Pd/tetraphosphine catalytic system for Cu-free Sonogashira reaction "on water"

Article abstract of DOI:10.1039/c3cy00831b

An efficient copper-free Sonogashira coupling reaction was performed on water at 100 °C with N,N,N′,N′-tetra(diphenylphosphinomethyl) pyridine-2,6-diamine (1) as a ligand, [Pd(η³-C₃H ₅)Cl]₂ as a catalyst precursor and K₃PO ₄ as a base. Both aryl and heteroaryl halides were successfully alkynylated in this system, and a high turnover number (TON) up to 860000 was obtained with a catalyst loading as low as 1 ppm.

Full text of DOI:10.1039/c3cy00831b

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Pd/tetraphosphine catalytic system for Cu-free
Sonogashira reaction “on water”†
Cite this: Catal. Sci. Technol., 2014,
4, 746
Rong Zhou,a Wei Wang,a Zhi-jie Jiang,a Hai-yan Fu,a Xue-li Zheng,a
b
a
a
*
Chun-chun Zhang, Hua Chen and Rui-xiang Li
Received 22nd October 2013,
Accepted 20th November 2013
An efficient copper-free Sonogashira coupling reaction was performed on water at 100 °C with N,N,N′,N′-
tetra(diphenylphosphinomethyl)pyridine-2,6-diamine (1) as a ligand, [Pd(η3-C3H5)Cl]2 as a catalyst precur-
sor and K3PO4 as a base. Both aryl and heteroaryl halides were successfully alkynylated in this system, and
a high turnover number (TON) up to 860 000 was obtained with a catalyst loading as low as 1 ppm.
DOI: 10.1039/c3cy00831b
www.rsc.org/catalysis
development of easily accessible and highly efficient
multidentate phosphines is highly desirable. We previously
Introduction
The palladium-catalyzed Sonogashira cross-coupling reaction
is one of the most useful methodologies in organic synthesis
between aryl halides and alkynes.1 The addition of copper is
beneficial for increasing the reactivity of the system. How-
ever, shortcomings have arisen from forming an alkyne
homocoupling by-product through a copper-mediated Hay–
Glaser reaction.2 To address this problem, some efficient
Cu-free catalytic systems have been developed in recent years.
Most of these reactions are carried out in the presence of
phosphine ligands.3 The bulky and electron-rich mono-
phosphines such as PtBu3 have proved to be very efficient in
the palladium catalyzed Cu-free system.4 However, their prac-
tical utility was limited by their high sensitivity to air. In past
decades, multidentate phosphines have emerged as an alter-
native to monodentate electron-rich phosphines in Cu-free
Sonogashira reactions. Two effective multidentate ligands are
cis,cis,cis,cis-1,2,3,4-tetrakis(diphenylphosphinomethyl) (Tedicyp)
developed by Santelli5 and 1,2-bis(diphenylphosphino)-1′-
(diisopropylphosphino)-4-tert-butylferrocene [Fc(P)2tBu(PiPr)]
developed by J.-C. Hierso,6 both ligands enabled the reaction
occur at an extremely low catalyst loading. For example, a
high TON of 2 800 000 was obtained in Pd-catalyzed
Sonogashira reactions in the presence of Tedicyp. And the
ligand Fc(P)2tBu(PiPr) associated [Pd(η3-C3H5)Cl]2 could also
afford a high TON around 250 000 in the coupling of
4-bromoacetophenone with phenylacetylene.7 However, a cop-
per salt was still required as a co-catalyst in these systems.
Furthermore, the long synthetic routes to these ligands and
their air-sensitivity might limit their applications. Thereby,
reported the synthesis and use of a tetraphosphine ligand
N,N,N′,N′-tetra(diphenylphosphinomethyl)-1,2-ethylenediamine
(2) in Heck,8 Suzuki9 and Sonogashira reactions.10 This conve-
niently obtained ligand showed excellent properties in these
catalytic reactions. Based on previous results, another
tetraphosphine ligand 1, using a similar synthesis strategy,
was synthesized. Compared with ligand 2, the molecular back-
bone of 1 is more rigid. The coordination mode of ligand 1
with palladium is assumed to be different from ligand 2. The
catalytic properties of [Pd(η3-C3H5)Cl]2/1 were evaluated in a
Sonogashira reaction.
