Visible-light-promoted aerobic oxidative hydroxylation of arylboronic acids in water by hydrophilic organic semiconductor

Article abstract of DOI:10.1016/j.tetlet.2020.152010

A green and sustainable catalytic system was developed based on perylenediimide (PDI) organic semiconductor for the aerobic oxidative hydroxylation of arylboronic acids in aqueous solution with visible light. By using PDI-SN, a hydrophilic organic semiconductor, which can activate oxygen to produce superoxide radicals in aqueous solution, this reaction proceeds under ambient conditions: water as the solvent and air as the oxidant, giving various phenols as products with high yields. In contrast to methods using organic solvents, this novel process has the potential of green industrial application.

Full text of DOI:10.1016/j.tetlet.2020.152010

Journal Pre-proofs
Visible-Light-Promoted Aerobic Oxidative Hydroxylation of Arylboronic
Acids in Water by Hydrophilic Organic Semiconductor
Kunyi Yu, Hanjie Zhang, Yuqiang Sheng, Yongfa Zhu
PII:
S0040-4039(20)30453-6
DOI:
Reference:
https://doi.org/10.1016/j.tetlet.2020.152010
TETL 152010
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Tetrahedron Letters
Received Date:
Revised Date:
Accepted Date:
17 March 2020
25 April 2020
4 May 2020
Please cite this article as: Yu, K., Zhang, H., Sheng, Y., Zhu, Y., Visible-Light-Promoted Aerobic Oxidative
Hydroxylation of Arylboronic Acids in Water by Hydrophilic Organic Semiconductor, Tetrahedron Letters
(2020), doi: https://doi.org/10.1016/j.tetlet.2020.152010
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Visible-Light-Promoted Aerobic Oxidative
Hydroxylation of Arylboronic Acids in
Water
by
Hydrophilic
Organic
Semiconductor
Kunyi Yua , Hanjie Zhanga , Yuqiang Shenga and Yongfa Zhua
aDepartment of Chemistry Tsinghua University, Beijing, 100084, PR China
A hydrophilic organic semiconductor PDI-SN was used for green and sustainable photocatalytic
synthesis of the aerobic oxidative hydroxylation of aryl boronic acids. This reusable catalytic system
proceeds under ambient conditions: water as solvent and air as oxidant, giving various phenols as
products with high yields.

3

1
Tetrahedron Letters
Visible-Light-Promoted Aerobic Oxidative Hydroxylation of Arylboronic Acids in
Water by Hydrophilic Organic Semiconductor
Kunyi Yua† , Hanjie Zhanga†, Yuqiang Shenga and Yongfa Zhua
aDepartment of Chemistry Tsinghua University, Beijing, 100084, PR China
†These authors contributed equally to this work.
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
Available online
A green and sustainable catalytic system was developed based on perylenediimide (PDI)
organic semiconductor for the aerobic oxidative hydroxylation of aryl boronic acids in
Keywords:
hydroxylation
visible light
organic semiconductor
aqueous reaction
boronic acid
aqueous solution with visible light. By using PDI-SN,
a hydrophilic organic
semiconductor, which can activate oxygen to produce superoxide radicals in aqueous
solution, this reaction proceeds under ambient conditions: water as the solvent and air as
the oxidant, giving various phenols as products with high yields. In contrast to methods
using organic solvents, this novel process has the potential of green industrial application.
———
 Corresponding author. e-mail: zhuyf@tsinghua.edu.cn

