4-Amino-1,2,4-triazoles-3-thiones and 1,3,4-oxadiazoles-2-thiones·palladium(II) recoverable complexes as catalysts in the sustainable Suzuki-Miyaura cross-coupling reaction

Article abstract of DOI:10.1016/j.jorganchem.2020.121353

The Suzuki-Miyaura cross-coupling reaction using 4-amino-1,2,4-triazoles and 1,3,4-oxadiazoles-2-thiones·palladium (II) is studied. The reaction is optimized and the most appropriate catalytic complex is tested with several aryl halides, boronic acids in an environmentally benign solvent system (H₂O/EtOH). The recovery of the catalytic species is also surveyed because of the nature of the employed solvent. A domino process is efficiently carried out following the standard conditions. Several surface parameters of the ligands are analyzed and the resulting values are extrapolated to the insoluble palladium catalyst.

Full text of DOI:10.1016/j.jorganchem.2020.121353

Journal Pre-proof
4-Amino-1,2,4-triazoles and 1,3,4-oxadiazoles·palladium(II) recoverable complexes
as catalysts in the sustainable Suzuki-Miyaura cross-coupling reaction
Manel Chehrouri, Cristina Moreno-Cabrerizo, Adil A. Othman, Ihssene Chabour,
Marcos Ferrándiz-Saperas, Inmaculada Sempere, H. Ali Döndaş, M. de Gracia
Retamosa, José M. Sansano
PII:
S0022-328X(20)30255-2
DOI:
https://doi.org/10.1016/j.jorganchem.2020.121353
JOM 121353
Reference:
To appear in: Journal of Organometallic Chemistry
Received Date: 5 April 2020
Revised Date: 22 May 2020
Accepted Date: 24 May 2020
Please cite this article as: M. Chehrouri, C. Moreno-Cabrerizo, A.A. Othman, I. Chabour, M. Ferrándiz-
Saperas, I. Sempere, H.A. Döndaş, M. de Gracia Retamosa, José.M. Sansano, 4-Amino-1,2,4-
triazoles and 1,3,4-oxadiazoles·palladium(II) recoverable complexes as catalysts in the sustainable
Suzuki-Miyaura cross-coupling reaction, Journal of Organometallic Chemistry (2020), doi: https://
doi.org/10.1016/j.jorganchem.2020.121353.
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-Amino-1,2,4-triazoles and 1,3,4-oxadiazoles·Palla-
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dium(II) recoverable complexes as catalysts in the
sustainable Suzuki-Miyaura cross-coupling reaction
Manel Chehrouri, Cristina Moreno-Cabrerizo, Adil A. Othman, Ihssene Chabour, Marcos Ferrándiz-Saperas, Inmaculada
Sempere, H. Ali Dondas, M. de Gracia Retamosa and José M. Sansano.