On the other hand, water, compared to typical solvents,
such as DMF (N,N-dimethylformamide), DMA (N,N-dimethyl-
acetamide), DMSO (dimethyl sulfoxide), toluene, 1,4-dioxane
or amine-bases, has attracted increasing attention in recent
years, not only due to its environmental sustainability, but
also for the sake of selectivity and activity.11 Most commonly,
in order to use the superiority of water, reseachers have made
great efforts to improve the water solubility of the catalyst. In
spite of the problems associated with the lack of solubility of
organic substrates in water, recent work by Bhattacharya and
Sengupta11g has demonstrated the feasibility of conducting
Sonogashira couplings in pure water without the need for sol-
uble catalysts. These couplings are described as “on water”
reactions according to the definition coined by Sharpless.12
In their system, bromobenzene could be smoothly coupled
a Key Lab of Green Chemistry and Technology, Ministry of Education, Sichuan
University, Chengdu, China. E-mail: liruixiang@scu.edu.cn; Fax: +86 28 85412904
b Analytical &Testing Centre of College of Chemistry, Sichuan University, China
† Electronic supplementary information (ESI) available. See DOI: 10.1039/
c3cy00831b
with phenylacetylene resulting in
a
high yield of
diphenylacetylene (82%) with 0.5 mol% of Pd(PPh3)4 and 1
mol% CuI after only 30 min at 70 °C. Subsequently, Antoni
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Costa succeeded in applying “on water” conditions to the syn-
thesis of aryl propargylic amines via a Sonogashira coupling.13
In their work, the use of less than 0.2 mol% of Pd(PPh3)4 and
1.5 mol% CuI in the presence of diisopropylethylamine allows
the coupling to proceed at 95 °C yielding moderate to good
yields (40–85%) of mono-, bis-, and tri-aminoalkynylbenzene
derivatives. And the “on water” method has attracted interest
because of its potential in alkynylation reactions.
In their work, approximate kinetic models and transition state
theory suggested that the dramatic on-water acceleration is due
mainly to the ease with which free OH groups of interfacial
water molecules could form H bonds with H-bond-accepting
groups in the transition state compared with those in the reac-
tants. Meanwhile, James K. Beattie and co-workers16 explained
that a simple acid-catalysis mechanism was facilitated by the
strong adsorption of hydroxide ions at the oil–water interface.
They thought that water at the interface with the organic reac-
tants provided the conditions for protonation of the substrate,
driven by adsorption of the hydroxide ions, with the associated
deuterium isotope effect, leading to acid catalysis and the
enhanced rate.
To optimize conditions, the effect of various reaction
parameters (palladium precursor, base) on the outcome of
the coupling reaction of phenylacetylene and bromobenzene
was explored. It was found that [Pd(η3-C3H5)Cl]2 was the
most efficient Pd source (Table 1, entries 1–6). The lowest
yield was obtained with water-soluble Na2PdCl4 as a palla-
dium precursor. Furthermore, K3PO4 was the best choice
among the bases (Table 1, entries 6–13) and if it was replaced
by KOH, the reaction conditions seemed to benefit the forma-
tion of alkyne homocoupling by-product. Compared with
other well known simple ligands, ligand 1 was favourable for
improving the catalyst activity (Table 1, entries 14–18). Good
to excellent results were obtained when the reactions were
carried out on water with 0.05 mol% of [Pd(η3-C3H5)Cl]2/1 in
the presence of K3PO4 at 100 °C.
Results and discussion
In our previous work,10 the concentration of water has affected
the reaction and water excess has hindered the reaction, so the
influence of water on the reaction was investigated in detail.
Based on the reported results,1a the Sonogashira coupling of
bromobenzene (0.5 mmol) with phenylacetylene (0.6 mmol) in
the presence of [Pd(η3-C3H5)Cl]2 (0.05 mol%) and 1 (0.1 mol%)
in 3 mL solvent (DMA and water) was used as a model reaction.
As shown in Fig. 1, the addition of water was found to play a
crucial role in this reaction.
