Visible-light, photoredox catalyzed, oxidative hydroxylation of arylboronic acids using a metal-organic framework containing tetrakis(carboxyphenyl)porphyrin groups

Article abstract of DOI:10.1039/c5cc06163f

A Zr-based metal-organic framework with tetrakis(carboxyphenyl)porphyrin groups (Zr-MOF-TCPP: MOF-525) has been utilized as a photoredox catalyst to promote oxidative hydroxylation of arylboronic acids under green LED light irradiation. Zr-MOF-TCPP displays a superior catalytic activity for this process over the corresponding homogeneous catalyst (H₄TCPP).

Full text of DOI:10.1039/c5cc06163f

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DOI: 10.1039/C5CC06163F.
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DOI: 10.1039/C5CC06163F
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Visible-light, photoredox catalyzed, oxidative hydroxylation of
arylboronic acids using a metal−organic framework containing
tetrakis(carboxyphenyl)porphyrin groups
Received 00th January 20xx,
Accepted 00th January 20xx
a
a
a
a,b
c
a
Takashi Toyao, Nana Ueno, Kenta Miyahara, Yasunori Matsui, Tae-Ho Kim, Yu Horiuchi,*
Hiroshi Ikeda and Masaya Matsuoka*a
a,b
DOI: 10.1039/x0xx00000x
www.rsc.org/
A
Zr-based
metal−organic
framework
with Numerous efforts have been made in recent years to identify MOFs
tetrkis(carboxyphenyl)porphyrin groups (Zr-MOF-TCPP: MOF-525) that serve as platforms for integrating different molecular functional
has been utilized as a photoredox catalyst to promote oxidative components to achieve efficient gas storage, gas separation, sensing,
5
hydroxylation of arylboronic acids under green LED light irradiation. and catalytic applications. Studies of photocatalysis by MOFs have
6
Zr-MOF-TCPP displays a superior catalytic activity for this process attracted a great deal of attention recently. Many MOF based
compared to the corresponding homogeneous catalyst (H
4
TCPP).
photocatalytic systems have been demonstrated to possess
advantageous features. Nevertheless, the reactions promoted by
visible light are still rare, and there are only a limited number of
reports describing organic transformation reactions over MOF
Recent developments made in the area of visible-light-driven
photoredox catalysis have attracted attention owing to the fact that
readily available and environmentally benign visible light is the key
reagent and that the processes generally take place efficiently under
7
photocatalysts under visible light.
Herein, we describe the results of a study in which we have
demonstrated that oxidative hydroxylation of arylboronic acids to
form phenols (Scheme 1) is promoted by visible light photoredox
catalysis using MOFs consisting of Zr-oxo clusters with tetrakis(4-
1
mild conditions. Photoredox catalysts can be used to carry out a
wide variety of organic transformations and, as such, they serve as a
powerful tools in organic synthesis as well as material chemistry. Ir
and Ru complexes are the most studied photoredox catalysts. These
substances display high activities and versatilities in many reactions.2
A major limitation of the utilization of Ir and Ru systems is that they
require precious metals, which often are toxic and expensive. In light
of the disadvantages associated with noble-metal based protocols,
recent interest has arisen in the development of noble-metal-free
catalytic systems that employ organic dye photoredox catalysts.3
However, these catalysts are homogeneous and, as a result, they
generally suffer from product contamination and limited recyclability.
Metal−organic frameworks (MOFs), also called porous
coordination polymers (PCPs), have received attention recently
because of their attractive properties including high specific surface
areas, well-ordered porous structures and structural designability.4
8
carboxyphenyl)porphyrin (TCPP) groups (Zr-MOF-TCPP; MOF-525).
It is well known that phenols are versatile intermediates and building
9
blocks in the chemical and pharmaceutical industries. Prior to this
effort, it was demonstrated that oxidative hydroxylation of
arylboronic acids to generate phenols can be promoted using
10a
homogeneous photoredox catalysts such as Ru and Ir complexes,
10b
and methylene blue (MB). Compared to these earlier methods, the
one developed in this investigation has the advantage that
a.Department of Applied Chemistry, Graduate School of Engineering, Osaka
Prefecture University, 1-1 Gakuen-cho, Naka-ku, Sakai, Osaka 599-8531, Japan
b.