1
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com
4
-Amino-1,2,4-triazoles and 1,3,4-oxadiazoles·palladium(II) recoverable complexes
as catalysts in the sustainable Suzuki-Miyaura cross-coupling reaction
a
b
a
b
Manel Chehrouri, Cristina Moreno-Cabrerizo, Adil A. Othman, * Ihssene Chabour, Marcos Ferrándiz-
b
b
c
d
b
Saperas, Inmaculada Sempere, H. Ali Döndaş, M. de Gracia Retamosa and José M. Sansano *
a
Laboratoire de Synthèse Organique Bioactive, Département de Chimie Physique, Faculté de Chimie, Université des Sciences et de la Technologie d’Oran,
Mohamed Boudiaf-USTO-MB, BP. 1505, El-M’naouer, 31003 Oran, Algeria
b
Departamento de Química Orgánica, Instituto de Síntesis Orgánica and Centro de Innovación en Química Avanzada (ORFEO-CINQA), Universidad de
Alicante 03080-Alicante, Spain.
c
Department of Chemistry, Faculty of Pharmacy, Mersin University, Yenisehir, 33169, Mersin, Turkey.
Universidad de Sevilla and Centro de Innovación en Química Avanzada (ORFEO-CINQA) Avda. Américo Vespucio, 49,41092 Sevilla (Spain).
d
*
indicates the main/corresponding author, adelaliothman@gmail.com, jmsansano@ua.es
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
The Suzuki-Miyaura cross-coupling reaction using 4-amino-1,2,4-triazoles and 1,3,4-
oxadiazoles·palladium(II) is studied. The reaction is optimized and the most appropriate
catalytic complex is tested with several aryl halides, boronic acids in an environmentally benign
2
solvent system (H O/ EtOH). The recovery of the catalytic species is also surveyed because of
Available online
the nature of the employed solvent. A domino process is efficiently carried out following the
standard conditions. Several surface parameters of the ligands are analyzed and the resulting
values are extrapolated to the insoluble palladium catalyst.
Keywords:
palladium
micellar
water/ethanol
recycling
2020 Elsevier Ltd. All rights reserved.
Suzuki-Miyaura
1
. Introduction
The Suzuki-Miyaura cross-coupling reaction is one of the
We have studied the already described long-chain attached to
46
most useful and versatile ways to achieve different series of
heterocyclic scaffolds 1 and 3, derived from palmitic acid, to
generate palladium(II) complexes 2 and 4 (Scheme 1) using
different metallic sources. These species, specially 2a and 2b
were efficient in conventional examples of both Tsuji-Trost and
Mizoroki-Heck reactions, in acetonitrile and toluene,
2
2
compounds (preferentially biaryls) where a new Csp -Csp bond
1-20
is formed.
The resulting molecules derived from this
transformation have different applications in many areas. For
example, in the preparation of natural products, nucleoside
surrogates, drugs, liquid crystals and pharmaceutically interesting
47
respectively.
21-23
compounds.
A large number of reports concerning the
Suzuki-Miyaura coupling reactions appeared showing
improvements. For example, conducting the Suzuki-Miyaura
coupling reaction in environmentally friendly solvents such as
24-42
water or alcohols have particular importance.
In this sense,
the importance of the nature of the ligands of the palladium
complex determine the availability to run couplings to perform a
later recovery or reuse of them in this media. The employment of
43
ligands with surfactant nature, coordinated to the palladium
atom, is crucial to recycle the catalytic system and is not very
44
frequent in organic chemistry. The most studied approach is
the use of additives with micellar/surfactant character facilitating
45
this coupling reaction in water or aqueous systems.

