Dichloroimidazolidinedione-activated one-pot Suzuki–Miyaura cross-coupling of phenols

Article abstract of DOI:10.1002/aoc.5383

The first general method for the Suzuki-type cross-coupling of phenols with aryl boronic acids using dichloroimidazolidinedione (DCID) as a new reagent is presented. In the presence of DCID and Pd/metal–organic framework (MOF), coupling of aryl boronic acids with a wide range of phenols, was carried out smoothly in tetrahydrofuran (THF) at reflux conditions to afford the cross-coupling products in good to excellent yields. The structures of all compounds were corroborated by ¹H- and ¹³C-NMR. A plausible mechanism for this type of reaction is proposed.

Full text of DOI:10.1002/aoc.5383

Received: 17 August 2019
DOI: 10.1002/aoc.5383
Revised: 2 November 2019
Accepted: 4 November 2019
F U L L P A P E R
Dichloroimidazolidinedione-activated one-pot Suzuki–
Miyaura cross-coupling of phenols
Kamelia Madankar | Javad Mokhtari
| Zohreh Mirjafary
Department of Chemistry, Science and
Abstract
Research Branch. Islamic Azad
University, PO Box 14515/775, Tehran,
Iran
The first general method for the Suzuki-type cross-coupling of phenols with
aryl boronic acids using dichloroimidazolidinedione (DCID) as a new reagent
is presented. In the presence of DCID and Pd/metal–organic framework
(MOF), coupling of aryl boronic acids with a wide range of phenols, was car-
ried out smoothly in tetrahydrofuran (THF) at reflux conditions to afford the
cross-coupling products in good to excellent yields. The structures of all com-
Correspondence
Javad Mokhtari, Department of
Chemistry, Science and Research Branch.
Islamic Azad University, PO Box
14515/775. Tehran, Iran.
pounds were corroborated by H- and 13C-NMR. A plausible mechanism for
1
Email: j.mokhtari@srbiau.ac.ir
this type of reaction is proposed.
K E Y W O R D S
dichloroimidazolidinedione (DCID), heterogeneous catalyst, Pd/MOF, phenols, Suzuki–Miyaura
cross-coupling
1 | INTRODUCTION
catalysts[15] and no new work except that of Nakao
et al.[16] has been done in this area. There is therefore a
The Pd-catalyzed Suzuki–Miyaura cross-coupling reac-
tion is a favorable and versatile method for forming
carbon–carbon bonds between aryls halides and boronic
acid in organic synthesis.[1–4] This is a versatile method
for the preparation of biaryls, which have applications in
natural products and pharmaceuticals.[5] In general, aryl
halides are good reagents in this coupling reaction. How-
ever, these halides are not ideal because they have several
drawbacks, such as the partial formation of dimeric and
using expensive and unavailable aryl iodides and
bromides.[6]
In recent years, the cross-coupling reactions of signifi-
cantly cheaper and more stable compounds, including
aryl triflates,[7] nonaflates,[8] aryl tosylates[9] and
mesylates[10] have become attractive due to the ubiqui-
tous presence of their starting materials – phenols – in
both the natural and synthetic worlds.[11,12] However, the
use of the aryl sulfonates limits their yield efficiency and
step economy.[13,14]
need for an innovative and general procedure for direct
Suzuki coupling of phenols that is devoid of the above-
mentioned problems.
The development of a more reliable and general
direct method for phenol coupling is needed. In this
paper, we report general, direct cross-coupling reactions
of phenols using dichloroimidazolidinedione (DCID)
using Pd/metal–organic framework (MOF) as heteroge-
neous catalyst. The coupling products were obtained by
one-pot reaction of the phenols, DCID and phe-
nylboronic acid in a single flask.DCID (2) is readily avail-
able from the reaction of dicyclohexylcarbodiimine
(DCC) with oxalyl chloride by known reported
methods.[17] From a simple search in the literature, it can
be seen that DCID has been used in very few
reactions, for example Schilter et al. reported the
chlorodehydroxylation of alcohols using DCID,[18] Guo
and coworkers have recently reported Beckman's
rearrangement of ketoximes[17] and Wang et al. have
reported chemoselective amidation from carboxylic acid
and amine using this compound.[19]
Studies in Suzuki cross-coupling reactions have
mainly focused on the development of new ligands and
Appl Organometal Chem. 2020;e5383.
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https://doi.org/10.1002/aoc.5383

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MADANKAR ET AL.
analysis and 1H NMR spectroscopy (see Supporting Infor-
mation). Pd/Cu-MOF was synthesized and characterized
as described in our previous report.[18] The loading of
Pd(0) was characterized by inductively coupled plasma
(ICP) analysis and found to be 0.9%. To investigate the
oxidation state information of palladium, X-ray photo-
electron spectroscopy (XPS) analysis of Pd 3d binding
energies was performed. Based on the peak areas of Pd
3d5/2 at 336.2 and 337.6 eV, the ratio of Pd(0) to Pd(II) in
Pd/MOF was calculated to be 1.5. To examine the effi-
ciency of DCID in the presence of Pd/MOF as catalyst in
the Suzuki cross-coupling reaction, a model coupling
reaction of phenol with phenylboronic acid was initially
tested. The results are summarized in Table 1. With
respect to applicability and availability, K2CO3 was
employed as the base in this study and the use of Et3N
gave 5a in lower yield (Table 1, entry 4). The best solvent
for this coupling reaction was THF (entry 3). We also
found that phenol was smoothly coupled with 1 equiva-
lence DCID. The chemical structure of produced interme-
Recently, we reported the use of Pd/MOF as an effi-
cient catalyst for Suzuki–Miyaura cross-coupling of aryl
halides and phenylboronic acids.[20] In continuation of
this work we introduce here a new reagent for one-pot
Suzuki–Miyaura cross-coupling of phenols by Pd/MOF
and an efficient heterogeneous catalyst (Scheme 1).
2 | RESULTS AND DISCUSSION
Synthesis of DCID was carried out according to literature
methods,[17] and the chemical structure and elemental
composition of the DCID were confirmed by elemental
SCHEME 1 One-pot Suzuki–
Miyaura cross-coupling of phenols
using DCID
TABLE 1 Optimization of the reaction conditions
Entry
Catalyst Pd/MOF (mg)
Base
Solvent
THF
Time (h)
T (ꢀC)
65
Yield (%)
1
10
20
20
20
20
20
20
20
20
20
K2CO3
K2CO3
K2CO3
Et3N
24
24
24
24
16
18
20
24
24
24
10
40
95
8
2
THF
25
3
THF
THF
65
4
65
5
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
THF
65
60
75
80
-
6
THF
65
7
8b
THF
65
THF
65
9
DMF
CH3CN
150
80
5
10
65
aReaction conditions: 1a (1.0 equiv), DCID (1.0 equiv), 4a (1.1 equiv), base (1.0 equiv) in THF (5 ml).
bReaction conditions: 1a (1.0 equiv), 4a (1.1 equiv), K2CO3 (1.0 equiv) in THF (5 ml).

DCID AS A NEW REAGENT FOR THE CROSS-COUPLING OF PHENOLS
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TABLE 2 Substrate scope of Suzuki–Miyaura cross-coupling of phenols with phenylboronic acids using DCIDa
Entry
Phenol 1
Boronic acid 4
Product 5
Yield (%)
M.p. (ꢀC)
1
95
68–70
89–90
76–78
49–50
76–78
49–50
89–90
2
3
4
5
6
7
80
82
79
82
91
86
8
15
112–113
(Continues)

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MADANKAR ET AL.
TABLE 2 (Continued)
Entry
Phenol 1
Boronic acid 4
Product 5
Yield (%)
M.p. (ꢀC)
9
68
oil
10
11
12
64
83
5
oil
oil
oil
13
90
105–107
14
15
89
66–67
No Reaction
-
-
aReaction conditions: 1 (1.0 equiv), 4 (1.1 equiv), DCID (1.0 equiv), Pd/MOF (0.01 mol% Pd), K2CO3 (1.0 equiv) in THF (5 ml) at 65 ꢀC.

DCID AS A NEW REAGENT FOR THE CROSS-COUPLING OF PHENOLS
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1
diate 3a was confirmed by H NMR spectroscopy. Inter-
After establishing optimal conditions, we explored
mediate 3a was partially coupled with phenylboronic
acid by Pd/MOF to give the expected 5a (Table 1, entries
1–9).
In another attempt, when the reaction was performed
in the presence of 10 mg of catalyst, 5a was obtained in
lower yields, therefore 20 mg catalyst (0.01 mol% Pd) was
chosen.
To further evaluate the influence of reaction time, the
coupling reaction was tested at 16, 18 and 20 h. The
results are summarized in Table 1. As shown in Table 1
lower yield of the product was achieved when the time
was reduced (Table 1, entries 5–7). To investigate the
importance of DCID in this reaction, an experiment was
performed in the absence of DICD and the results
showed that the Suzuki reaction did not proceed
(Table 1, entry 8). Finally, complete conversion to 5a
from 1a and 4a was achieved using DCID (1.0 equiv),
K2CO3 (1.0 equiv) and Pd/MOF (0.01 mol% Pd) in THF
at reflux (Table 1, entry 3).
the scope of the direct Suzuki–Miyaura coupling of
phenols
1 with arylboronic acids 4 using DCID
(Table 2). Phenols bearing electron-donating groups
were directly converted into biaryls in 82–91% isolated
yields while an electron-withdrawing nitro group in
the para position in phenol 1e (entry 8) reduced the
yield to 15%. This may be due to the slow reaction of
deactivated phenol with DCID. A sterically set of
substituted phenols 1f–g coupled with 4a to provide
the corresponding biphenyls in moderate yields under
identical conditions and the highly sterically hindered
phenol 1i resulted in a sharp drop in reaction yield
(Table 2, entry 12).
In addition, a set of 2-naphtols 1j−k coupled with 4a
to provide the products 5m–n in excellent yields under
identical conditions. An interesting point in this reaction
is selectivity in the 1-bromo-2-naphthol compound
(Table 2, entry 14). As shown in this table, in the pres-
ence of bromine, the coupling is carried out in phenolic
carbon. This shows that the activity of intermediate 3 is
greater than that of bromine in the Suzuki cross-coupling
reaction.
TABLE 3 Recovery and reusability of Pd/MOF in
Suzuki-Miyaura cross-couplinga
The catalyst Pd/MOF also exhibited good recyclability
and stability. For instance, the catalyst was recovered by
simple filtration, washed with methanol, dried in an oven
and reused four times (Table 3). The catalyst could be
stored for a long time under air atmosphere without sig-
nificant loss of catalytic activity.
A plausible mechanism for the DCID-activated direct
Suzuki–Miyaura cross-coupling of phenols by Pd/MOF is
shown in Scheme 2.
Run
1
2
3
4
Yield (%)
75
75
74
72
First, intermediate 3a is generated from the reaction
of phenol and DCID. Second, oxidative addition of 3a to
Pd(0) produces complex 6a, which undergoes
aReaction conditions: phenol (1.0 equiv), phenyl boronic acid (1.1 equiv),
DCID (1.0 equiv), Pd/MOF (0.01 mol% Pd), K2CO3 (1.0 eq) in THF (5 ml) at
65 ꢀC.
SCHEME 2 Proposed mechanism for
direct Suzuki cross-coupling using DCID
catalyzed by Pd/Cu-MOF