The Research Institute for Molecular Electronic Devices (RIMED), Osaka
Prefecture University, 1-1 Gakuen-cho, Naka-ku, Sakai, Osaka 599-8531, Japan
Division of Mechanics and ICT Convergence Engineering, Sun Moon University,
c.
GalSan-Ri, Tangjung-Myon, Asan Chungnam 336708, Republic of Korea
Scheme 1. Visible-light photocatalyzed, oxidative hydroxylation of
arylboronic acids using Zr-MOF-TCPP.
Electronic Supplementary Information (ESI) available: [Experimental details, XRD,
N adsorption-desorption, FT-IR, SEM, UV-vis, LFP and TGA measurements. Results
2
of catalytic reactions and a leaching test]. See DOI: 10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
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DOI: 10.1039/C5CC06163F
Fig. 2. Wavelength-dependent apparent quantum yield for oxidative
hydroxylation of phenylboronic acid over Zr-MOF-TCPP and the diffuse-
reflectance spectrum of Zr-MOF-TCPP.
Fig. 1. Time courses of oxidative hydroxylation of phenylboronic acid
using Zr-MOF-TCPP, H TCPP and in the absence of catalyst under green
4
LED (523 nm) light irradiation. Yields were determined by GC.
heterogeneous catalysts are used and, as a result, recovery and explored using green LED (523 nm) light irradiation at room
recycling of the photocatalyst can be readily achieved. Moreover, in temperature and triethylamine (TEA) as a sacrificial electron donor.
1
1a,b
contrast to the recent protocols utilizing MOFs
and porous Figure 1 shows time courses of the oxidative hydroxylation reaction
organic framework (POF) as heterogeneous photoredox catalysts, of phenylboronic acid using Zr-MOF-TCPP, homogeneous H TCPP
11c
4
the new system developed in the current effort does not rely on and in the absence of a catalyst. The results show that phenylboronic
expensive metals and it displays a higher catalytic activity and acid is quantitatively converted to phenol within 9 h when Zr-MOF-
broader substrate scope for oxidative hydroxylation of arylboronic TCPP is employed as the catalyst. The turnover number (TON) was
acids to phenols.
Zr-MOF-TCPP (MOF-525), comprised of TCPP groups and groups in Zr-MOF-TCPP. Moreover, the reaction does not take place
(OH)
, was synthesized using a slight modification of the when the catalyst is not present or when another Zr-based MOF
previously-reported method.
characterized by using XRD, N
adsorption-desorption, FT-IR, diffuse is used (entries 3 and 7 in Table 1). These results suggest that TCPP
calculated to be 70 based on the number of equivalents of TCPP
6
Zr O
4
4
8
13
Synthetic Zr-MOF-TCPP was consisting of Zr-oxo cluster and terephthalic acid (Zr-MOF; UiO-66)
2
reflectance UV-vis and SEM methods (Fig. S1−5). The XRD pattern groups in Zr-MOF-TCPP act as photocatalytically active centers for
observed for Zr-MOF-TCPP is in good agreement with that previously this process. Interestingly, the progress of the phenol producing
8
reported. No diffraction peaks corresponding to bulk ZrO
2
were reaction promoted by Zr-MOF-TCPP was found to be faster than that
TCPP, even
. The specific though equivalent amounts of TCPP groups are present. This
observed in this spectrum, suggesting that Zr-MOF-TCPP is not promoted by the corresponding homogeneous catalyst H
contaminated by the presence of crystalline ZrO
surface area of Zr-MOF-TCPP was determined to be 1485 m g using observation is attributed to suppression of the well-known,
4
2
2
−1
1
4
the BET (Brunauer-Emmett-Teller) method. Also, Zr-MOF-TCPP has a efficiency diminishing, aggregation capacity of TCPP groups by
broad Soret absorption band in the visible region at 350−500 nm and formation of the MOF structure. Support for this proposal has come
12
a Q band at 500−750 nm. Finally, synthesized Zr-MOF-TCPP was from the results of UV-vis absorption measurements, which show
found to have a particle size of 1−5 m.
that H TCPP forms aggregates in the homogeneous phase (Fig. S6).
