The light “on-off” stepwise one-pot method for 3,4-diaryl coumarins with potential AIE properties

Article abstract of DOI:10.1016/j.tet.2020.131677

An efficient one-pot method involving visible-light-induced cyclization and Pd-catalyzed Suzuki cross-coupling processes to construct 3,4-diaryl coumarins is developed. Under the light on-off optimized conditions, a series of alkynoates and aryl boronic a

Full text of DOI:10.1016/j.tet.2020.131677

Journal Pre-proof
The light “on-off” stepwise one-pot method for 3,4-diaryl coumarins with potential AIE
properties
Huijuan Zhang, Qingrui Li, Yunnian Yin, Jung Keun Kim, Mengmeng Huang, Yabo Li,
Yangjie Wu
PII:
S0040-4020(20)30890-5
https://doi.org/10.1016/j.tet.2020.131677
TET 131677
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 1 September 2020
Revised Date: 8 October 2020
Accepted Date: 12 October 2020
Please cite this article as: Zhang H, Li Q, Yin Y, Kim JK, Huang M, Li Y, Wu Y, The light “on-off”
stepwise one-pot method for 3,4-diaryl coumarins with potential AIE properties, Tetrahedron, https://
doi.org/10.1016/j.tet.2020.131677.
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Graphical
Abstract
The light “on-off” stepwise one-pot method
for 3,4-diaryl coumarins with potential AIE
properties
Huijuan Zhang,# Qingrui Li,# Yunnian Yin, Jung Keun Kim, Mengmeng Huang, Yabo Li and Yangjie Wu
College of Chemistry, Henan Key Laboratory of Chemical Biology and Organic Chemistry, Key Laboratory of
Applied Chemistry of Henan Universities, Zhengzhou University, Zhengzhou 450052, P.R. China.

Graphical Abstract
The light “on-off” stepwise one-pot method
for 3,4-diaryl coumarins with potential AIE
properties
Huijuan Zhang,# Qingrui Li,# Yunnian Yin, Jung Keun Kim, Mengmeng Huang, Yabo Li and Yangjie Wu
College of Chemistry, Henan Key Laboratory of Chemical Biology and Organic Chemistry, Key Laboratory of
Applied Chemistry of Henan Universities, Zhengzhou University, Zhengzhou 450052, P.R. China.

1
Tetrahedron
journal homepage: www.elsevier.com
The light “on-off” stepwise one-pot method for 3,4-diaryl coumarins with potential
AIE properties
Huijuan Zhang,# Qingrui Li,# Yunnian Yin, Jung Keun Kim, Mengmeng Huang, Yabo Li and Yangjie Wu
College of Chemistry, Henan Key Laboratory of Chemical Biology and Organic Chemistry, Key Laboratory of Applied Chemistry of Henan Universities,
Zhengzhou University, Zhengzhou 450052, P.R. China.
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
An efficient one-pot method involving visible-light-induced cyclization and Pd-
catalyzed Suzuki cross-coupling processes to construct 3,4-diaryl coumarins is
developed. Under the light on-off optimized conditions, a series of alkynoates and aryl
boronic acids were well suitable for this catalytic system, and were successfully
transformed into the corresponding products in moderate to high yields. Meanwhile,
this synthetic system has good applicability for other Pd-catalyzed coupling reactions,
such as Heck and Sonogashira reactions. 3,4,7-Triphenyl coumarin could be produced
not only via the Suzuki reaction of 3-bromo-4,7-diphenyl with PhB(OH)2, but also via
the Pd-catalyzed C-H activation. Based on the spectral studies, we found that some of
the 3,4-diaryl coumarins may have AIE activities. This work provides a straight
forward way to create valuable multi-substituted coumarins with potential AIE
properties.
Available online
Keywords:
one-pot synthesis
light on-off
3,4-diaryl coumarin
aryl alkynoate
AIE activity
2009 Elsevier Ltd. All rights reserved
.
———
Corresponding author. Tel.: +86-371-67767993; e-mail: wyj@zzu.edu.cn (Yangjie Wu).
Corresponding author. Tel.: +86-371-67767993; e-mail: ybli@zzu.edu.cn (Yabo Li).
#These authors contributed equally to this work.

2
Tetrahedron
1. Introduction
amount of Py1 (Table 1, entries 16-18). The molecular structure
of product 4a was determined by single crystal X-ray diffraction
(Table S1 in ESI).
Coumarins as one of the typical heterocyclic compounds are
present in many natural products, [1] pharmaceuticals [2] and
organic synthetic intermediates. [3] Coumarin derivatives not
only have various potential biological activities, [4] but also have
been applied in the field of luminescent materials. [5] Recently,
we found that 3-arylvinyl-4-aryl-coumarins and 3-arylacetylene-
4-aryl-coumarins have fascinating optical properties. [6,7]
Especially, the excellent aggregation-induced emission (AIE)
optical properties of 3-arylacetylene coumarins allows us to study
the optical activity of 3,4-diaryl coumarins. [8] Up to now, 3,4-
diaryl coumarins are synthesized by oxidative cyclization
reaction, [8] Knoevenagel reaction [9] and transition metal-
catalyzed coupling reactions (Scheme 1). [10] On the basis of the
above literature investigations, we found that the existing
synthetic methods need either expensive precursors or multi-step
synthesis. In order to solve these shortcomings, the stepwise one-
pot synthetic strategy is considered as the effective pathway.
