Nickel-catalyzed oxidative hydroxylation of arylboronic acid: Ni(HBTC)BPY MOF as an efficient and ligand-free catalyst to access phenolic motifs

Article abstract of DOI:10.1016/j.catcom.2019.105911

A straightforward and mild oxidative ipso-hydroxylation of arylboronic acids has been achieved using a simple and non-noble metal, nickel-based reusable heterogeneous catalyst Ni(HBTC)BPY MOF (HBTC = benzene-1,3,5-tricarboxylate, BPY = 4,4′-bipyridine) in the presence of benign hydrogen peroxide as an oxidant under ambient reaction condition. The Ni(HBTC)BPY MOF exhibits excellent catalytic activity towards the formation of phenols from diverse arylboronic acids within short time and can be reused up to five times without any notable loss in its activity as well as shown high functional group tolerance even in the presence of sensitive functionalities and useful to achieve hydroxyl group in heterocycles.

Full text of DOI:10.1016/j.catcom.2019.105911

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Nickel-catalyzed oxidative hydroxylation of arylboronic acid:
Ni(HBTC)BPY MOF as an efficient and ligand-free catalyst to
access phenolic motifs
Ganesapandian Latha, Nainamalai Devarajan, Murugan Karthik,
Palaniswamy Suresh
PII:
S1566-7367(19)30372-3
DOI:
https://doi.org/10.1016/j.catcom.2019.105911
CATCOM 105911
Reference:
To appear in:
Catalysis Communications
Received date:
Revised date:
Accepted date:
11 November 2019
16 December 2019
18 December 2019
Please cite this article as: G. Latha, N. Devarajan, M. Karthik, et al., Nickel-catalyzed
oxidative hydroxylation of arylboronic acid: Ni(HBTC)BPY MOF as an efficient and
ligand-free catalyst to access phenolic motifs, Catalysis Communications (2019),
https://doi.org/10.1016/j.catcom.2019.105911
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Nickel-Catalysed Oxidative Hydroxylation of Arylboronic Acid:
Ni(HBTC)BPY MOF as an Efficient and Ligand-Free Catalyst to Access
Phenolic Motifs
Ganesapandian Latha, Nainamalai Devarajan, Murugan Karthik and Palaniswamy Suresh*
Supramolecular and Catalysis Lab, Dept. of Natural Products Chemistry, School of Chemistry,
Madurai Kamaraj University, Madurai-625021, India.
*Corresponding author:
E-mail address: ghemistry@gmail.com, suresh.chem@mkuniversity.org
Abstract:
A straightforward and mild oxidative ipso-hydroxylation of arylboronic acids has
been achieved using a simple and non-noble metal, nickel-based reusable heterogeneous
catalyst Ni(HBTC)BPY MOF (HBTC=benzene-1,3,5-tricarboxylate, BPY=4,4’-
bipyridine) in the presence of benign hydrogen peroxide as an oxidant under ambient
reaction condition. The Ni(HBTC)BPY MOF exhibits excellent catalytic activity towards
the formation of phenols from diverse arylboronic acids within short time and can be
reused up to five times without any notable loss in its activity as well as shown high
functional group tolerance even in the presence of sensitive functionalities and useful to
achieve hydroxyl group in heterocycles.
Keywords: Ni(HBTC)BPY MOF; ipso-Hydroxylation; Metal-Organic Frameworks;
Heterogeneous catalysis; Boronic acids.
1. Introduction
Phenols are one of the important and commonly used fine chemical
compounds both in industries and academics.[1] Phenolic compounds and its
derivatives exhibit wide biological properties such as antioxidant,
antihyperglycemia, antihypertension, antimicrobial and anticancer activities.[2-4]
Phenolic motifs are present in numerous natural products such as aryl steroids,
macrolides, quinines, terpenoids, and alkaloids.[5] Owing to the prevalent