For the sake of comparison, the relationship between the
conversion and the addition of water was studied with 2 as
the ligand. For ligand 2, the results showed that an appropri-
ate quantity of water promoted the reaction while if the ratio
of water to 1,4-dioxane exceeded 1 : 2 the reaction would be
hindered, consistent with previous work,10 the conversion
showed a slight increase on water. To our surprise, ligand 1
didn't show the same trend of excess water hindering the
reaction. The cross-coupling rate was very slow in anhydrous
DMA, and only 10% GC yield was obtained. The conversion
increased to 54% when the ratio of water/DMA was increased
to 2. The coupling reaction afforded the product in 93% GC
yield when water was the only solvent. As observed experimen-
tally, the reaction in the “on water” system is intrinsically
accelerated. Similar rates have been observed by Greaney for
reactions run on water compared to neat reactions,14 but a
moderate yield (63%) was given under neat conditions in our
system. However the actual mechanism is not presently clear.
In 2007, Jung and Marcus15 proposed an alternative mecha-
nism to explain the phenomenon of the on water system.
A control experiment was performed for the coupling reac-
tion of 4-trifluoromethylbromobenzene and phenylacetylene
with 0.05 mol% [Pd(η3-C3H5)Cl]2 as the catalyst in the
Table 1 Effect of Pd-catalyst on the Sonogashira coupling of bromo-
benzene with phenylacetylenea
Entry
Pd source
Base
Yield (%)
1
2
3
4
5
6
7
8
PdCl2
Pd(OAc)2
Na2PdCl4
Pd(dba)2
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
NaHCO3
Na2CO3
K2CO3
NaOtBu
KOH
71
71
45
75
81
93
25
47
53
91
33
88
30
59b
35c
35d
24e
17f
Pd(COD)Cl2
[Pd(η3-C3H5)Cl]2
[Pd(η3-C3H5)Cl]2
[Pd(η3-C3H5)Cl]2
[Pd(η3-C3H5)Cl]2
[Pd(η3-C3H5)Cl]2
[Pd(η3-C3H5)Cl]2
[Pd(η3-C3H5)Cl]2
[Pd(η3-C3H5)Cl]2
[Pd(η3-C3H5)Cl]2
[Pd(η3-C3H5)Cl]2
[Pd(η3-C3H5)Cl]2
[Pd(η3-C3H5)Cl]2
[Pd(η3-C3H5)Cl]2
9
10
11
12
13
14
15
16
17
18
Et3N
Pyridine
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
a
Reaction conditions: 0.5 mmol PhBr, 0.6 mmol phenylacetylene,
H2O 3 mL, base 1 mmol, 2.5 × 10−4 mmol [Pd], 5 × 10−4 mmol
ligand 1, 100 °C, 5 h, GC yield. Ligand 2. GC yield. PPh3, GC
yield. Tris(3-sulfonatophenyl)phosphine, sodium salt (TPPTS), GC
b
c
d
e
yield.
1,2-Bis(diphenylphosphino)ethane (dppe), GC yield.
f
Fig. 1 Conversion dependence on the addition of water after 5 hours.
1,4-Bis(diphenylphosphino)butane (dppb), GC yield.
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Table 2 [Pd(η3-C3H5)Cl]2/1-catalyzed Sonogashira coupling reaction
of aryl bromide with phenylacetylenea
Table 2 (continued)
Entry Ar–Br
S/C
Time/h Product Yield (%)
Entry Ar–Br
S/C
Time/h Product Yield (%)
22
1000
20
24
45
1
1000
5
3
88
2
1000
3
4
92
23
1000
20
25
31
3
4
5
1000
1000
1000
3
6
6
5
6
7
91
94
91
a
Conditions: catalyst [Pd(η3-C3H5)Cl]2/1 = 1/2, aryl bromides 0.5 mmol,
phenylacetylene 0.6 mmol, K3PO4 1 mmol, H2O 3 mL, 100 °C, under
argon, isolated yields. b Phosphine-free. c GC yield.
6
7
1000
20
8
9
57
absence of ligand 1 (Table 2, entry 7). Only a low 58% yield
of compound 9 was obtained after 3 h. With the addition of
0.1 mol% tetraphosphine 1, the yield significantly increased
to 95%. It is evident that ligand 1 was favorable for improving
the catalyst activity. Then, the limitations of the catalyst were
tested in this [Pd(η3-C3H5)Cl]2/1 catalytic system (Scheme 1).