2
Tetrahedron
1. Introduction
2. Results and discussions
Phenols, as a common structural unit, widely exist in nature
In our previous studies, efficient aerobic oxidation of
cycloamines was realized using a hydrophilic photocatalyst PDI-
SN,34 which consists of SiO2 nanoparticles containing amino
groups and PDI molecules. The high photo-oxidative activity was
observed due to the minute aggregates of PDI molecules on the
products and pharmaceuticals, are used for the synthesis of fine
chemicals as useful intermediates.1 For its important value, the
approaches to their preparation has been widely concerned.2
Among the methods as reported,3 the oxidative hydroxylation of
arylboronic acids is considered to be a very effective way to
prepare phenols. Various oxidants (mCPBA, Oxone, TBHP,
surface of SiO2 nanospheres forming organic semiconductor and
-
was detectable as the key reactive oxygen species. Therefore,
4-11
PhI(OAc)2, H2O2, etc.) are used for the synthesis of phenols.
our studies started with the aerobic oxidative hydroxylation of
benzeneboronic acid (1a) using PDI-SN as the photocatalyst. To
our delight, the desired product phenol (2a) was obtained in a
yield of 92% with triethylamine (TEA) as the electron donors and
H2O as the solvent under irradiation with 20 W 400 nm LED for
42 hours (Table 1, entry 1). Inspired by the result, some control
experiments including catalysts, electron donors, air and light
irradiation were performed. These results clearly demonstrated
that all factors are essential (Table 1, entries 2-5). Subsequently,
the wavelengths of visible light sources were studied, with 400
nm leading to the highest catalytic activity (see Table S1. in the
Supporting Information). It is worth mentioning that methanol
(MeOH) as a solvent gave the best result and the substrate can be
completely transformed to the corresponding phenol within 7
hours in 93% yield (see Table S2. in the Supporting Information).
It may be that MeOH acted as a role of electron donors.
In comparison with these stoichiometric oxidants, molecular
oxygen (O2 and air) attracts more attention due to its cheap and
readily availablity.12 Consequently, the aerobic methods for the h
oxidative hydroxylation of arylboronic acids using molecular
oxygen have also been developed.13-15 Despite their
achievements, more green protocols for this transformation are
still highly desirable, and it would be valuable to develop a new
catalytic system to avoid the use of transition-metals and violent
organic solvents.
The development of green and sustainable approaches to the
synthesis of fine chemicals is a primary aim nowadays. Recently,
visible-light catalysis is considered as promising to achieve this
objective.16 Some photocatalytic systems based on transition
metal complexes,17 solid materials containing transition metals,18-
23
porous-organic frameworks,24 fullerenes,25 covalent-organic
frameworks,26 and organic photocatalysts27 have been applied for
the visible-light-promoted aerobic oxidative hydroxylation of
aryl boronic acids. Despite the high level of efficiency, these
protocols usually require the use of non-reusable organic
photosensitizers, transition metals or volatile organic solvents.
From the perspective of sustainable and green chemistry, a
reusable metal-free catalytic system using water as reaction
medium is desirable for synthetic chemists. Therefore, the
application of this system for the oxidative hydroxylation of
arylboronic acids is highly expected.
Table 1. Control experiments.a, b
In recent years, organic semiconductor photocatalysts have
been extensively applied in splitting water into H2 and O2,28 the
degradation of pollutants29 and CO2 reduction30 due to its high
catalytic stability. These heterogeneous catalytic systems were
favored by synthesis chemists as well because the catalysts can
be reused and the products can be easily separated.31 Recently,
Xu and Chen’s group reported a reusable photocatalytic system
based on organic semiconductor C3N4 to realize the aerobic
oxidative hydroxylation of arylboronic acids using EtOH as the
solvent.32 However, the performance for this transformation was
poor when water as the reaction medium. Based on their studies
a
Reaction conditions: benzeneboronic acid (1a, 0.3 mmol), PDI-SN (10 mg), TEA (0.6
and others,17-27 superoxide radicals ( -) is considered to be a
mmol), H2O (1 mL), ambient air atmosphere under 20 W 400 nm LED irradiation for 42
h. Yield determined by GC analysis with an internal standard (dodecane). n.r. = no
reaction.
b
critical oxidative specie for this transformation. According to the
recent research by our group,33 the efficient production of - in
In order to improve the reaction efficiency in water, others
electron donors such as diisopropylethylamine (DIPEA),
triethanolamine (TEOA) were also investigated. To our delight,
we found that TEOA was more efficient as electron donor,
because complete transformation taked the shortest time with a
comparable yield (Table 2, entry 3). This may be attributed to
TEOA being water-soluble, which is consistent with the
hydrophilic catalyst. Encouraged by this results, control
experiments involving in the catalyst components were carried
out. The hydrophilic nanospheres SN-NH2 containing amino
groups, as the precursors of PDI-SN, showed no catalytic activity
(Table 2, entry 4). Poor performance was found when a self-
assembly semiconductor PDINH as catalyst (Table 2, entry 5).
the water medium based on perylene diimide (PDI) organic
semiconductor driven by visible light is certainly feasible.
Following our continuing study of green synthesis,34 we
envisioned that the photocatalytic oxidative hydroxylation of aryl
boronic acids in water could be achieved by PDI semiconductor
catalytic system. In this regard, a green and sustainable method
was developed for this transformation. This protocol has the
following advantages: (1) A green catalytic system with metal-
free, air as the oxidant and water as the solvent. (2) Good photo-
oxidative selectivity and high functional-group tolerance; (3)
operationally simple and reusable catalyst. In contrast to methods
using volatile organic solvents, this novel process has the
potential of green industrial application.