Comparing to the multi-step synthesis, economic and
environment-friendly one-pot synthetic strategy has been
regarded as a promising way in organic chemistry, which
increases product yield without the separation and purification of
intermediate compounds. Recently, the stepwise one-pot
synthetic method with the combination of various approaches
have been developed to expand the application of this strategy in
organic synthesis. [6,7,11,12] Inspired by the previous work, the
one-pot synthesis with multi-step procedures involving
photocatalysis [13] and thermocatalysis processes will be a good
way to synthesize 3,4-diaryl coumarins. Herein, we demonstrate
a mild stepwise one-pot method involving visible-light-induced
cyclization and Pd-catalyzed Suzuki reaction to synthesize 3,4-
diaryl coumarins from alkynoates, and their AIE activity have
been preliminary studied.
Table 1. Optimization of the one-pot reaction conditions.a
Entry
1
[Pd]
PdCl2
Pd(OAc)2
Py1
Base 2
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
Na2CO3
K3PO4
CsOAc
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
T/oC
100
100
100
100
100
100
100
100
100
100
100
80
Yield/%
59
2
68
3
70
4
Q1
62
5
Py4
53
6
Py6
66
7b
Py1
67
8c
9c
Py1
78
Py1
53
10c
11c
12c
13c
14c, d
15c, e
16c, f
17c, g
18c, g, h
Py1
63
Py1
57
Py1
81
Py1
60
21
Py1
80
77
Py1
80
65
Py1
80
76
Py1
80
80
Py1
80
80
aReaction conditions: 1) 1a (0.2 mmol), 2 (3 equiv.), [Ir(ppy)2(dtbbpy)PF6] (5
mol %), CsOAc (2 equiv.), DMF (2 mL), 3 W blue LED (λ = 450-465 nm),
room temperature, under air atmosphere for 14 h; 2) 3a (2 equiv.), [Pd] (5
mol %), base 2 (4 equiv.), H2O (0.2 mL), under air atmosphere for 12 h at 100
oC, isolated yield.
bBase 2 (1 equiv.).
cBase 2 (2 equiv.).
dH2O (0.4 mL).
eH2O (0.1 mL).
fTime 2: 6 h.
gTime 2: 8 h.
hPy1 (2 mol %).
Scheme 1. Synthetic methods of 3,4-diaryl coumarins.
On the basis of the optimal conditions, the scope of the
substrates was investigated (Scheme 2). Generally, various aryl
alkynates and aryl boronic acids were well tolerated in the
stepwise one-pot transformation (4a-v). The activity of aryl
alkynoates possessing the electron-donating group on the para-
position of the phenoxy ring were higher than that with the
electron-withdrawing group (4a-i). 3,5-Dimethylphenyl 3-
phenylpropiolate (1j) and naphthalen-2-yl 3-phenylpropiolate
(1k) could be also transformed into their corresponding products
in good yield. It was worth to note that 4,7-diphenyl-2H-
chromen-2-one (4h1) were selectively produced in good yield
under the optimal conditions. It might be afforded by the
debromination of 3-bromocoumarin. In the presence of excess
phenylboronic acid (3a), the yield of 3,4,7-triphenyl coumarin
(4h2) was up to 68%, meanwhile, a small amount of 4,7-diphenyl
coumarin (4h1) was isolated. Both electron-donating and
electron-withdrawing phenylboronic acids could participate in
this one-pot reaction to give products (4n-s) in moderate to good
yields. The poor yields were obtained with the steric hindrance of
2. Results and discussion
Based on the previous work, [14] the visible-light-induced
reaction of p-tolyl 3-phenylpropiolate (1a) and diethyl
bromomalonate (2) was chosen to construct the important
intermediate 3-bromocoumarin (5a). The optimization of Suzuki
reaction conditions between phenylboronic acid (3a) and 3-
bromocoumarin (5a) to produce the target product 4a was our
main investigation (Table 1). The cyclopalladium(II) complex
with N,O-ligand Py1 [15] was better choice for the one-pot
synthesis (Table 1, entries 1-6). The amount of K2CO3 which was
used in the Suzuki process could be reduced to 2 equivalents
(Table 1, entries 7-8). Other tested bases such as Na2CO3, K3PO4
and CsOAc, gave the comparatively poor results (Table 1, entries
9-11). The better result was obtained when the Suzuki reaction
temperature was reduced to 80 °C (Table 1, entries 12 and 13).
Changing the amount of water, the product yield was not
improved (Table 1, entries 14 and 15). The efficiency did not
decrease due to the shortened reaction time or reducing the

3
ortho-substituted aryl boronic acids (4t and 4u). 2-Naphthalene
boronic acid was well tolerated in this one-pot reaction to afford
the corresponding product (4v) in 51% yield.
(Scheme 4, b). Although the photolysis of intermediate 5a was
not detected during our previous works under the standard
conditions for the model reaction, [6] the debromination product
4h1 was observed for the synthesis of compound 4h2 (Scheme 2).
It might be related to more active intermediate 5h. Based on our
investigation, it was found that the debromination product 4h1
could be transformed into 4h2 via the Pd-catalyzed C-H
activation (Scheme 4, c). The results obtained will further
broaden the research on N,O-ligand palladacycle catalysts.
[15,16]
Scheme 4. Control experiments for the one-pot reaction.