As shown in Table 2, various aryl bromides, regardless of their
electron-rich or electron-poor characteristics, could couple
with phenylacetylene efficiently in the presence of 0.05 mol%
[Pd(η3-C3H5)Cl]2 (Table 2, entries 2–5, 7–19). In the literature,5
a high palladium loading is usually employed for the electron-
rich aryl bromides such as 2-bromobenzene, 2-bromoanisole
and 2-bromo-p-xylene. We were pleased to find that very high
yields (85–93%) were obtained in our system, whereby only
0.05 mol% [Pd(η3-C3H5)Cl]2 was used (Table 2, entries 13–14, 19).
As expected, 2-bromo-m-xylene, 1-bromo-2-methylnaphthalene
and 1-bromo-2-methoxynaphthalene gave 17, 24 and 25 in lower
yields of 45%, 31% and 59%, respectively due to hindrance
(Table 2, entries 15, 22–23). In this case, a good yield still can be
achievable by increasing the Pd loading. For example, the highly
sterically congested 2-bromo-m-xylene was transformed into 17
in 93% isolated yield when the palladium loading was increased
to 1 mol% (Table 2, entry 15). The system also exhibited good
functional group tolerance. The aryl bromides bearing –CF3,
–NO2, –CN, –CHO or –COCH3 group all reacted smoothly and
produced desired compounds 4–7, 9–12 in good to excellent
yields (71–95%, Table 2, entries 2–5, 7–10). It should be noted
that only 57% of 2-bromobenzonitrile was transformed into prod-
uct 8, this relatively lower activity is in a good agreement with
the reported results (Table 2, entry 6) .
1000
1000
10 000
1 000 000 92
3
3
24
95
58b
99
86
8
1000
3
10
92
9
1000
1000
6
6
11
12
75
71
10
11
12
1000
1000
20
20
13
14
83
95
13
14
15
1000
1000
20
20
20
15
16
17
90
93
1000
100
59c
93
16
17
18
1000
1000
1000
20
20
20
18
19
20
90
83
91
Subsequently, several heteroarylbromides including
3-bromoquinoline,
2-bromopyridine,
3-bromopyridine,
5-bromopyrimidine, 2-bromothiazole and 2-bromothiophene
19
20
21
1000
1000
1000
20
20
20
21
22
23
85
53
54
Scheme 1
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were also investigated on water. According to the literature,17
the 2-bromopyridine should be more susceptible to oxidative
addition to palladium than 3-bromopyridine because the
C–Br bond is closer in electronegativity to the nitrogen atom.
However, whichever of 2-bromopyridine or 3-bromopyridine was
used as a substrate in our system both gave almost the same
conversion (Table 3 entries 2, 3). To test the efficiency and lon-
gevity of the catalyst, as little as 0.005 mol% [Pd(η3-C3H5)Cl]2
was used in Sonogashira coupling of 2-bromopyridine. The
expected coupling product 28 was obtained in 91% yield after
72 h, the TON was up to 9100 (Table 3 entry 3), which is compa-
rable with the TON value achieved by Tedicyp in 20 h for
the same substrate (8000).18 These results indicated that the
combination of [Pd(η3-C3H5)Cl]2 with 1 proved a robust and
stable catalyst. This can be attributed to its good stabilizing
effect upon active palladium species. Heteroaryl bromides
contain N or S atoms, which have the potential to bind to
palladium, thus poisoning the catalyst. Nevertheless, they were
all proved to be suitable substrates in this system. Good to
excellent yields of the desired coupling products (in the range
of 87–99%) were obtained for these heteroaryl bromides except
for 2-bromothiophene (Table 3). Under similar conditions, the
reaction of 2-bromothiophene with phenylacetylene only pro-
vided a 34% GC yield (Table 3 entry 6), possibly due to the
π-electron properties of the thiophenyl groups.18 It was also
noted that the attempt to carry out the reaction in DMA instead
of water led to a significant decrease in the yield (Table 3
entries 1, 4, 5). Again, the positive effect of carrying out the reac-
tion “on water” was testified.
with their (hetero) aryl bromides. Despite this, the electron-poor
aryl chlorides such as 3- or 4-trifluoromethylchlorobenzene,
4-chloronitrobenzene, 4-chloroacetophenone and 2-chloroquinoline
were still transformed into products 5, 9–11, 33 in moderate
yields of 44–69% (Table 4 entries 2–8), while the electron-rich
4-chloroanisole, and 3-chloropyridine afforded the corre-
sponding coupling products in very low GC yields of 27%
and 12%, respectively. The above results revealed that it was
possible to gain activity for the relatively inert chloride sub-
strates by tuning their electronic properties. Indeed, when the
more electron-deficient 4-trifluoromethyl-2-nitrochlorobenzene
was employed, the product 32 was produced in 97% yield.
