaction was totally suppressed.
We interpret these results as evidence that our transformation occurs through a radical
mechanism.
On the basis of the above control experiments and previous reports, a plausible mechanism for
this catalytic reaction is proposed in Scheme 2.
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Scheme 2. Proposed mechanism.
First, DTBP reacts with copper ferrite to form intermediate 4 which adds to dialkyl phosphonate,
and phosphonyl radical 5 is generated. Subsequently, addition of the phosphonyl radical 5 to the
double bond of alkenes 1 produces the alkyl radical 6, and copper ferrite was regenerated to
continue the catalytic cycle. Because the reaction temperature is 85 °C, the formed radical 6
interacts with the hydroxyl radical. Finally, the intermediate 7 would undergo oxidation to give
the desired product 3.
Conclusion
In summary, oxyphosphorylation of alkenes was performed successfully using ferromagnetic
copper ferrite nanoparticles as a very efficient heterogeneous catalytic system.
The proposed conditions applied here for the oxyphosphorylation of alkenes compared to
previous reports using homogeneous catalytic systems lead to a more convenient procedure and
better yields. β-ketophosphonates are important intermediates for the synthesis of many
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biologically active compounds and natural products such as (-)-diospongin in the synthetic
community [13]. By employing inexpensive, recyclable, and reusable ferromagnetic copper
ferrite nanoparticles as catalyst, our transformation is both sustainable and practical.
Acknowledgement
We gratefully acknowledge the funding support received for this project from the Sharif
University of Technology (SUT), Islamic Republic of Iran.
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CRediT author statement
Manuscript title:
Copper Ferrite Nanoparticles Catalyzed Formation of β-Ketophosphonates via
Oxyphosphorylation of Styrenes with H‑ Phosphonates: a DFT study on UV-Vis
absorption spectra
1) Firouz Matloubi Moghaddam: Conceptualization, Methodology, Funding acquisition, Project
administration, Validation (Corresponding Author).
2) Maryam Daneshfar: Investigation, Formal analysis, Software, Data Curation, Writing -
Original Draft (First Co-Author).
3) Reza Azaryan: Resources, Visualization, Writing - Review and Editing (Second Co-Author).
4) Jean-Luc Pirat: Supervision (Third Co-Author).
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Declaration of interests
The authors declare thatthey have no known competing financial interests orpersonal relationships
that could have appeared to influence the work reported in this paper.
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



One-potsynthesis of β-ketophosphonates usingaheterogeneous catalyst.
Broad substrate scope and wide functional group tolerance.
Formation of products in excellentyields and shortreaction times.
Recyclable and reusable catalyst without loss of activity.
18