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importance of phenolic motifs, a number of methods have been developed for their
direct synthesis or through functional group transformations including non-
oxidative electrophilic substitution,[6] hydroxylation of aryl halides using
hydroxide salts,[7] ligand-assisted, water-mediated hydroxylation of aryl
halides[8] and hydrolysis of diazonium salts,[9] etc., Indeed, the development of
alternative strategies for the formation of phenolic motifs has continuously
attracted more attention in synthetic organic chemistry. Besides, the existing
methodologies, ipso-hydroxylation of arylboronic acids has widespread gain
attraction owing to an extensive abundant of boronic acid derivatives that can be
converted to desired moieties even in the presence of other functionalities. Various
catalysts and reagents were studied for the ipso-hydroxylation of arylboronic acids
to corresponding phenols. Metal-based catalyst using both noble and non-noble
metals such as copper,[10] iron,[11] palladium,[12] Zinc,[13] silver[14] and
gold[15] either in the presence of a strong base or under base-free conditions using
thermal or photochemical conditions were explored. Instead, metal-free oxidations
were also developed using air[16] and stoichiometric amounts of oxidants such as
hydrogen peroxide,[17] TBHP,[18] m-CPBA,[19] oxone,[20] hydroxylamine,[21]
N-oxide,[22] PhI(OAc)2,[23] NaClO2[24] and Na2SO3.[25] Recently ipso-
hydroxylation based on a carbocatalyst was also reported.[26] However some of
the above-developed methodologies involved arduous experimental procedure or
stochiometric equivalent of oxidants, which are difficult to practice neither in
academic nor industrial applications. Thus, identifying a straightforward
methodology employing benign catalyst without any waste generation with high
selectivity is more desirable, which is still under investigation.
Metal-organic frameworks (MOFs) as a new class of crystalline
micromesoporous hybrid materials which recently attracted significant attention
that has been used in diverse synthetic applications.[27] Owing to their inherent
large surface areas, uniform and easy tunable pore make MOFs as a promising

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heterogeneous catalyst for a variety of organic reactions.[28] Though nickel-based
catalysis is well recognized in synthetic transformations, as like other transition
metal-based MOFs, the catalytic potential of nickel-based MOFs are not much
explored. Scarcely, nickel-based MOFs reported as a heterogeneous catalyst for
the oxidative coupling of alkynes and arylboronic acids,[29] cyanosilylation of
aromatic aldehydes[30] and synthesis of cyclic carbonates.[31] Ni(HBTC)BPY
MOF (HBTC = benzene-1,3,5-tricarboxylate, BPY = 4,4’-bipyridine) is explicit
in the ipso-hydroxylation of arylboronic acids. Previously this MOF was used as a
heterogeneous catalyst for the arylation of aldehydes.[32] To the best of our
knowledge there is only one report was available in homogeneous nickel salt with
BODIPY used as a photocatalyst for the synthesis of phenol from aryl halides.[33]
Herein we are reporting the Ni(HBTC)BPY MOF as a significant heterogeneous
catalyst for the ipso-hydroxylation of arylboronic acids to phenols. The present
methodology utilizes the environment-friendly hydrogen peroxide as an oxidant in
minimal equivalent, under a greener renewable ethanolic medium within short
reaction time. This non-noble metal-based nickel MOF catalyst is highly stable
and quickly recovered from the reaction medium by simple filtration and reused
several times. To our delight, this work is the first report on the heterogeneous
nickel as a catalyst employed for the ipso-hydroxylation of arylboronic acids.
2. Results and Discussion
To develop a benign and environmental friendly methodology for the ipso-
hydroxylation of arylboronic acids, using Ni(HBTC)BPY MOF as
a
heterogeneous catalyst, the required primary reaction parameters such as solvent,
temperature, time and catalyst loading are screened using phenylboronic acid (1a)
as a model substrate. Initially to screen the catalytic activity of the catalyst in
different solvents and choose the best medium, a spectrum of solvents were tested
using 30% aqueous hydrogen peroxide as an oxidant at room temperature for the
period of 60 mins. From the solvent screening results, we could observe the fact