2
Journal of Organometallic Chemistry
a
Reaction conditions: 5a and 6a (0.2 mmol each), base (0.4 mmol), [Pd] (0.5
Scheme 1. Synthesis of palladium complexes 2 and 4.
mol%), solvent (2 mL), 12 h at the bath temperature indicated.
b
Isolated crude conversions determined by gas chromatography.
c
0
.25 mol% of 4b was employed.
The potential amphiphilic properties of entities 2 and 4
envisage the success of reactions run in aqueous media. So, in
this work, the ability of these complexes to operate in Suzuki-
Miyaura cross-couplings, performed in aqueous solutions, is
studied. This character would also permit to recover the catalyst
and reuse it with total efficiency.
With the more suitable conditions, and inside of a pressure
tube, the scope of the reaction was surveyed (Table 2). Aryl
iodides 5 reacted with arylboronic acids 6 affording excellent
yields of biaryls 7 using a bath of 100 ºC for 12 h (Table 2,
entries 1-15). Apparently, there is no important effects of the
substituents in the final yield of products 7. Both electron-
donating and electron-withdrawing groups can be used. Also,
heterocyclic components are appropriate to run this reaction
Table 2, entries 8 and 9). Aryl bromides needed a 120 ºC bath to
promote the reaction successfully in very high yields too (Table
, entries 16-23). However, the reaction of aryl chlorides is very
slow and despite increasing the temperature up to 150-160 ºC
bath) very small conversions were obtained. These results
allowed the total chemoselective transformation in 4-
iodochlorobenzene and 4-chlorobromobenzene (Table 2, entries
5 and 20). In addition, nonsteroidal anti-inflammatory drug
Felbinac, 7s) was prepared and isolated in 90% yield in a 2
mmol scale.
2
3
. Results and Discussion
(
Initially, the preparation of known heterocyclic ligands 1 and
was performed, according to the literature, starting from
47
2
palmitic acid. Next, the preparation of the palladium(II)
complexes 2 and 4 was done according to the procedure depicted
in Scheme 1. We proposed these tentative structures on the basis
of elemental analysis, and various instrumental techniques, since
it was not possible to isolate an appropriate crystal to run X-ray
(
46,47
1
(
diffraction analysis.
The optimization of the benchmark
Suzuki-Miyaura cross-coupling between iodoanisol and p-
tolylboronic acid was done using conditions reported in the
48
literature with heterocyclic palladium(II) complexes. Looking
for an environmental friendly process, EtOH was selected as
solvent and KOH as base at 78 ºC. The four complexes afforded
very good conversions (Table 1, entries 1-4) being selected 4b
Table 2. Pd-Catalyzed allylation of 3-acetyl-2-oxindoles
1
because the reaction crude was very clean ( H NMR) and traces
of the homocoupled product were not detected. The reaction in
neat water was not complete after 12 h (Table 1, entry 5).
However, the combination of water/ethanol in equal proportions
afforded an excellent conversion and very clean reaction product
7
a (Table 1, entry 6) in a bath at 100 ºC. The employment of
potassium carbonate as base or assaying lower catalyst loading
0.25 mol%) gave the final coupling product in 95 and 55%
1
2
a,b
(
Ent.
Hal
Ar
Ar
Yield (%)
7
conversion (this reaction was not completed after 12 h),
respectively (Table 1, entries 7 and 8).
1
2
3
4
5
6
7
8
9
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
4-(MeO)C
4-(MeO)C
4-(MeO)C
4-(MeO)C
4-(MeO)C
4-(MeO)C
3-(MeO)C
6
6
6
6
6
6
6
H
H
H
H
H
H
H
4
4
4
4
4
4
4
4-MeC
4-(CF )C
4-(CHO)C
4-FC
6
H
4
7a
7b
7c
7d
7e
7f
96
89
91
93
89
91
88
91
85
84
92
92
89
89
88
77
85
90
92
90
89
86
3
6
H
4
6
H
4
Table 1. Optimization of the Suzuki-Miyaura cross-coupling
between iodoanisol and p-tolylboronic acid.
6
H
4
2-(BnO)C
Ph
6 4
H
4-MeC
4-MeC
4-MeC
4-MeC
4-MeC
Ph
6
6
6
6
6
H
H
H
H
H
4
4
4
4
4
7g
7h
7i
2-Pyridyl
2-Thienyl
2-Naphthyl
1
1
1
1
1
1
1
1
1
1
2
2
2
2
0
1
2
3
4
5
6
7
8
9
0
1
2
3
7j
4-MeC
Ph
6
H
4
7k
7l
4-MeC
6
H
4
Ph
7m
7n
7o
7f
4-FC
4-ClC
4-(MeO)C
4-(CN)C
4-(CHO)C
6
H
4
Ph
a,b
Ent.
[Pd]
Solvent
Base
T (ºC)
Conv. (%)
6
H
4
Ph
c
Br
Br
Br
Br
Br
Br
Br
Br
6
H
4
Ph
1
2
3
4
5
6
7
8
2a
2b
4a
4b
4b
4b
4b
EtOH
EtOH
EtOH
EtOH
KOH
KOH
KOH
KOH
KOH
KOH
78
78
98
83
99
96
20
99
95
55
c
c
c
c
c
c
c
6
H
4
Ph
7p
7q
7r
7o
7a
7j
6
H
4
Ph
78
4-(NO
2
)C
6
H
4
Ph
78
4-ClC
6
H
4
Ph
H
2
O
100
100
100
100
4-(MeO)C
2-Naphthyl
4-(CH CO H)C
6
H
4
4-MeC
4-MeC
Ph
6
6
H
4
4
H
H
H
2
2
2
O/EtOH
O/EtOH
O/EtOH
H
K
2
CO
3
d
c
2
2
6
H
4
7s
92
4b
KOH