Even with as low as 1.0 × 10−4 mol% of palladium, a moderate
yield of 56% was still achieved, with up to 560 000 TON,
which is much higher than the best value reported in the litera-
ture (9100).19
Finally, to our delight, the catalytic system was also effec-
tive towards the coupling of bromobenzene and various
alkynes, giving the corresponding products in moderate to
excellent yields with a low catalyst loading of 0.1 mol%
(Table 5 entries 1–6). For example, 2, or 3-pyridylacetylene
underwent the Sonogashira coupling with bromobenzene
to afford the desired products in 64% and 97% yields,
respectively (Table 5 entries 1–2). Aryl alkynes whether
electron-poor (1-ethynyl-4-fluorobenzene) or electron-rich
(3, or 4-ethynylanisole), reacted smoothly with bromobenzene
to provide the corresponding cross-coupling products (Table 5
Furthermore, the low-cost but less-active (hetero) aryl chlo-
rides were examined in the “on water” conditions. As expected,
much lower yields of product were observed in comparison
Table 4 [Pd(η3-C3H5)Cl]2/1-catalyzed Sonogashira coupling reaction
of aryl chloride with phenylacetylenea
Entry Ar–Cl
S/C
Time (h) Product Yield (%)
Table 3 [Pd(η3-C3H5)Cl]2/1 catalyzed Sonogashira coupling reaction
1
1000
10 000
100 000
20
20
40
32
96
99b
97b
56b
of heteroaryl bromide with phenylacetylenea
1 000 000 92
Entry
1
HetAr–Br
S/C
Time (h)
Product
Yield (%)
2
3
4
5
6
7
1000
1000
1000
1000
1000
1000
1000
20
20
20
20
20
20
20
9
69
1000
1000
6
6
26
94
40b
10
11
5
65
2
3
1000
3
2
1
3
2
1
20
72
27
28
96
84c
65c
96
50b
52b
27b
44
1000
1000
1000
5000
10 000
85c
65c
99c
91c
19
33
27
4
5
1000
1000
20
20
29
30
31
87
76b
1000
1000
20
20
89
Traceb
8
12b
6
1000
20
34
a
a
Conditions: catalyst [Pd(η3-C3H5)Cl]2/1 = 1/2, heterocyclic bromides
0.5 mmol, phenylacetylene 0.6 mmol, K3PO4 1 mmol, H2O 3 mL, 100 °C,
under argon, isolated yields. b DMA as solvent, GC yields. c GC yields.
Conditions: catalyst [Pd(η3-C3H5)Cl]2/1 = 1/2, aryl and aryl chloride
0.5 mmol, phenylacetylene 0.6 mmol, K3PO4 1 mmol, H2O 3 mL,
100 °C, under argon, isolated yields. b GC yields.
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Table 5 [Pd(η3-C3H5)Cl]2/1-catalyzed Sonogashira coupling reaction
appeared to be different in our system. It could be that the
closer nitrogen atom of 2-pyridylacetylene coordinates more
easily with Pd in the form of the complex 36. This should be a
stable intermediate and which slows down the next step.
4-Ethynylanisole bearing an electron donating group should
show a slow reaction rate according to Carmen Nájera's mech-
anism, but it showed the highest rate in our system.
of bromobenzene with alkynea
Entry
1
Alkyne
Time (h)
20
Product
Yield (%)
64
28
2
3
4
5
20
6
27
34
19
20
35
97
85
79
69
88
Conclusions
In conclusion, the use of the tetradentate ligand 1 associated with
[Pd(η3-C3H5)Cl]2 provides a convenient catalyst for the coupling
of aryl halides with alkynes on water. A variety of aryl halides,
even heteroaryl halides were reacted with phenylacetylene in good
to excellent yields at low catalyst loadings.