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that the solvent plays a critical role in the Ni(HBTC)BPY MOF catalyzed
formation of phenol. The reactions involving non-polar solvents such as toluene,
DCM and DCE proceed with moderate yield. In the case of polar solvents such as
THF, chloroform, 1,4-dioxane, acetone, acetonitrile and DMF resulted in moderate
to good yield, meanwhile the protic polar solvents such as methanol, ethanol and
isopropyl alcohol afforded good to excellent yield, where ethanol gave the
maximum yield (Table 1, entry 11). With the green chemistry perspective, water
also tested as one of the solvents (Table 1, entry 2), albeit it provided a good yield,
the catalyst is not stable which turned as a paste and stacked on the walls of
reaction vessel, further analysis revealed that the catalyst was decomposed.
Among the solvent screening results, the catalyst was more efficient in ethanol
medium and as per green chemistry recommendations, ethanol is greener and
renewable solvent.[34] Finally, ethanol was fixed as a medium for the ipso-
hydroxylation of phenylboronic acid which gave phenol as a sole product with
98% yield. Furthermore, to elucidate the role of oxidants in the ipso-
hydroxylation, other oxidants such as K2S2O8, molecular oxygen, TBHP and
TEMPO were tested. Molecular oxygen does not initiate the reaction, even after
using azobisisobutyronitrile (AIBN) as an external initiator. Similarly, reaction
was inert with the K2S2O8 and TEMPO.
Table 1. Effect of solvent on the oxidation of phenylboronic acid.a
Entry
Solvents
IPA
Oxidants
H2O2
Yield (%)b
1
2
3
68
82
60
H2O
H2O2
MeCN
H2O2

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4
CHCl3
H2O2
H2O2
H2O2
H2O2
H2O2
H2O2
H2O2
H2O2
H2O2
H2O2
-
58
5
DCM
50
6
DCE
60
7
Acetone
Toluene
1,4-dioxane
THF
72
8
69
9
90
10
11
12
13
14
15
16
17
18
56
Ethanol
Methanol
DMF
98, 98c, 98d
83
50
-
Ethanol
Ethanol
Ethanol
Ethanol
Ethanol
Ethanol
TBHP
K2S2O8
O2
48e
-
-
O2, AIBN
TEMPO
-
19
25
a
Reaction conditions: Phenylboronic acid (0.4 mmol), 30% H2O2 (0.4
b
mmol), Ni(HBTC)BPY (30 wt%), solvent (1 mL) at 60 min., RT.
Isolated yield. 10 min., 2.0 eq of TEMPO was added, 2 mmol of
TBHP used.
c
d
e
Only when TBHP used as an oxidant, reaction ended up with 48% yield
after using 2 mmol equivalents, which is five times higher than that of H2O2 used
in the present study. Further to understand the mechanistic pathway of the
Ni(HBTC)BPY MOF catalyzed oxidative ipso-hydroxylation of arylboronic acid,
with the optimized condition along with hydrogen peroxide, TEMPO was used
which gave the excellent phenol formation without any drop in the yield (Table 1,
entry 11), which clearly demonstrate the reaction does not proceed through
radical pathway.

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Fig. 1 Effect of catalyst load on the Ni(HBTC)BPY catalyzed ipso-hydroxylation of arylboronic acids.
After optimized the above parameters, the exact quantity of the catalyst
required for the hydroxylation of boronic acid was systematically focused by
controlling the catalyst load. Though the optimization studies were performed up
to 40 wt% of the catalyst, initially it was started from a minimum value of 10 wt%,
which resulted only in 56% yield (Fig. 1). Upon increasing the catalyst load, a
remarkable increase in the yield was observed. The desired complete conversion
with the maximum yield 98% was reached with 30 wt% of catalyst and on further
enhancing the catalyst load does not show any improvement in the yield.
The preliminary screening studies revealed that the Ni(HBTC)BPY MOF
acts as an efficiently heterogeneous catalyst with 30% H2O2 as an oxidant in the
ethanolic medium is a suitable condition for the ipso-hydroxylation of
phenylboronic acid (1a). Furthermore, to extend the scope of the catalyst, various
arylboronic acids were subjected to ipso-hydroxylation under the above-optimized
conditions and the results were depicted in table 2.