3
a
Reaction conditions: 5 (0.2 mmol), boronic acid (0.2 mmol), 4b (0.5
mol%), KOH (0.4 mmol), 1:1 water/EtOH (2 mL), pressure tube at 100 ºC
bath temperature) 12 h.
Isolated yield after flash chromatography.
Reaction performed at 120 ºC (bath temperature).
Performed in 2 mmol scale.
B(OH)2
(
I
b
4b (1.0 mol%)
1:1 H O/EtOH, 100 ºC,
c
N
2
d
O
O
12 h, KOH (2 equiv)
N
8
6a
With the aim of recovering the catalyst, taking advantage of
9
PdX
the suspension/dispersion of the catalytic species in water, the
ethanol was evaporated after completing the first batch of the
coupling of p-iodoanisole. Then, ethyl acetate was added
extracting the product 7a. The aqueous suspension was again
submitted to a new process giving high chemical yields. The
procedure was repeated up to the fifth recycled experiment
arising very high yield of 7a (Figure 1). We stopped the study in
this point, but we are sure that it is possible to run another 5
catalytic cycles more with the same catalyst. The catalyst
demonstrated to be very stable and did not lost its catalytic
efficiency. A new cross-coupling reaction was performed using
the aqueous phase resulting from the first cycle, previously
filtered, and an extremely low conversion (<10%) was obtained.
This result indicated the heterogeneous character of this catalysis.
(81%)
O
N
Scheme 2. Synthesis of product 9 through a domino sequence.
The nature of palladium complex 4b was a brown sticky dense
oil. After finishing a catalytic cycle, the catalyst was filtered of
and a similar aspect was observed. If a new catalytic cycle is
attempted with this filtered solution the reaction did not occur, so
this ensures the heterogeneous character of this catalysis. The
presence of nanoparticles was very difficult to observe after
analysis of TEM. We studied the XPS results of the catalyst
before and after the Suzuki-Miyaura cross-coupling concluding
that the reduction of palladium(II) to zero-valent palladium
occurred during the chemical process (Figure 2). Although the
mercury test is a rapid and accepted used method for identifying
homogeneous molecular catalysis from nanoparticle metal
catalysis, it has been published that this test is generally
-
1
The estimated TON is very close to 200 and the TOF is 16.7 h .
This study was also repeated twice in the preparation and
isolation, by precipitation in acidic media, of drug 7s, affording
this product in 89% yield after the second catalytic bath.
51
inadequate under certain conditions. The mixture of the freshly
prepared complex in the first catalytic cycle for the synthesis of
compound 7a was treated with 100 equiv of mercury for 1 d at
1
00
9
6
95
96
96
95
80
60
40
20
0
1
00 ºC (300 rpm, magnetic stirrer rotation rate) and the observed
conversion decreased to 58%. Besides, when the same poisoning
conditions were applied to the reaction performed using the
recovered catalytic complex (for example, second cycle of Figure
1
) the Suzuki-Miyaura coupling occurred only in a 15%
conversion. At this point, the presence of palladium nanoparticles
could be confirmed but operating in an heterogeneous mode.
According to all these facts and the literature precedents, a
plausible mechanistic formation of these nanoparticles can be
1
2
3
4
5
44a
Catalytic cycle
draw (Scheme 3).
a)
Figure 1. Synthesis of compound 7a using the same recycled
catalyst.
The catalyst 4b was also submitted to a domino process
involving an intramolecular Mizoroki-Heck type reaction in 8.
Here, the alkene acted as internal relay system, which inhibited
the β-hydride elimination of the intermediate organometallic
4
9,50
species, after the 5-exo-trig-cyclization step.
The resulting
3
palladium-Csp intermediate finally underwent the expected
Suzuki-Miyaura cross-coupling with p-tolylboronic acid. This
2
3
sequential double Csp -Csp formation occurred in the presence
of 1 mol% of the catalyst in 81% yield (Scheme 2). Again, the
catalyst could be recovered from the aqueous suspension and
reused in another new reaction affording the same result.
b)