In order to investigate the photocatalytic activity of Zr-MOF- In addition, the fact that use of a mixture of Zr-MOF and H TCPP as
4
4
TCPP, oxidative hydroxylation reactions of phenylboronic acid were the catalyst promotes only a 70% yielding reaction (entry 8, Table 1)
indicates the importance of the site isolation
Table 1. Results of oxidative hydroxylation of phenylboronic acid.a
of TCPP units in the MOF. In addition, the
nanoporous structure of Zr-MOF-TCPP could
play a role in its catalytic activity through an
Entry Catalyst
Light
Atmosphere Time (h) Yield (%)
1
2
3
4
5
6
7
Zr-MOF-TCPP
TCPP
None
Zr-MOF-TCPP
Zr-MOF-TCPP
Zr-MOF-TCPP
Zr-MOF (UiO-66)
Zr-MOF (UiO-66)
Green LED
Green LED
Green LED
None
Green LED
Green LED
Green LED
O
O
O
O
Ar
O
O
2
2
2
2
9
9
9
9
9
9
9
100
63
15
adsorptive enrichment effect.
H
4
Several reactions were carried out (Table
n.d.
n.d.
n.d.
n.d.
n.d.
1) as controls and to explore the effects of
b
c
2
2
8d
Green LED
O
9
70
2
+
4
H TCPP
9
Zr-MOF-TCPP
Zr-MOF-TCPP
Green LED
Simulated sunlight
Air
O
2
24
24
100
100
1
0
a
Reaction conditions: phenylboronic acid (0.6 mmol), TEA (3.0 mmol), catalyst (0.002 mmol of
b
TCPP) in 4 ml of MeCN:H
2
O (4:1) at pH = 7, r.t. Yields were determined by GC. The reaction was
performed without TEA. c 10 mg of the catalyst was used. d A mixture of Zr-MOF (10 mg) and
H
4
TCPP (0.002 mmol) was used as a catalyst.
2
| J. Name., 2012, 00, 1-3
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solvents and amines (Table S1 and S2). The results (entries 3−6,
Table 1) reveal that light irradiation as well as the presence of Zr-
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DOI: 10.1039/C5CC06163F
2
MOF-TCPP, O and TEA are essential for the progress of the reaction.
A survey of solvents and amines showed that a mixture of
acetonitrile (MeCN) and water as solvent and TEA as the sacrificial
electron donor are ideal for this process (Table S1 and S2, Supporting
Information). In addition, oxygen in air instead of pure O can be
2
employed as the oxidant even though a longer reaction time is
required (entry 9, Table 1). It was also found that a quantitative
yielding reaction takes place when simulated sunlight (AM1.5) is Fig. 4. (a) Recycling tests for oxidative hydroxylation of phenylboronic
acid using Zr-MOF-TCPP under green light irradiation. (b) XRD patterns
of Zr-MOF-TCPP before and after the catalytic reaction.
employed as the light source (entry 10 in Table 1). The results of an
investigation showed that the wavelength dependence of the
efficiency of the oxidation reaction (Fig. 2) matches the absorption respectively. These data show that the photoreaction is initiated by
3
profile of the TCPP groups. This result suggests that the reaction single electron transfer (SET) oxidation of TEA by Zr-MOF-TCPP*
•
+
•–
proceeds through the light absorption by TCPP units. In addition, generating TEA and Zr-MOF-TCPP (Scheme 2). The succeeding
•
–
•–
irradiation with light absorbed in the Soret band of TCCP reduction of O
chromophores is more effective for promoting than that Q band.
steps in the reaction are equivalent to those proposed previously for
It has been suggested that the key step in the oxidative this process (box in Scheme 2). Note that a direct reduction of O
2 2
by SET from Zr-MOF-TCPP gives O . The remaining
1
0
2
3
•−
•+
hydroxylation of arylboronic acids is generation of superoxide radical by Zr-MOF-TCPP* that forms O
2
and Zr-MOF-TCPP is not likely
•
−
1
anion (O
2
) through photoredox catalyzed reduction of molecular O
2
because the energy transfer affording O
In order to gain insight into heterogeneous nature of Zr-MOF-
in the visible-light photocatalyzed TCPP, a leaching test was performed. Specifically, we observed that
2
is rather favorable.