Based on the above results and the previous studies, [10,14] a
possible mechanism was proposed (Scheme 5). The investigated
light on-off synthetic method proceeds via the photocatalytic and
thermocatalytic processes. After the photocatalytic cycle studied
by our previous work, [6,14c] the main intermediate 3-
bromicoumarins 5 undergoes sequential Pd-mediated oxidative
addition and reduction elimination reactions to give 3,4-diaryl
coumarins 4. In addition, more active intermediate 5h could
proceed debromination to afford compound 4h1. The product 4h2
might be isolated via two pathways: 1) the Pd-catalyzed C-H
activation between compound 4h1 and PhB(OH)2; 2) the Suzuki
reaction of intermediate 5h with PhB(OH)2.
Scheme 2. Scope of the one-pot reaction.a
aReaction conditions: 1a (0.2 mmol), 2 (3 equiv.), [Ir(ppy)2(dtbbpy)PF6] (5
mol %), CsOAc (2 equiv.), DMF (2 mL), 3 W blue LED (λ = 450-465 nm),
room temperature, under air atmosphere for 14 h; then 3 (2 equiv.), Py1 (2
mol %), K2CO3 (2 equiv.) and H2O (0.2 mL) were added under air at 80 °C
for 8 h. Isolated yield.
bPhB(OH)2 (6 equiv.).
Furthermore, the two-step one-pot catalytic system could be
also applied to construct 3-styryl coumarin (7) and 3-
phenylacetylene coumarin (9) in moderate yields without any
other optimization (Scheme 3). We believe that the one-pot
synthetic method may have a significantly broader application in
the synthesis of valuable multi-substituted coumarins.
Scheme 5. Possible pathway for the light on-off one-pot transformation.
Considering the outstanding photoluminescence property of
coumarin derivatives, AIE activity of three synthesized
coumarins 4a, 4h1 and 4h2 have been preliminary studied (Figure
1 and figure S1 in ESI). To our delight, all the three compounds
could emit different intensities of blue to blue-green fluorescence
under 365 nm UV light in solid-state (Figure 1, a and b). This
phenomenon indicates that these coumarin derivatives may have
AIE-active. Then, the absorption and emission properties of the
three compounds in pure THF and THF/H2O mixtures were
measured (Figure 1, c-h and Figures S1 in ESI). All compounds
exhibit weak fluorescence with different intensities in pure THF
Scheme 3. The extended experiments of the one-pot reaction.
To get insight into the reaction mechanism, several control
experiments were studied (Scheme 4). The result of the reaction
between 3-bromocoumarin (5a) and phenyl boronic acid (3a)
indicated that the compound 5a might be the main intermediate
for the two-step one-pot transformation (Scheme 4, a). When the
three starting materials were added in the first step, the yield of
the target compound was obviously reduced, which proves the
two-step one-pot reaction should be carried out step by step

4
Tetrahedron
solution, peaked at around 441, 421 and 443 nm, respectively.
for the catalytic system. A series of 3,4-diaryl coumarins were
obtained in moderate to high yields under the stepwise
conditions. The studied light “on-off” catalytic approach
proceeds via the photocatalysis and thermocatalytic processes. 3-
Bromocoumarins might be the main intermediates for this
transformation. In addition, this reaction system has good
applicability for other Pd-catalyzed coupling reactions, such as
Heck and Sonogashira reactions. It was found that more active
intermediate 3-bromo-4,7-diphenyl coumarin could proceed both
of the Suzuki coupling reaction and Pd-catalyzed C-H activation.
Based on the spectral studies, we found that some of the 3,4-
diaryl coumarins may have AIE activities. The investigation of
the detailed AIE mechanism of these multi-substituted coumarins
is under way in our laboratory.
With the increase of water fraction in the mixed system, the
fluorescence intensity of compounds 4a and 4h2 increased
slowly, and gradually showed bright blue emission; when the
water fraction increased to 90%, they exhibited 12 and 18-fold
enhancement in fluorescence intensity compared to that in pure
THF, respectively. However, different from compounds 4a and
4h2, the fluorescence intensity of 4h1 increased very slowly with
the increase of water fraction, almost no fluorescence was
emitted. These results preliminary indicates that some of the
synthesized 3,4-diaryl coumarins have AIE-active. The
investigation of the detailed AIE mechanism of the synthesized
3,4-diarylcoumarins is under way in our laboratory.
4. Experimental section
4.1. General information
All reactions were performed under air atmosphere using a
quartz tube. Solvents were dried by standard methods before they
were used. Silica gel was purchased from Qing Dao Hai Yang
Chemical Industry Co., Ltd. All reactions were carried out with a
photoreactor (Serial No: PEA12) which was purchased from
LUOYANG
JINFENG
ELECTROMECHANICAL
EQUIPMENT Co., Ltd. The LCD digital hotplate magnetic
stirrer MS-H-Pro+ was purchased from Dragon Laboratory
Instruments Limited. 1H NMR and 13C NMR spectra were
recorded on 400 and 100 MHz NMR instruments using CDCl3 as
the solvent and TMS as the internal standard. 19F NMR spectra
were recorded at 376.5 MHz on Bruker DPX-400, the chemical
shifts δ are reported relative to CFCl3 (δ = 0 ppm) as the internal
standard. The multiplicity of signals is designated by the
following abbreviations: s (singlet), d (doublet), t (triplet), q
(quartet), m (multiplet), dd = doublet of doublet. High resolution
mass spectra (HRMS) were obtained on an Agilent LC-MSD-
Trap-XCT spectrometer with micromass MS software using
electrospray ionization (ESI). UV/vis absorption spectra were
measured by SP-1900 ultraviolet-visible spectrophotometer. The
fluorescence emission spectra were recorded using a F-4500 FL
spectrophotometer. The melting point data of synthesized product
is derived from XT4A type melting point. The measurement of
the detector is unrevised. The X-ray single crystal structure is
determined by the Oxford Diffraction Xcalibur CCD single
crystal diffractometer.