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Almost all the tested arylboronic acids smoothly undergo the ipso-
hydroxylation under the optimized condition within 10 min., without the formation
of any other by-products such as hydroquinone, quinine, and homocoupled
products of arylboronic acids. The electronic nature of the substituents present on
the arylboronic acid does not influence much in this oxidative ipso-hydroxylation.
When the electron releasing substituents like methyl, methoxy and isopropyl (2b,
2d, 2n) are present in the para- position gave excellent yield of corresponding
phenols (94-96%); meanwhile arylboronic acids possessing substituents on ortho
position (2c) resulted with a mild drop in the yield (88%). Similarly, boronic acids
with electron-withdrawing groups like chloro, bromo, iodo and nitro groups on the
para position (2f, 2h-2j) gave excellent yield 93-97%, albeit when they present on
the ortho or meta position (2g, 2k, 2l, 2m) there was a mild decrease in the yield
(84-88%) was noted. In the case of di-substituted arylboronic acid (2e) with
methoxy groups at para and meta positions gave good yield (87%). Aryl
substituents like biphenyl (2o), diphenyl ether (2q), and terphenyl (2r) were also
produced excellent yields of 89-92%. Fused ring system like naphthyl gave good
yield of 90%. Considering arylboronic acids containing heteroatoms (2x-2z) a
notable decrease in the yield (72-79%) was observed. It might be owing to the
coordination of the hetero atom with the active metal sites present in the catalyst
which prevents the further progress of the reaction. In the case of hydroxylation of
1,4-phenyldiboronic acid (2w), it required two-fold excess of oxidant with
extended reaction time up to 30 min producing 91% of yield without prone to
further oxidation. Remarkably, the catalyst is chemoselective towards ipso-
hydroxylation even in the presence of sensitive functional groups such as nitrile
(2n), formyl (2v), secondary amine (2z, 2aa) and multiple functional groups like
carbonyl with secondary amine (2ab) is also stable under the optimized condition
gave the corresponding hydroxylated product with a reasonable yield of 72-89%.
Finally, the optimized system was also well suitable for the alicyclic compound

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Table 2. Ni(HBTC)BPY MOF Catalyzed ipso-hydroxylation of arylboronic acids.a

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aReaction conditions: Phenylboronic acid (0.4 mmol), H2O2 (0.4 mmol), Ni(HBTC)BPY MOF
b
(30 wt%), EtOH (1 mL), 10 min., RT, All are isolated yields. Gram scale, cTON, dTOF (min.-1)

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which also produced the corresponding cyclohexanol (2u) in a good yield of 90%
confirmed that the developed protocol is not only restricted to arylboronic acids.
The potential of the catalyst Ni(HBTC)BPY MOF has also been tested for the
gram scale ipso-hydroxylation of phenylboronic acid which produced 97% yield.
Table 3. Effect of nickel sources on the oxidation of phenylboronic acid.a
Entry
Catalyst
Yield(%)b
trace
25c
30c
35c
1
2
3
4
5
-
Ni(NO3).6H2O
NiCl2.6H2O
Ni(OAc)2.4H2O
Ni(OH)2
30c
6
Ni(HBTC)BPY MOF
98d
a
Reaction conditions: Phenylboronic acid (0.4 mmol),
H2O2 (0.4 mmol), catalyst (0.4 mmol), EtOH (1 mL), 10
min., RT, Isolated yield. After 120 min., d Catalyst (30
b
c
wt%).
To figure out the role of nickel present in the framework and to ascertain its
true catalytic efficiency, various other homogeneous nickel sources were also
examined under the identical condition, and the results were given in table 3. All
the homogeneous nickel salts reacted almost, in the same manner, resulted in the
poor formation of phenol even after longer reaction time (120 min.). These results
are strongly emphasizing the role of nickel ions supported by the framework
which enhances its catalytic efficiency than the free metal ions. Further to
understand the competence of the framework nickel ions in the ipso-
hydroxylation, other Lewis acidic MOFs such as Cu(tpa), Cu(BTC), Fe(BTC), Fe-