4
Journal of Organometallic Chemistry
a
-5
Measured in chloroform, x10 (M).
In kJ·mol .
b
c
d
-1
Calculated from Griffin’s equation.
Established according to HLB values.
55
3
. Conclusions
The efficiency of the palladium complex 4b in the Suzuki-
Miyaura cross-coupling reaction, with surfactant character, was
demonstrated. Unfortunately, aryl chlorides were not appropriate
substrates for this catalytic complex. The required mild
conditions and the recycling of the catalytic species were
important parameters to consider. The surface properties could be
extrapolated from measurements done to the heterocyclic
precursor. The robustness of this catalytic system was evaluated
by the successful domino reaction performed. In comparison with
analogous systems operating in water or aqueous solvents, the
results are in the same ranges as depicted in Table 4. The most
important feature of this catalytic complex is the high percentage
during the recovery and its ability to run a new process with the
same efficiency (>5 cycles).
Figure 2. XPS of 4b (a), and XPS of the catalyst filtered after the
reaction (b).
Het
N
_
Het
Het
N
EtOH:H
2
O
S
(
)
14
O
100 ºC
Table 4. Comparison between the results of this work with the
2
2 2
Pd Cl
Het
a
4
b
other ones published previously.
Micellar nanoparticles
[
Pd]
Catal.
cycles
Scheme 3. Plausible formation of micellar nanoparticles.
Ref.
time
T (ºC)
HalAr
(
mol%)
4
4
4
4
4
4a
4b
4c
4d
4e
0
0
.1
.5
24 h
30 min
4 h
80
100
50
Br
Br, I
5
10
The evaluation of same surface properties of palladium
complexes 2 and 4 were very difficult due to their scarce
solubility in organic solvents. However, a closer information can
be obtained by the assessment of these properties of the
heterocyclic ligands 1 and 3. Critical micelle concentration
b
0.5
Br, I
nr
b
0.1-2.0
2-22 h
24
rt-100
100
50
Cl
nr
0
.005
Br, I
10
44f
0
0
.1
.1
2.5-4.5 h
Cl, Br, I
Br
5
(CMC) values were determined plotting the electrical
44g
c
b
5 min
100
85
nr
conductivity of the solutions in chloroform versus the
44h
b
52
0.05
0.5
2 h
24 h
12 h
6 h
Br
nr
concentration (M) (Table 3). The two values are in the same
4
4
4i
4j
b
52,53
100
rt
Cl
nr
range and corresponded to classical non-ionic surfactants.
The micellization free energy was calculated from the CMC
b
0
.1
Cl, Br, I
Cl, Br
Br, I
nr
52
44k
4l
b
value (ΔGºmic = 2.303·R·T·log CMC). The similar results
obtained for both samples confirmed the spontaneous
micellization processes. Measurements of the hydrophilic
0.5
80
nr
4
0.06
1-24 h
0.5-10 h
5
45
8
8
44m
44n
0
.01
-5
70
Cl, Br, I
Cl, Br, I
Cl, Br, I
Br, I
54
lipophilic balance (HLB) using Griffin’s equation provided
parameters of 7.05 and 6.47 (Table 3). These values predict that
the ligands 1 and 3 can be classified as wetting/spreading agent
and water in oil emulsifying agent, respectively, but both of them
1
60
5
4
2
0
.2
.5
24
80-120
100
6
d
0
12
>5
a
b
c
d
55
All data are referred for a similar chemical yield.
nr: no reported.
Under microwaves irradiation.
This work.
are water dispersible substances. By extrapolation of these
results towards the catalyst 4b, the CMC value would be higher
than the corresponding ligand due to its more ionic character,
and, in consequence the negative micellization free energy would
ensure a spontaneous micellization. In addition, it would be
expected a HLB ~ 10 value, affording a water dispersion and oil
in water emulsifying agent.
4
. Experimental section
4
.1 General information.
All commercially available reagents and solvents were used
without further purification, only aldehydes were also distilled
prior to use. Analytical TLC was performed on Schleicher &
Schuell F1400/LS 254 silica gel plates, and the spots were
visualized under UV light (l ¼ 254 nm). Flash chromatography
was carried out on hand-packed columns of Merck silica gel 60
Table 3. Determination of surface properties of ligands 1 and 3.
a
b
c
d
Ligand
CMC
ΔGºmic HLB
Classification
Water dispersible
Wetting/spreading agent
Water dispersible
1
3
9.0
7.8
-23.10 7.05
-23.45 6.47
(0.040-0.063 mm). The structurally most important peaks of the
Water in oil emulsifying agents
IR spectra (recorded using a Nicolet 510 PFT) are listed and