21
fw (vol %)
200
0
60
70
80
90
150
100
50
14
7
0
400
0
450
500
550
600
650
0
20
Water fraction (vol %)
dc
40
60
80
100
Wavelength/nm
(
)
(c)
21
14
7
fw (vol %)
320
240
160
80
0
60
70
80
90
0
0
400
450
500
Wavelength/nm
(e)
550
600
0
20
40
60
80
100
Water fraction (vol %)
(f)
21
14
7
fw (vol %)
1600
1200
800
400
0
0
4.2. General procedure for the synthesis of compounds 4a-v
60
70
80
90
To a reaction tube equipped with a magnetic stir bar was added
phenyl 3-phenylpropiolate (0.2 mmol), [Ir(ppy)2(dtbbpy)PF6]
(0.0092 g, 5 mol %, 0.05 equiv.) and cesium acetate (0.0768 g,
0.4 mmol,
2
equiv.). Under air atmosphere, diethyl
bromomalonate (108 µL, 0.6 mmol, 3 equiv.) and DMF (2 mL)
were added. The resulting mixture was stirred under 3 W blue
LED (λ = 450-465 nm) at room temperature for 14 hours. Then
Py1 (0.0033 g, 2 mol %, 0.02 equiv.), phenylboronic acid (0.4
mmol, 2 equiv.) and potassium carbonate (0.0558 g, 0.4 mmol, 2
equiv.) were added. The resulting mixture was heated at 80 °C
for 8 hours. The solvent was removed under vacuum, and the
residue was purified by flash chromatography on silica gel
(eluent: dichloromethane or petroleum ether/ethyl acetate = 9/1)
to give the desired product 4.
0
400
450
500
550
600
650
0
20
40
60
80
100
Wavelength/nm
Water fraction (vol %)
(g)
(h)
Figure 1. (a) Photos of solid powders and on the water fractions in THF
solutions of compounds 4a, 4h1 and 4h2 under natural light and (b) 365 nm
UV light. (c) FL spectra changes of 4a, (e) 4h1 and (g) 4h2 depending on the
water fractions (0% and 60%-90%) in THF solutions. (d) Plot of relative PL
intensity (I/I0) versus the composition of THF/H2O mixture of 4a, (f) 4h1 and
(h) 4h2, where I0 = PL intensity in pure THF solution. Inset: photographs of
4a, 4h1 and 4h2 in THF/H2O mixtures with different water fractions taken
under irradiation of 365 nm UV light.
4.2.1. 7-methyl-3,4-diphenyl-2H-chromen-2-one (4a). [17]
3. Conclusions
Yellow solid (50.1 mg, 80%). m. p. 244.1-244.7 °C (lit. 243
°C). 1H NMR (400 MHz, CDCl3): δ = 7.28-7.27 (m, 3H), 7.22 (s,
1H), 7.16-7.08 (m, 8H), 6.99-6.97 (m, 1H), 2.44 (s, 3H). 13C
NMR (100 MHz, CDCl3): δ = 161.4, 153.2, 151.5, 142.6, 134.5,
In summary, an efficient stepwise one-pot method to construct
3,4-diaryl coumarins using aryl alkynoates as the starting
materials was developed. The high substrate tolerance was found

5
133.9, 130.5, 129.2, 128.2, 128.1, 127.6, 127.4, 127.3, 125.7,
125.2, 118.0, 116.8, 21.5. HRMS (ESI) calcd. for C22H17O2
(M+H)+: 313.1223; found: 313.1220.
4H), 7.51-7.46 (m, 5H), 7.44-7.41 (m, 1H), 6.38 (s, 1H). 13C
NMR (100 MHz, CDCl3): δ = 160.9, 155.5, 154.6, 145.0, 139.0,
135.2, 129.7, 129.1, 128.9, 128.6, 128.4, 127.3, 127.2, 123.0,
117.9, 115.4, 114.8. HRMS (ESI) calcd. for C21H15O2 (M+H)+:
299.1067; found: 299.1070.
4.2.2. 7-(tert-butyl)-3,4-diphenyl-2H-chromen-2-one (4b).
1
Light yellow solid (51.0 mg, 72%). m. p. 137.9-138.3 °C. H
4.2.9. 3,4,7-triphenyl-2H-chromen-2-one (4h2).
NMR (400 MHz, CDCl3): δ = 7.45-7.44 (d, J = 1.76 Hz, 1H),
7.30-7.29 (m, 3H), 7.24-7.21 (m, 1H), 7.18-7.16 (m, 3H), 7.14-
7.10 (m, 5H), 1.36 (s, 9H). 13C NMR (100 MHz, CDCl3): δ =
161.6, 156.0, 153.2, 151.5, 134.7, 134.0, 130.6, 129.3, 128.2,
128.1, 127.7, 127.5, 127.3, 126.0, 121.6, 118.0, 113.5, 35.1, 31.0.