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MIL-53 and Ni(BDC)DABCO were compared under the optimized condition.
Other metals present in the framework such as copper (Table 4, entries 1, 2) and
iron (Table 4, entries 3, 4) are not competent under the present screened condition
and shown inferior performance, which resulted in the poor formation of phenol
(25-35%).
Table 4. Effect of catalyst on the oxidation of phenylboronic acid.a
Entry
Catalyst
Yield(%)b
1
2
3
4
5
6
Cu(tpa) MOF
30
38
25
32
69
98
18c
Cu3(BTC)2 MOF
Fe(BTC) MOF
Fe-MIL-53
Ni(BDC)(DABCO) MOF
Ni(HBTC)BPY MOF
Ni(NO3).6H2O:BTC:BPY
7
a
Reaction conditions: Phenylboronic acid (0.4 mmol),
H2O2 (0.4 mmol), catalyst (30 wt%), EtOH (1 mL) at 10
min., RT, b Isolated yield. As a 1:1:1 mixture.
c
Meanwhile, another nickel MOF, Ni(BDC)DABCO catalyzed the ipso-
hydroxylation under the identical reaction condition, however gave only moderate
yield (69%) of phenol. The above reports prove that the Ni2+ present in the
framework of Ni(HBTC)BPY catalyzes the ipso-hydroxylation of arylboronic acid
proficiently within the shorter reaction time. The observed results strongly suggest
that the presence of high surface area 1232 m2g−1, (Fig. S4, SI), porous nature, and
the coordinatively unsaturated nickel center ligated by the trimesic acid and 4,4’-
bipyridine are all together made a potential catalytic center in Ni(HBTC)BPY
MOF and shows excellent reactivity towards ipso-hydroxylation. Further, in order
to confirm the role of framework metal structure in the present hydroxylation

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reaction, a control experiment was performed using the corresponding precursors
of Ni(HBTC)BPY MOF such as Ni(NO3).6H2O, trimesic acid and bipyridine as a
physical mixture in 1:1:1 ratio under the optimized condition, they gave only 18%
(Table 4, entry 7) yield and also the product separation from the reaction medium
is highly complicated. This control study strongly ascertains the catalytic role of
nickel, when it presents in the framework is responsible for the catalysis.
Further, to fortify the true heterogeneity of the Ni(HBTC)BPY MOF
catalyst, a filtration test was performed with the optimized reaction parameters
(Table S2, SI). This filtration test revealed that the catalyst is high stability in
ethanol medium and Ni(HBTC)BPY MOF behaving truly in heterogeneous nature
under the optimized reaction conditions without leaching of metal ions due to
breaking or deforming the frameworks. Obtained results were endorsed by the
inductively coupled plasma optical emission spectroscopy (ICP-OES)
measurements of the ethanol filtrate from the reaction mixture, where no proof of
metal leaching was observed, manifesting the true heterogeneity of the
Ni(HBTC)BPY MOF.
The reusability aspect determines the stability and strength of the
heterogeneous catalyst. To ascertain the sustainability, the catalyst was filtered at
the end of the reaction, dried under vacuum at 120 °C for 2 h, and reused. This
practice was repeated at the end of each cycle, and the catalyst was reused up to
five times without any remarkable loss in its activity (Fig. S17, SI). Besides, the
stability of the catalyst was confirmed by subjecting the reused catalyst to the
analytical tools such as FTIR, Powder XRD and SEM (Fig. S18 to Fig. S20, SI).
All the evidence mentioned above strongly endorses the stability of the reused
catalyst even after five successive runs.
With these intriguing results, a plausible mechanism was proposed based
on the literature reports [29, 35] for the Ni(HBTC)BPY MOF catalyzed ipso-
hydroxylation of arylboronic acids as shown in scheme 1. MOF based
heterogeneous catalysis offers advantages such as large pores, high surface area