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MADANKAR ET AL.
transmetalation with phenylboronic acid to generate
complex 8a. Finally, reductive elimination of 8a produces
the desired coupling product 5a.
flask containing dry THF was added phenol (0.047 g,
0.5 mmol) and NaH (0.012 g, 0.5 mmol). The reaction
mixture was stirred for 30 min at room temperature
and then DCID (0.165 g, 0.5 mmol) was added. The
reaction mixture was stirred for 1 h at room tempera-
ture and completion of the reaction was monitored by
TLC. After completion of the reaction salt was filtered
and the filtrate was evaporated under reduced pres-
sure to yield 0.1 g of a white solid material (yield
97%). The chemical structure of intermediate 3a was
confirmed by FT-IR and NMR.
3 | EXPERIMENTAL SECTION
3.1 | General information
Pd/Cu2(BDC)2DABCO (Pd/MOF) was synthesized
according to our previous work.[20] X-ray powder diffrac-
tion (XRD) measurements were performed using an
X'pert MPD Philips diffractometer with Cu radiation
source (λ = 1.54050ꢀA) at 40 kV and 40 mA. XPS mea-
surements were conducted on a PHI Quantum 2000 XPS
system equipped with an Al X-ray source (1486.6 eV).
The Brunauer–Emmett–Teller (BET) surface area of the
samples was determined from N2 adsorption–desorption
isotherms using a micrometrics ASAP 2020 analyzer. The
sample was characterized using a scanning electron
microscope (SEM) from ZEISS at 30 kV with gold coat-
ing. Transmission electron microscopy (TEM) was carried
out using an EM10C-100 kV series microscope from Zeiss
(Germany) and the actual loading of palladium was
determined by ICP analysis from Shimadzu (ICPS-7000
FT-IR (ν cm−1): 2929.44, 2859.75, 1742.45, 1399.83,
1241.28, 1060.46 cm−1. 1H NMR (499.70 MHz, CDCl3):
δ 1.15 ppm (m, 4H), 1.18 (m, 4H), 1.65 ppm (m, 2H),
1.71 ppm (m, 4H), 1.79 ppm (m, 6H), 3.95 ppm (m,
1H), 6.76 ppm (d,3J = 7.59, 2H), 6.82 ppm (t,
3
3J = 8.14, 2H), 7.16 ppm (t, J = 7.44, 1H).13C NMR
(125.66 MHz, CDCl3): δ 24.41, 28.73, 28.94, 31.87,
114.74, 116.35, 121.22, 128.93, 156.27, 156.79.
3. One-pot direct Suzuki–Miyaura cross-coupling of phe-
nols
Typically, for the synthesis of 5a phenol (0.047 g,
0.5 mmol) and NaH (0.012 g, 0.5 mmol) were added to
an oven-dried 25-ml round-bottomed flask containing
dry THF. The reaction mixture was stirred for 30 min
at room temperature and then DCID (0.165 g,
0.5 mmol) was added. The reaction mixture was
stirred for 1 h at room temperature and completion of
the reaction monitored by TLC. After completion of
the reaction phenylboronic acid (0.073 g, 0.6 mmol),
K2CO3 (0.065 g, 0.5 mmol), and Pd/Cu-MOF (20 mg,
0.01 mol% Pd) weꢀre added and the reaction mixture
was stirred at 65 C for the 24 h (TLC monitoring).
After completion, the catalyst was separated by centri-
fugation and chromatography on silica gel was per to
purify the products formed. The structures of the
biaryls were confirmed by melting point and NMR
spectroscopy.
1
ver. 2). H NMR spectra were measured (CDCl3) with a
Bruker DRX-500 and 600 AVANCE spectrometer at
499.74 MHz. Chemical shifts (δ) are reported in parts per
million (ppm) relative to residual undertreated solvent as
an internal reference (1H: δ 7.26 for CDCl3; 13C: δ 77.16
for CDCl3). The following abbreviations were used to
explain NMR peak multiplicities: s = singlet, d = doublet,
t = triplet, q = quartet, m = multiplet. Melting points
were measured on an Electrothermal 9100 apparatus.
1. Synthesis of DCID
The process of Guo et al.[17] was used with minor
modification. To 2 g (1 mmol) of N,N0-DCC in 25 ml
dry dichloromethane at 0ꢀC, was added 0.9 ml
(1.05 mmol) oxalyl chloride dropwise. The reaction
mixture was stirred for 1 h at room temperature. The
solid material was separated by filtration and washed
with cold dichloromethane. The recrystallization of
white solid in ethanol yield 2.5 g DCID (yield: 97%).
Biphenyl (0.073 g, 95% yield) (5a): white solid;
mp 68–70 ꢀC; 1H NMR (499.74 MHz, CDCl3): δ
7.39 ppm (m, 2H), 7.48 ppm (m, 1.84, 4H), 7.64 ppm
(m, 4H).
1
m.p. = 174–176ꢀC. H NMR (499.77 MHz, CDCl3): δ
4 | CONCLUSION
=1.17–1.36 ppm (m, 6H), 1.66–1.69 ppm (m, 2H),
1.71–1.75 ppm (m, 4H), 1.73–1.87 ppm (m, 4H),
2.02–2.10 ppm (m, 3j = 12.59, 2j = 2.74, 4H),
3.97-4 ppm (m, j = 12.44, 3.94 Hz, 2H). (Supporting
Information)
We have developed palladium-catalyzed direct cross-
coupling reactions of phenols 1 using air-stable and inex-
pensive DCID. This method does not require the isolation
of the intermediate 3 and is therefore more convenient
than the traditional methods. Further studies on the
development of DCID in organic synthesis are in progress
and will be presented in due course.
3
2. Synthesis and characterization of 2-chloro-1,-
3-dicyclohexyl-2-phenoxyimidazolidine-4,5-dione (3a)
Typically, to an oven-dried 25-ml round-bottomed

DCID AS A NEW REAGENT FOR THE CROSS-COUPLING OF PHENOLS
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How to cite this article: Madankar K,
Mokhtari J, Mirjafary Z.
Dichloroimidazolidinedione-activated one-pot
Suzuki–Miyaura cross-coupling of phenols. Appl
Organometal Chem. 2020;e5383. https://doi.org/10.
1002/aoc.5383