HRMS (ESI) calcd. for C25H23O2 (M+H)+: 355.1693; found:
355.1696.
1
Yellow solid (51.3 mg, 68%). m. p. 187.3-187.9 °C. H NMR
(400 MHz, CDCl3): δ = 7.64-7.62 (m, 3H), 7.50-7.46 (m, 2H),
7.43-7.39 (m, 2H), 7.32-7.28 (m, 4H), 7.21-7.14 (m, 7H). 13C
NMR (100 MHz, CDCl3): δ = 161.3, 153.6, 151.3, 144.5, 139.1,
134.5, 133.9, 130.5, 129.3, 129.1, 128.5, 128.4, 128.3, 128.1,
127.7, 127.6, 127.1, 126.6, 122.9, 119.4, 114.8. HRMS (ESI)
calcd. for C27H19O2 (M+H)+: 375.1380; found: 375.1377.
4.2.3. 7-methoxy-3,4-diphenyl-2H-chromen-2-one (4c). [10a]
4.2.10. 3,4-diphenyl-7-(trifluoromethyl)-2H-chromen-2-one (4i).
Light yellow solid (53.6 mg, 82%). m. p. 168.4-168.9 °C (lit.
180-182 °C). H NMR (400 MHz, CDCl3): δ = 7.30-7.28 (m,
1
1
Yellow solid (22.7 mg, 31%). m. p. 152.4-153.2 °C. H NMR
3H), 7.18-7.11 (m, 8H), 6.93-6.92 (d, J = 2.20 Hz, 1H), 6.77-6.74
(dd, J = 8.93 Hz, 2.45 Hz, 1H), 3.89 (s, 3H). 13C NMR (100
MHz, CDCl3): δ = 162.5, 161.6, 154.9, 151.8, 134.8, 134.1,
130.7, 129.3, 128.8, 128.3, 128.2, 127.7, 127.4, 123.7, 114.0,
112.2, 100.6, 55.8. HRMS (ESI) calcd. for C25H17O3 (M+H)+:
329.1172; found: 329.1173.
(400 MHz, CDCl3): δ = 7.67 (s, 1H), 7.41-7.34 (m, 5H), 7.20-
7.13 (m, 7H). 13C NMR (100 MHz, CDCl3): δ = 160.4, 152.8,
150.4, 133.7, 133.2, 133.0 (d, J = 33.01 Hz), 130.3, 129.2, 129.0,
128.7, 128.6, 128.5, 128.0, 127.8, 123.2, 123.1 (d, J = 272.90
Hz), 120.6 (d, J = 3.67 Hz), 114.1 (q, J = 4.40 Hz). 19F NMR
(376.5MHz, CDCl3): δ = -62.9. HRMS (ESI) calcd. for
C22H14F3O2 (M+H)+: 367.0940; found: 367.0942.
4.2.4. 7-phenoxy-3,4-diphenyl-2H-chromen-2-one (4d).
4.2.11. 6,8-dimethyl-3,4-diphenyl-2H-chromen-2-one (4j). [10a]
1
Light yellow solid (63.1 mg, 81%). m. p. 188.7-189.0 °C. H
NMR (400 MHz, CDCl3): δ = 7.43-7.39 (m, 2H), 7.30-7.28 (m,
3H), 7.24-7.19 (m, 1H), 7.18-7.08 (m, 10H), 6.95 (d, J = 2.26 Hz,
1H), 6.84-6.81 (dd, J = 8.78 Hz, 2.51 Hz, 1H). 13C NMR (100
MHz, CDCl3): δ = 161.3, 160.9, 155.2, 154.5, 151.5, 134.6,
133.9, 130.6, 130.1, 129.3, 129.1, 128.3, 128.2, 127.7, 127.5,
125.0, 124.7, 120.2, 115.6, 114.2, 105.0. HRMS (ESI) calcd. for
C27H19O3 (M+H)+: 391.1329; found: 391.1326.
Yellow solid (48.9 mg, 75%). m. p. 153.8-154.7 °C (lit. 156-
157 °C). H NMR (400 MHz, CDCl3): δ = 7.30-7.28 (m, 3H),
1
7.21 (s, 1H), 7.18-7.15 (m, 3H), 7.12-7.09 (m, 4H), 6.80 (s, 1H),
2.51 (s, 3H), 2.25 (s, 3H). 13C NMR (100 MHz, CDCl3): δ =
161.5, 152.0, 149.7, 134.9, 134.2, 133.9, 133.1, 130.5, 129.3,
128.1, 127.7, 127.5, 127.4, 126.6, 125.8, 125.2, 119.9, 20.9, 15.7.
HRMS (ESI) calcd. for C23H19O2 (M+H)+: 327.1380; found:
327.1381.
4.2.5. 3,4-diphenyl-2H-chromen-2-one (4e). [10f]
4.2.12. 1,2-diphenyl-3H-benzo[f]chromen-3-one (4k). [10a]
Light yellow solid (40.5 mg, 68%). m. p. 237.3-238.2 °C (lit.
232-234 °C). H NMR (400 MHz, CDCl3): δ = 7.55-7.51 (m,
1
Light yellow solid (49.3 mg, 71%). m. p. 243.2-243.9 °C (lit.