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and porosity together with a high number of active sites and exposed apical
coordination sites. Owing to this advantages nickel in Ni(HBTC)BPY MOF
promotes ipso-hydroxylation of arylboronic acids. Notably, in the present metal-
organic framework, the Ni2+ ion is coordinated with the two carboxylic groups and
one nitrogen from the bipyridine organic linker, which stabilises the variable
oxidation states nickel ion during the oxidative addition process through
expanding coordination sphere. This phenomenon missing with the other
homogeneous nickel salts. Hence, when Ni2+ is more reactive and promotes the
oxidative hydroxylation when it presents in the framework. It is also revealed by
the controlled experiment by a physical mixture of precursors of Ni(HBTC)BPY
MOF (Table 4, entry 7). In the proposed mechanism. initially, phenylboronic acid
coordinated to the nickel present in the MOF through transmetalation and form II
which was further oxidized using hydrogen peroxide resulted in the formation of
III and IV. During the oxidation Ni2+ gets oxidized into Ni3+ and form an
intermediate III. Then the intermediate III undergoes rearrangement by
eliminating a water molecule to form IV. The rearranged adduct IV upon
subsequent hydrolysis gives the hydroxylated product. Finally, the metal gets back
to its original oxidation state in the framework and ready for next cycle of
hydroxylation.

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Scheme 1. A plausible mechanism for the Ni(HBTC)BPY MOF-catalyzed ipso-hydroxylation of
phenylboronic acid.
3. Conclusions
In conclusion, we have demonstrated a simple and efficient protocol for the
ipso-hydroxylation of arylboronic acids using Ni(HBTC)BPY MOF as a
heterogeneous catalyst. Using this catalyst, ipso-hydroxylation has been achieved
in a shorter time using a minimal amount of H2O2 as an environmentally benign
oxidant under renewable ethanol medium. This catalyst shows wide functional
group tolerance under mild conditions with excellent yield. The present nickel
mediated ipso-hydroxylation is compatible for the synthesis of phenols possessing
electron releasing, electron-withdrawing and heterocyclic substituents an attractive
yield. The as-synthesized and reused Ni(HBTC)BPY MOF catalyst was
characterized using FTIR, PXRD and SEM analyses, which shows that the catalyst
was highly stable even after five consecutive reuses. Besides, this is the first report
in heterogeneous nickel catalyzed ipso-hydroxylation of arylboronic acids.
Acknowledgments
GL thank UGC for Non-NET fellowship under XII plan scheme. PS
gratefully acknowledge the financial support from the Science and Engineering

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Research Board (SERB), New Delhi, India (Grant No. SR/FT/CS-53/2011) and
Council for Scientific and Industrial Research, New Delhi, India (CSIR Grant No.:
02(0191)14/EMR-II). Also, PS gratefully acknowledges UGC, New Delhi for
UGC-Raman Postdoctoral fellowship. We thank University Grants Commission
under University with Potential for Excellence program (UGC-UPE), DST-FIST
(for LC-MS), and DST-PURSE (for FTIR, SEM, and EDX) for the instrumental
facility.
Author Contributions Section
Ganesapandian Latha: Conceptualization, Methodology, Investigation
Nainamalai Devarajan: Methodology, Investigation
Murugan Karthik: Validation, Investigation
Palaniswamy Suresh*: Conceptualization, Supervision, Writing - Review & Editing
Declaration of interests
The authors declare thatthey have no known competingfinancial interests orpersonal relationships
that could have appeared to influence the work reported in this paper.
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Graphical abstract:
Highlights
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The firstreport on heterogeneous nickel as a catalystfor ipso-hydroxylation of arylboronicacids
Ni(HBTC)BPYMOF was used as a heterogeneous catalystfor ipso-hydroxylation undermild
condition
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Chemoselective towards ipso-hydroxylation in the presence of sensitive functional groups
Short reaction time with aminimumoxidantload and renewableethanolas a greenersolvent
Ni(HBTC)BPYMOF is stable and reusable forseveral cycles with excellentcatalyticefficiency