6
6
6
20
Experimental
General remarks
a
Conditions: catalyst [Pd(η3-C3H5)Cl]2/1 = 1/2, bromobenzene 0.5 mmol,
alkyne 0.6 mmol, S/C = 1000, K3PO4 1 mmol, H2O 3 mL, 100 °C, under
argon, isolated yields.
All chemicals were purchased from commercial suppliers.
Except for some liquid reagents being sensitive to light and
moisture (DMA, toluene, methanol and alcohol) which were
redistilled prior to use, there is no further treatment. 1H NMR,
13C NMR and 31P NMR spectra were recorded on a Bruker AV
II-400 MHz. Mass spectroscopy data of the products were col-
lected using an MS-ESI instrument. All products were isolated
by short chromatography on silica gel (300–400 mesh) using
petroleum ether (60–90 °C), unless otherwise noted. Com-
pounds described in the literature were characterized by 1H
NMR spectroscopy and compared to the reported data.
Synthesis of N,N,N′,N′-tetra(diphenylphosphinomethyl)pyridine-
2,6-diamine 1
A solution of pyridine-2,6-diamine (110 mg, 1 mmol) in 5 mL
alcohol and 8 mL triethylamine was added slowly to a stirred
suspension of [Ph2P(CH2OH)2]Cl21 (1.4 g, 5 mmol) in 15 mL
toluene and 10 mL alcohol under nitrogen, then the mixture
was refluxed for 40 h. At the end of the reaction, the mixture
solution was washed with degassed water and the organic
layer was dried over MgSO4. The organic layer was filtered
and the solvent was removed under vacuum. The residue was
recrystallized in 1.5 mL dichloromethane and 15 mL metha-
nol. After the resulting crude product was refluxed in 10 mL
methanol for 1 h and slowly cooled to room temperature, a
light yellow solid product was obtained. Yield: 0.76 g (84%).
Compared with the literature,22 we used a new and easier
method to synthesize this ligand, and got a higher productiv-
Fig. 2 Relationship between conversion and time, obtained by GC, for
the Sonogashira reaction with the substituted alkynes as in Table 5.
1
ity. The product was characterized by H NMR and 31P NMR,
entries 3–5). The reaction mechanism of the Pd-catalyzed
Cu-free Sonogashira reaction was discussed by means of den-
sity functional theory (DFT).20 The progress of the reaction is
favored depending on the electronic nature of the substituted
group on the alkyne. The more acidic the proton of the alkyne
is, the higher reaction rate is. In our system, as shown in
Fig. 2, the reactivity of the substrates is almost consistent with
this suggestion, but 2-pyridylacetylene and 4-ethynylanisole
and the results were in accordance with the reported results.22
1H NMR (400 MHz, DMSO, 25 °C): δ = 7.15–7.35 (m, 41H, Ph,
3
2
Py4), 5.88 (d, JH,H = 8.1 Hz, 2H, Py3,5), 4.14 (d, JH,H = 3.4 Hz,
8H, NCH2P) ppm. 13C NMR (101 MHz, CDCl3): δ = 155.49
(s, Py2,6), 137.93 (S, Py4), 137.40 (d, J = 15.5 Hz, Ar1), 132.89
(d, J = 19.3 Hz, Ar2,6), 128.38–127.78 (m, Ar3–5), 95.08 (s, Py3,5),
49.75 (s, NCH2P) ppm. 31P NMR (162 MHz, CDCl3) δ = −24.62 ppm.
MS (ESI) [C58H52N2P4]: m/z (M + H)+: 902.
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K3PO4 (212 mg, 1 mmol), aryl halides (0.5 mmol), terminal
alkynes (0.6 mmol) and degassed H2O (3 mL) were added suc-
cessively into a dried Schlenk tube with a magnetic bar under
nitrogen. Then a DMA (N,N-dimethylacetamide 0.05 mL) solu-
tion of tetraphosphine 1 (0.0005 mmol) and [Pd(η3-C3H5)Cl]2
(0.00025 mmol), which was reacted at 100 °C for 30 min prior
to use, were added into the mixture. The reaction was
performed at 100 °C. At the end of reaction, the solution was
cooled to room temperature and was extracted with ethyl ace-
tate (3 × 3 mL). The organic layer was dried over MgSO4, fil-
tered and purified with silica gel chromatography (petroleum
ether) to give the corresponding product.
Acknowledgements
This project was supported by the National Natural Science
Foundation of China (no. 21202104).
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