1
1H), 7.44-7.42 (m, 1H), 7.33-7.27 (m, 3H), 7.24-7.11 (m, 9H).
13C NMR (100 MHz, CDCl3): δ = 161.2, 153.2, 151.5, 134.4,
133.8, 131.4, 130.5, 129.3, 128.3, 128.2, 127.8, 127.7, 127.6,
126.9, 124.1, 120.4, 116.7. HRMS (ESI) calcd. for C21H15O2
(M+H)+: 299.1067; found: 299.1069.
245-246 °C). H NMR (400 MHz, CDCl3): δ = 8.66-8.64 (m,
1H), 7.83-7.81 (m, 1H), 7.66-7.60 (m, 2H), 7.55-7.53 (m, 1H),
7.34-7.31 (m, 3H), 7.22-7.13 (m, 8H). 13C NMR (100 MHz,
CDCl3): δ = 161.2, 152.4, 150.2, 134.8, 134.5, 134.0, 130.6,
129.3, 128.6, 128.2, 127.7, 127.6, 127.5, 127.1, 127.0, 126.3,
123.8, 123.2, 123.0, 122.6, 115.5. HRMS (ESI) calcd. for
C25H17O2 (M+H)+: 349.1223; found: 349.1220.
4.2.6. 7-fluoro-3,4-diphenyl-2H-chromen-2-one (4f).
1
Light yellow solid (42.4 mg, 67%). m. p. 167.3-168.0 °C. H
4.2.13. 4-(4-methoxyphenyl)-7-methyl-3-phenyl-2H-chromen-2-
one (4l). [14b]
NMR (400 MHz, CDCl3): δ = 7.31 (s, 3H), 7.18-7.12 (m, 9H),
6.93 (s, 1H). 13C NMR (100 MHz, CDCl3): δ = 164.2 (d, J =
253.82 Hz), 161.0, 154.2 (d, J = 13.20 Hz), 151.1 (d, J = 1.47
Hz), 134.3, 133.6, 130.5, 129.5 (d, J = 10.27 Hz), 129.2, 128.5,
128.4, 127.8, 127.7, 125.8 (d, J = 2.93 Hz), 117.2 (d, J = 2.93
Hz), 112.1 (d, J = 22.01 Hz), 104.2 (d, J = 25.68 Hz). 19F NMR
(376.5 MHz, CDCl3): δ = -106.1. HRMS (ESI) calcd. for
C21H14FO2 (M+H)+: 317.0972; found: 317.0974.
Light yellow solid (42.8 mg, 63%). m. p. 229.9-230.4 °C (lit.
1
226-228 °C). H NMR (400 MHz, CDCl3): δ = 7.22-7.11 (m,
7H), 7.04-6.99 (m, 3H), 6.83-6.81 (d, J = 8.68 Hz, 2H), 3.79 (s,
3H), 2.46 (s, 3H). 13C NMR (100 MHz, CDCl3): δ = 161.6, 159.4,
153.3, 151.4, 142.6, 134.3, 130.8, 130.6, 127.8, 127.5, 127.4,
126.7, 125.8, 125.2, 118.3, 116.9, 113.7, 55.2, 21.6. HRMS (ESI)
calcd. for C23H19O3 (M+H)+: 343.1329; found: 343.1330.
4.2.7. 7-chloro-3,4-diphenyl-2H-chromen-2-one (4g).
4.2.14. 4-(4-fluorophenyl)-7-methyl-3-phenyl-2H-chromen-2-one
(4m).
1
Light yellow solid (36.5 mg, 55%). m. p. 176.4-176.9 °C. H
NMR (400 MHz, CDCl3): δ = 7.45 (s, 1H), 7.33-7.32 (m, 3H),
7.20-7.12 (m, 9H). 13C NMR (100 MHz, CDCl3): δ = 160.7,
153.4, 150.9, 137.3, 134.0, 133.5, 130.4, 129.2, 128.7, 128.5,
128.4, 127.8, 127.7, 126.9, 124.7, 119.2, 116.9. HRMS (ESI)
calcd. for C21H14ClO2 (M+H)+: 333.0677; found: 333.0679.
1
Light yellow solid (44.6 mg, 68%). m. p. 194.8-195.6 °C. H
NMR (400 MHz, CDCl3): δ = 7.23 (s, 1H), 7.20-7.19 (m, 3H),
7.11-7.06 (m, 5H), 7.02-6.97 (m, 3H), 2.46 (s, 3H). 13C NMR
(100 MHz, CDCl3): δ = 162.4 (d, J = 248.69 Hz), 161.3, 153.3,
150.6, 142.9, 133.9, 131.2 (d, J = 8.07 Hz), 130.6, 130.5, 127.9,
127.4 (d, J = 43.28 Hz), 126.3, 125.4, 117.9, 117.0, 115.6, 115.4,
21.6. 19F NMR (376.5 MHz, CDCl3): δ = -112.5. HRMS (ESI)
calcd. for C22H16FO2 (M+H)+: 331.1129; found: 331.1130.
4.2.8. 4,7-diphenyl-2H-chromen-2-one (4h1).
1
Light yellow solid (36.8 mg, 62%). m. p. 124.3-124.9 °C. H
NMR (400 MHz, CDCl3): δ = 7.65-7.63 (m, 3H), 7.57-7.53 (m,

6
Tetrahedron
1
4.2.15. 7-methyl-4-phenyl-3-(p-tolyl)-2H-chromen-2-one (4n).
[14b]
Light yellow solid (14.9 mg, 15%). m. p. 187.0-187.9 °C. H
NMR (400 MHz, CDCl3): δ = 7.32-7.19 (m, 5H), 7.10-7.05 (m,
3H), 7.00-6.95 (m, 3H), 6.92-6.90 (m, 1H), 2.45 (s, 3H), 2.20 (s,
3H). 13C NMR (100 MHz, CDCl3): δ = 160.9, 153.5, 152.2,
142.7, 136.8, 134.5, 133.8, 130.6, 129.8, 129.3, 128.3, 128.2,
128.0, 127.9, 127.4, 125.3, 126.0, 117.9, 117.0, 21.6, 19.9.
HRMS (ESI) calcd. for C23H19O2 (M+H)+: 327.1380; found:
327.1383.
Yellow solid (43.3 mg, 70%). m. p. 237.3-238.1 °C (lit. 232-
1
234 °C). H NMR (400 MHz, CDCl3): δ = 7.32-7.29 (m, 3H),
7.22 (s, 1H), 7.13-7.10 (m, 2H), 7.08-7.06 (m, 1H), 7.02-6.97 (m,
5H), 2.45 (s, 3H), 2.24 (s, 3H). 13C NMR (100 MHz, CDCl3): δ =
161.6, 153.2, 151.2, 142.5, 137.2, 134.8, 130.9, 130.4, 129.3,
128.4, 128.2, 128.1, 127.4, 125.8, 125.2, 118.1, 116.8, 21.6, 21.2.
HRMS (ESI) calcd. for C23H19O2 (M+H)+: 327.1380; found:
327.1381.
4.2.22.
one (4u).
3-(2-chlorophenyl)-7-methyl-4-phenyl-2H-chromen-2-
1
4.2.16. 3-(4-methoxyphenyl)-7-methyl-4-phenyl-2H-chromen-2-
one (4o).
Yellow solid (10.8 mg, 16%). m. p. 155.8-156.5 °C. H NMR
(400 MHz, CDCl3): δ = 7.36-7.30 (m, 2H), 7.28-7.25 (m, 3H),
7.23-7.20 (m, 1H), 7.17-7.12 (m, 2H), 7.11-7.06 (m, 2H), 7.05-
7.03 (m, 1H), 7.00-6.98 (m, 1H), 2.48 (s, 3H). 13C NMR (100
MHz, CDCl3): δ = 160.2, 153.6, 153.0, 143.1, 134.4, 134.1,
133.7, 131.9, 129.2, 128.7, 128.5, 128.1, 127.8, 127.5, 126.4,
125.4, 124.2, 117.6, 117.0, 21.6. HRMS (ESI) calcd. for
C22H16ClO2 (M+H)+: 347.0833; found: 347.0834.
1
White solid (43.1 mg, 63%). m. p. 199.7-200.4 °C. H NMR
(400 MHz, CDCl3): δ = 7.32-7.30 (m, 3H), 7.22 (s, 1H), 7.13-
7.10 (m, 2H), 7.07-7.03 (m, 3H), 6.99-6.97 (m, 1H), 6.72-6.70
(m, 2H), 3.73 (s, 3H), 2.45(s, 3H). 13C NMR (100 MHz, CDCl3):
δ = 161.8, 158.8, 153.2, 151.1, 142.4, 134.9, 131.9, 129.4, 128.3,
128.2, 127.4, 126.2, 125.4, 125.3, 118.2, 116.8, 113.2, 55.1, 21.6.
HRMS (ESI) calcd. for C23H19O3 (M+H)+: 343.1329; found:
343.1331.
4.2.23. 7-methyl-3-(naphthalen-2-yl)-4-phenyl-2H-chromen-2-
one (4v).
1
4.2.17.
3-(4-chlorophenyl)-7-methyl-4-phenyl-2H-chromen-2-
Light brown solid (34.9 mg, 48%). m. p. 205.7-206.1 °C. H
one (4p).
NMR (400 MHz, CDCl3): δ = 7.75-7.66 (m, 3H), 7.41 (s, 2H),
7.29-7.24 (m, 4H), 7.12-7.10 (m, 3H), 7.02-7.00 (m, 1H), 6.95-
6.92 (m, 1H), 6.84-6.82 (m, 1H), 2.47 (s, 3H). 13C NMR (100
MHz, CDCl3): δ = 161.1, 153.7, 153.6, 142.9, 134.4, 133.2,
132.2, 132.0, 128.8, 128.5, 128.4, 128.2, 128.1, 127.7, 127.5,
126.2, 125.7, 125.4, 125.1, 125.0, 124.8, 117.9, 117.0, 21.6.
HRMS (ESI) calcd. for C26H19O2 (M+H)+: 363.1380; found:
363.1382.
1
White solid (44.9 mg, 65%). m. p. 220.9-221.7 °C. H NMR
(400 MHz, CDCl3): δ = 7.34-7.32 (t, J = 3.18 Hz, 3H), 7.23 (s,
1H), 7.16-7.14 (m, 2H), 7.11-7.05 (m, 5H), 7.01-6.99 (m, 1H),
2.46 (s, 3H). 13C NMR (100 MHz, CDCl3): δ = 161.3, 153.3,
152.0, 143.0, 134.4, 133.5, 132.5, 132.0, 129.3, 128.5, 128.4,
128.0, 127.6, 125.5, 124.6, 117.9, 117.0, 21.6. HRMS (ESI)
calcd. for C22H16ClO2 (M+H)+: 347.0833; found: 347.0834.
4.3. Applications and transformations
4.2.18. 3-(4-acetylphenyl)-7-methyl-4-phenyl-2H-chromen-2-one
(4q).
4.3.1. (E)-7-methyl-4-phenyl-3-styryl-2H-chromen-2-one (7). [6]
Yellow solid (42.6 mg, 63%). m. p. 171.0.-171.7 °C (lit. 169.8-
1
Light yellow solid (26.3 mg, 37%). m. p. 204.6-205.3 °C. H
1
NMR (400 MHz, CDCl3): δ = 7.78-7.76 (m, 2H), 7.32-7.30 (m,
3H), 7.25-7.23 (m, 3H), 7.12-7.10 (m, 3H), 7.03-7.01 (m, 1H),
2.53 (s, 3H), 2.47 (s, 3H). 13C NMR (100 MHz, CDCl3): δ =
197.8, 161.1, 153.4, 152.4, 143.3, 139.2, 135.9, 134.2, 131.0,
129.2, 128.7, 128.4, 127.7, 127.6, 125.5, 124.7, 117.8, 117.0,
26.6, 21.7. HRMS (ESI) calcd. for C24H19O3 (M+H)+: 355.1329;
found: 355.1330.
171.6 °C). H NMR (400 MHz, CDCl3): δ = 7.93-7.89 (d, J =
16.26 Hz, 1H), 7.57-7.55 (m, 3H), 7.31-7.19 (m, 8H), 6.97-6.92
(m, 2H), 6.70-6.66 (d, J = 16.26 Hz, 1H), 2.44 (s, 3H). 13C NMR
(100 MHz, CDCl3): δ = 160.1, 152.3, 150.5, 142.4, 137.8, 135.1,
134.8, 129.0, 128.8, 128.5, 127.9, 127.2, 126.8, 125.4, 121.8,
120.3, 118.5, 116.6, 21.6.
4.3.2. 7-methyl-4-phenyl-3-(phenylethynyl)-2H-chromen-2-one
(9). [7]
4.2.19. 3-(3,5-dimethylphenyl)-7-methyl-4-phenyl-2H-chromen-
2-one (4r).
Light yellow solid (30.9 mg, 46%). m. p. 171.9.-172.6 °C (lit.
171.7-172.9 °C). 1H NMR (400 MHz, CDCl3): δ = 7.56-7.47 (m,
5H), 7.22-7.19 (m, 6H), 7.16-7.14 (m, 1H), 7.02-7.00 (m, 1H),
2.44 (s, 3H). 13C NMR (100 MHz, CDCl3): δ = 159.7, 156.3,
152.8, 143.5, 134.4, 131.6, 129.2, 129.0, 128.6, 128.3, 128.1,
127.2, 125.7, 122.5, 117.2, 117.1, 109.8, 98.1, 83.7, 21.6.
1
Yellow solid (34.1 mg, 50%). m. p. 180.1-180.8 °C. H NMR
(400 MHz, CDCl3): δ = 7.29-7.28 (m, 3H), 7.22 (s, 1H), 7.11-
7.06 (m, 3H), 6.98-6.96 (m, 1H), 6.77-6.72 (m, 3H), 2.44 (s, 3H),
2.15 (s, 6H). 13C NMR (100 MHz, CDCl3): δ = 161.6, 153.2,
151.3, 142.4, 136.9, 134.7, 133.7, 129.2, 128.7, 128.2, 128.0,
127.4, 127.2, 126.1, 125.2, 118.1, 116.8, 21.5, 21.1. HRMS (ESI)
calcd. for C24H21O2 (M+H)+: 341.1536; found: 341.1537.
Declaration of Competing Interest
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.
4.2.20.
one (4s).
3-(3-chlorophenyl)-7-methyl-4-phenyl-2H-chromen-2-
1
Light yellow solid (35.7 mg, 51%). m. p. 179.0-180.4 °C. H
NMR (400 MHz, CDCl3): δ = 7.56-7.52 (m, 1H), 7.33-7.28 (m,
3H), 7.23-7.20 (m, 1H), 7.14-7.07 (m, 5H), 7.01-6.93 (m, 2H),
2.46 (s, 3H). 13C NMR (100 MHz, CDCl3): δ = 161.0, 153.3,
152.3, 143.1, 135.8, 134.1, 133.5, 130.7, 129.2, 128.9, 128.8,
128.5, 128.3, 127.7, 127.6, 125.4, 124.4, 117.8, 116.9, 21.6.
HRMS (ESI) calcd. for C22H16ClO2 (M+H)+: 347.0833; found:
347.0835.
Acknowledgements
We greatly acknowledge partial financial support from the
National Natural Science Foundation (NSF) of China (21172200
and 21302172) and Basic Research Training Project of
Zhengzhou University (JC2020053021).
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Highlights
1) The one-pot method involves photocatalysis and thermocatalytic processes.
2) The light “on-off” stepwise one-pot method has excellent substrate tolerance.
3) A straight forward way to obtain various types of multi-substituted coumarins.
4) Some of the synthesized 3,4-diaryl coumarins have potential AIE activities
.