10
with simultaneous oxidation of the amine additive. In order to gain
insight into the formation of O
•
−
2
process described above, a laser flash photolysis (LFP) study was following removal of the MOF catalyst 3 h after initiation of the
1
6
conducted (Fig. S7). Owing to the low solubility of the Zr-MOF-TCPP reaction (Fig. S8). Almost no further reaction took place after the
catalyst and an ease of the salt formation of TCPP and TEA,17 removal of the catalyst. This finding suggests that no leaching of the
measurements
carbomethoxyphenyl)porphyrin (TCMPP), which is the tetramethyl a heterogeneous catalyst. The reusability of Zr-MOF-TCPP was also
ester of TCPP and gives a homogeneous solution in MeCN:H O (4:1). investigated (Fig. 4a). Following each reaction, the catalyst was
Figure 3 shows the relationships between rates of decay of transient separated, washed with methanol, dried in air and then reused for
were
carried
out
using
tetrakis(4- catalytically active sites occurs and that Zr-MOF-TCPP acts as purely
2
3
18
absorption of TCMPP* at 440 nm in the presence of TEA and O
2
at the ensuing reaction. The results indicate no significant loss of
3
*
various concentrations. The quenching rate constants for TCMPP
activity of the catalyst occurs even after 5 cycles (See also Fig. S9). In
by TEA and O
of kdecay and [TEA] and [O
respectively. Furthermore, at the concentrations utilized in the patterns of Zr-MOF-TCPP. Thermogravimetric analysis (TGA) curves
2
, obtained from slopes of Stern–Volmer type analysis addition, XRD measurements performed after the reaction (Fig. 4b)
6
7
−1 −1
2
], were 2.6 x 10 and 8.7 x 10 M s , showed that no significant change takes place in the diffraction
preparative reactions, the quenching rates for TEA (0.75 M) and O
(
2
of Zr-MOF-TCPP before and after the reactions showed no significant
3.8 mM) were calculated to be 2.0 x 106 and 3.3 x 10 s , difference (Fig. S10), indicating its high durability. These results are
5
−1
Chart 1. Yields of various phenols obtained through oxidative
hydroxylation of arylboronic acids over Zr-MOF-TCPP under green LED
irradiation.a
Fig. 3. Relationships between rates for transient absorption decay of
3
TCMPP* traced at 440 nm and concentrations of (a) TEA and (b) O .
2
Scheme 2. Proposed mechanism for oxidative hydroxylation of
arylboronic acids photocatalyzed by Zr-MOF-TCPP. PC represents the
photocatalyst (Zr-MOF-TCPP). The route in box was adopted from the
a
Reaction conditions: aryllboronic acid (0.6 mmol), TEA (3.0 mmol), Zr-
MOF-TCPP (0.002 mmol of TCPP) in 4 ml of MeCN:H O (4:1) at pH = 7,
green LED (523 nm), r.t. Yields were determined by GC.
2
10
previously-reported mechanism.
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(a) H. Furukawa, K. E. Cordova, M. O’Keeffe andVieOw.AMrtic.leYOagnlhinie,
4
5
in good agreement with the reports describing that Zr-based MOFs
are robust for catalytic applications.19
Finally, the Zr-MOF-TCPP-catalyzed oxidative hydroxylation
process was extended to other arylboronic acids. The results (Chart
Science, 2013, 341, 974−986; (b) S. F
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for the oxidative conversion of arylboronic acids to phenols.
In conclusion, oxidative hydroxylation of arylboronic acids is
promoted by Zr-MOF-TCPP (MOF-525) in the presence of air
and TEA under green LED irradiation conditions. Zr-MOF-TCPP
exhibits a higher catalytic activity than the corresponding
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These findings demonstrate the benefits of active site isolation
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The investigation was financially supported by “ACCEL Project”
from the Japan Science and Technology Agency, by Grants-in-
Aid for Scientific Research from the Ministry of Education,
Culture, Sports, Science and Technology of Japan (No. 25410241
and 15K17903) and by Global Research Program of the National
Research Foundation of Korea (NRF) funded by Ministry of
Education, Science and Technology (MEST), Korea (grant
number: 2010-00339). T. T. thanks the JSPS Research
Fellowships for Young Scientists. H. I. gratefully acknowledges
financial support in the form of a Grant-in-Aid for Scientific
Research on Priority Area “Stimuli-responsive Chemical Species”
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A
Zr-based
metal−organic
framework
with
tetrkis(carboxyphenyl)porphyrin groups catalyzes oxidative
hydroxylation of arylboronic acids as a photoredox catalyst.
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