3
Table 3. Visible-light-promoted aerobic oxidative hydroxylation of
This observation suggested the catalytic activity of PDI-SN in
water is enhanced with the assistance of hydrophilic carrier SiO2.
Comparatively, the bulky g-C3N4, which was frequently used in
semiconductor photocatalysis, was studied under the standard
reaction conditions, but poor performance was observed (Table 2,
entry 6).
arylboronic acids.a, b
Table 2. Optimization of the reaction conditions.a, b
a
Reaction conditions: benzeneboronic acid (1a, 0.3 mmol), catalyst (10 mg), electron
donor (0.6 mmol), H2O (1 mL), ambient air atmosphere under 20 W 400 nm LED
a
Reaction conditions: Benzeneboronic acid (1a, 0.3 mmol), PDI-SN (10 mg), TEOA
(0.6 mmol), H2O (1 mL), ambient air atmosphere under 20 W 400 nm LED irradiation
for 18 h. b Isolated yield. c 4-trifluoromethyl phenoboric acid (1k, 8 mmol), PDI-SN (150
mg), TEOA (16 mmol), H2O (15 mL), Combination of the light source of 2 X 20W 400
nm LED irradiation for 52 h.
irradiation. b Yield determined by GC analysis with an internal standard (dodecane).
With the optimal condition in hand, this green and
sustainable catalytic protocol was then applied to the aerobic
hydroxylation of diverse arylboronic acids. As shown in Table 3,
various substituted arylboronic acids were compatible. The
benzeneboronic acids bearing a methyl, as substituted at 2-, 3-,
and 4- positions were well tolerated, and the 2-position
substitution afforded slightly lower yields, which is possibly
attributed to the greater steric hindrance at the 2-position than
that at the other positions (Table 3, 2b-2d). Consequently,
sterically hindered 2,4,6-trimethyl substituted benzeneboronic
acid generated the desired product in lower yields of 66% (Table
3, 2e). In addition to alkyl substitution, the substrate containing
other electron-donating group like 4-methoxyl substituted
benzeneboronic acid worked in this system as well in a more
moderate yield (Table 3, 2f). On the other hand, the substrates
containing the electron-withdrawing groups such as 4-F, 4-Cl, 4-
Br and 4-I were converted into the corresponding phenols in
good yields (Table 3, 2g-2j). Moreover, the substrates carrying
stronger electron-withdrawing groups like 4-cyano-, 4-
trifluoromethyl-, 4-methoxycarbonyl- and 4-acyl phenyl boronic
acids were transformed into the desired products in excellent
yields (Table 3, 2k-2n). Particularly, such oxidative sensitive
substrates as aldehyde, benzyl alcohol and aniline were also
compatible with this procedure, affording the desired phenols in
78-86% yields (Table 3, 2o-2q). Additionally, the fused ring
arylboronic acid like 1-naphthalenyl boronic acid was subjected
to this reaction system, and the desired product 1-naphthalenol
was obtained in 90% yield (Table 3, 2r). Furthermore, the
heterocyclic arylboronic acids such as 6-quinolinylboronic acid,
and (1H-indol-5-yl) boronic acid and 4-pyridinylboronic acid
were also applicable in this protocol, generating the desired
products in 76-92% yields (Table 3, 2s-2u).
To gain insight into the heterogeneous nature of PDI-SN,
photostability and reusability tests were performed (see the
Supporting Information for details of the tests). The catalyst and
filtrate were separated by filtration after photo-oxidation. The
colorless filtrate suggested that the catalyst is stable because PDI
molecules as a red dye have a high molar absorption coeffcient.
After being washed with acetone and dried in the air, the catalyst
was reused in the aerobic oxidative hydroxylation of
benzeneboronic acid once again, and no significant loss of
activity was observed even after 6 cycles (Figure 1). In addition,
after comparing with the U-Vis and IR absorption spectra before
and after the reaction, there was no significant change (see Figure
S3 in the Supporting Information). These results indicated the
organic semiconductor PDI-SN can be applied as a robust
heterogeneous photocatalyst.

4
Tetrahedron
Figure 1. Recycling test of the PDI-SN catalyst. Reaction conditions: benzeneboronic
acid (1a, 0.3 mmol), TEOA (0.6 mmol), PDI-SN (30 mg), and H2O (1 mL), ambient air
atmosphere under 20 W 400 nm LED irradiation for 18 h.
In order to determine the source of oxygen atom in the
product phenol, isotope labeling experiments were carried out
(Scheme 1a). When the air was replaced by isotope-labeled
molecule oxygen (18O2) balloon, the 18O-2a phenol as product
was obtained, suggesting that the oxygen atom of the product
comes from air. A series of quenching experiments were
conducted with the focus placed on the involved reactive oxygen
species (ROS).35 When isopropyl alcohol (IPA), a common
hydroxyl radical (H ) quencher,36 was added in this reaction
system, the yield of phenol was the same as without quencher,
which implied that no involvement of H (Scheme 1b).
Likewise, the yield of phenol was slightly lower than that without
quencher when singlet oxygen (1O2) quencher bicyclo2.2.2-1,4-
diazaoctane (DBACO) was added,37 suggesting that (1O2) was not
the reactive oxygen species (Scheme 1c). In the presence of
Scheme 2. Proposed mechanism for the aerobic hydroxylation of aryl boronic acids.
TEOA are oxidized by photo-generated holes through a single
electron transfer (SET) process, thus forming radical
-
cation . Next, the substrate 1a reacts with to generate
the radical anion intermediate A, which then reacts with
through
a
well-established HAT mechanism39 to form
superoxide radical ( - ) quencher butylated hydroxytoluene
intermediate B. Finally, the product 2a phenol is obtained by
rearrangement of intermediate B into intermediate C with
(BHT),38 the results of severe inhibition indicated that the
subsequent hydrolysis. In this way, both - as the intermediates
-
reaction may involve (Scheme 1d) and it was supported by
of hole-oxidation and as the intermediates of electron-
EPR studies. The DMPO- - signal could be detected when the
reduction are applied to the path of aerobic oxidative
hydroxylation of aryl boronic acid.
PDI-SN were irradiated for 2 min and no signals were observed
without light irradiation (see Figure S4 in the Supporting
-
In conclusion, a green and sustainable photocatalytic system
based on a hydrophilic organic semiconductor PDI-SN was
developed for the aerobic oxidation hydroxylation of aryl boronic
acids in aqueous solution. In this reaction, various phenols were
obtained with high yields under metal-free and ambient
conditions using air as green oxidant and water as green solvent.
The photostability and reusability tests indicated that the PDI-SN
is a robust heterogeneous photocatalyst. More green and
sustainable synthetic strategies using water as reaction medium
are going on in our laboratory.
Information). The aforementioned results demonstrated that
may be the ROS in this reaction system.
Acknowledgments
This work was partly supported by Natural Science
Foundation of China (21437003, 21673126, 21761142017,
21621003, and 21972094), Beijing Municipal Science and
Technology Project (Z181100005118007), Collaborative
Innovation Center for Regional Environmental Quality. The
authors thank Miss Caifeng Xu, Shenzhen Research Institute,
The Hong Kong Polytechnic University for providing important
advice in preparing manuscripts.
Scheme 1. Reactive oxygen species quenching experiments. Reaction conditions:
benzeneboronic acid (1a, 0.3 mmol), TEOA (0.6 mmol), PDI-SN (30 mg), quencher (0.9
mmol) and H2O (1 mL), ambient air atmosphere under 20 W 400 nm LED irradiation for
18 h.
References and notes
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and the previous literatures,32 a plausible mechanism of the
aerobic oxidative hydroxylationof arylboronic acids is proposed
(Scheme 2). At first, the organic semiconductor PDI-SN is
excited under visible-light irradiation to generate electron-hole
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Highlights:
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Kumar, R.; Sharma, U. Adv. Synth. Catal. 2018, 360, 2013−2019;
 A new green method for
hydroxylation of arylboronic
acids was developed.

6
Tetrahedron
 Water as solvent and air as
oxidant.
 Reusable catalytic system.
 A hydrophilic organic
semiconductor as
photocatalyst.