5
-
1
58
wave numbers are given in cm . NMR spectra were obtained
using a Bruker AC-300 or AC-400 and were recorded at 300 or
4
2-(p-Tolyl)thiophene (7i).
1-(p-Tolyl)naphthalene (7j).
4,4'-Dimethyl-1,1'-biphenyl (7k).
58
1
13
64
00 MHz for H NMR and 75 or 100 MHz for C NMR, using
CDCl as solvent and TMS as internal standard (0.00 ppm). The
following abbreviations are used to describe peak patterns where
appropriate: s singlet, d doublet, t triplet, q quartet, m multiplet or
unresolved and br s broad signal. All coupling constants (J) are
given in Hz and chemical shifts in ppm. C NMR spectra were
referenced to CDCl at 77.16 ppm. DEPT-135 experiments were
performed to assign CH, CH and CH . Low resolution electron
impact (EI) mass spectra were obtained at 70 eV using a
Shimadzu QP-5000 by injection or DIP; fragment ions in m/z are
given with relative intensities (%) in parentheses. High resolution
mass spectra (HRMS) were measured on an instrument using a
quadrupole time-of-flight mass spectrometer (QTOF) and also
through the electron impact mode (EI) at 70 eV using a Finnigan
VG Platform or a Finnigan MAT 95 S.
61
1,1'-Biphenyl (7l).
4-Methoxy-1,1'-biphenyl (7m).
4-Fluoro-1,1'-biphenyl (7n).
4-Chloro-1,1'-biphenyl (7o).
3
5
9
65
66
13
67
[1,1'-Biphenyl]-4-carbonitrile (7p).
68
Biphenyl-4-carbaldehyde (7q).
69
4-Nitro-1,1'-biphenyl (7r).
2-[(1,1'-Biphenyl)-4-yl]acetic acid (7s).
3
2
3
70
71
1,3-Dimethyl-3-(4-methylbenzyl)indolin-2-one (9).
Conflicts of interest
There are no conflicts to declare.
4
7
.2. General procedure for the preparation of known compounds
.
Acknowledgements
To a solution of the aryl iodide or bromide (0.2 mmol) and the
corresponding boronic acid (0.2 mmol) in a 1:1 water:EtOH
mixture (2 mL), complex 4b (1 mg, 0.5 mol%) and KOH (11.5
mg, 0.4 mmol) were added and the resulting suspension was
stirred at 100 ºC (oil bath) for 12 h. Then ethanol was evaporated
We gratefully acknowledge financial support from the
Spanish Ministerio de Ciencia, Innovación y Universidades
(projects
CTQ2016-76782-P,
CTQ2016-81797-REDC
CTQ2016-81893REDT, and RED2018-102387-T) the Spanish
Ministerio de Economía, Industria y Competitividad, Agencia
Estatal de Investigación (AEI) and Fondo Europeo de Desarrollo
Regional (FEDER, EU) (projects CTQ2016-76782-P), the
Generalitat Valenciana (PROMETEOII/2014/017), USTO-MB
and the Universities of Mersin and Alicante. One of us (M.C.)
thanks USTO-MB for scientific leave.
(
under vacuo) and the aqueous solution extracted with ethyl
acetate (3x5 mL). The combined organic phases were dried
MgSO ) filtered and evaporated. The resulting crude material
(
4
was purified by flash chromatography (n-hexane:ethyl acetate).
For the recycling series, once the reaction finished, ethanol
was evaporated (under vacuo) and the water suspension extracted
with ethyl acetate (3x5 mL). The combined organic portions were
treated as above, whilst the aqueous suspension was combined
with another batch of the aryl iodide and boronic acid dissolved
(0.2 mmol each) in ethanol (1 mL).
5
6
4
4
4
4
2
4
3
3
-Methoxy-4'-methyl-1,1'-biphenyl (7a).
-Methoxy-4'-(trifluoromethyl)-1,1'-biphenyl (7b).
57
58
'-Methoxy-[1,1'-biphenyl]-4-carbaldehyde (7c).
59
-Fluoro-4'-methoxy-1,1'-biphenyl (7d).
-(Benzyloxy)-4'-methoxy-1,1'-biphenyl (7e).
60
61
-Methoxy-1,1'-biphenyl (7f).
-Methoxy-4'-methyl-1,1'-biphenyl (7g).
62
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7

HIGHLIGHTS
Resistant micellar palladium nanoparticles
Sustainable palladium-catalysed Suzuki-Miyaura coupling
Highly recoverable micellar palladium nanoparticles
Bromo/iodoarenes react with boronic acids using micellar palladium nanoparticles

Declaration of interests
☒
The authors declare that they have no known competing financial interests or personal relationships
that could have appeared to influence the work reported in this paper.
☐
The authors declare the following financial interests/personal relationships which may be considered
as potential competing interests: