Domino: N-/C-or N-/N-/C-arylation of imidazoles to yield polyaryl imidazolium salts via atom-economical use of diaryliodonium salts

Article abstract of DOI:10.1039/c9cc05237b

Herein, we disclose a Cu-mediated domino di-/triarylation reaction of imidazoles to efficiently access polyaryl imidazolium salts in a single step by using two aryls as well as an anion of a diaryliodonium salt. The diarylation shows high atom economy and

Full text of DOI:10.1039/c9cc05237b

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DOI: 10.1039/C9CC05237B
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Domino N-/C- or N-/N-/C-arylation of imidazoles to yield polyaryl
imidazolium salts via atom-economical use of diaryliodonium salts
Received 00th January 20xx,
Accepted 00th January 20xx
Shiqing Li,*a Hongxu Lv,a Yu Yu,a Xiuqing Ye,a Baisong Li,a Songming Yang,a Yanru Moa and Xiangfei
Kong*a
DOI: 10.1039/x0xx00000x
Herein, we disclose Cu-mediated domino di-/triarylation reaction of 2-formylbenzonitrile and aryl-mesityl iodonium salts with
of imidazoles to efficiently access polyaryl imidazolium salts in a utilization of the iodine atom, while the atom economy was
single step via using two aryls as well as anion of a diaryliodonium dramatically lowered due to two equivalents of iodonium salts
salt. The diarylation shows high atom economy and excellent were wasted.[14] Since in most cases the mass of anions, such
selectivity with unsymmetrical iodonium salts.
as OTfˉ, OTsˉ and PF6ˉ, generally abandoned in previous
reports are weightier than iodine atom, the overall atom
economy (AE) is not that high.[15] To our knowledge, atom-
economical use of the anion as well as the two aryls of a
diaryliodonium salt to form ionic compounds has not been
reported yet.
Diaryliodonium salts, as old brand compounds discovered in
1894,[1] have blossomed into one of the most efficient
arylating reagents owing to the advantages of high reactivity
and easy preparation.[2] However, poor atom economy is their
common drawback since at least one equivalent of aryliodide
residual is generated as “waste“. In recent years, a new
pattern, namely atom-economical use of both aryl groups of
the diaryliodonium salt, has emerged.[3] In most of the atom-
economical cases cyclic diaryliodonium salts are utilized, which
undergo an intramolecular reaction in the second process.[4]
The intramolecular aryl migration of acyclic iodonium salts
have been reported by Shafir[5] and Wang[6]. The concept
about atom-economical application of alkynyl iodine(III)
derivatives[7] and ArI(OAc)2[8] have also been demonstrated.
Comparatively, the acyclic diaryliodonium salts undergoing a
tandem intermolecular arylation is more challenging and the
examples are relatively rare. Dual arylation at the same site of
S[9] and N[10] have been reported to synthesize diaryl sulfides
and triarylamines, respectively. The first example of
bondforming at two different positions was tandem C-/N-
Previous work (utilizing two aryls)
(a) Tandem C-H and N-H arylation of indoles[11]
1) CuI (20 mol%)
Ar
dtbpy(1.1 eq)
dioxane, 60 oC, 24 h
X
I
+
Ar
Ar
2) DMEDA (30 mol%)
K3PO4(2 eq)
110 oC, 16 h
N
N
H
Ar
1.05-1.1 eq
(b) Domino N-/C-arylation of pyrazoles[12]
1) K2CO3 (1.2 eq)
N
xylene, 70 oC, 12 h
X
N
I
N
+
Ar
Ar
Ar
N
2) [RuCl2(p-cymene)]2 (10 mol%)
MesCOOH (0.3 eq)
K2CO3 (2.0 eq)
H
1.2 eq
Ar
140 oC, 18 h
(c) Domino borylation/Suzuki-Miyaura cross-coupling[13]
1) B2pin2 (1.5 eq)
X
MeOH, 50 oC, 24 h
I
Ar
Ar
Ar
Ar
2) Pd(PPh3)4(10 mol%)
Cs2CO3(2 eq)
arylation reaction of indoles reported by Greaney (Fig. 1a)[11]
.
toluene, 80 oC, 16 h
Subsequently, Greaney performed a domino N-/C-arylation
reaction of pyrazoles via generation of a directing group in situ
(Fig. 1b).[12] Muñiz described a domino borylation/Suzuki–
Miyaura reaction of diaryliodonium salts to form biaryl
skeletons (Fig. 1c).[13] In these domino reactions two
differential conditions are necessary and both iodine atom and
anion are abandoned. Li and co-workers reported a cyclization
This work (Utilizing two aryls and the anion)
(d) Domino N-/C- and N-/N-/C-arylation of imidazoles:
Ar
R
R
N
X
Ar
X
Ar
I
I
N
N
N
N
(2 eq)
(1 eq)
Ar
Ar
I
Ar
Ar
R = aryl, alkyl
R = H
N-/N-/C-arylation
N
only waste
X
X
N-/C-arylation
Ar
Ar
Fig. 1 Atom-economical use of diaryliodonium salts for different bond formation
in one pot.
In order to enhance the AE by utilizing the two aryls and anion,
we turned our attention to polyaryl azolium salts, which are
important organic optoelectronic materials,[16] anion exchange
materials[17] and abnormal N-heterocyclic carbenes (aNHCs)
precursors.[18] While the synthesis of polyaryl imidazoliums,
a. Guangxi Key Laboratory of Electrochemical and Magneto-Chemical Function
Materia, College of Chemistry and Bioengineering, Guilin University of
Technology, Guilin 541004, P. R. China. E-mail: lisq@glut.edu.cn;
xiangfei.kong@glut.edu.cn.
†Electronic Supplementary Information (ESI) available: Experimental procedures
and NMR data. See DOI: 10.1039/x0xx00000x
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in the highest yield of 86% with a high AE of 65V%iew(eArntitcrleyO1nl2in)e.
DOI: 10.1039/C9CC05237B
Treatment of Ph2IOTf with 1a could also afford 4a-OTf in a high
yield of 80% (AE= 61%), indicating that the weightier anions were
compatible well in this reaction (entry 13).
especially pentaaryl imidazoliums, needed tedious procedure or
noble metal catalyst.[19] Imidazoles could be quaternized by
diaryliodonium salts leaving the aryl iodides as “waste”,[20] while the
C2-H of imidazolium salts could be arylated by aryl iodides.[21]
Hence, a question is formed in our mind: if the aryl iodide residuals,
generated in the N-quaternization, could be captured to initiate the
following C-arylation to form polyaryl imidazolium salts (Fig. 1d).
Herein, we report the domino N-/C-arylation of N-substituted
imidazoles with high atom economy and selectivity in an identical
condition, leaving an iodine atom as the only “waste”. Furthermore,
a novel N-/N-/C-arylation reaction of imidazoles to form pentaaryl
imidazoliums in a single step is revealed for the first time.
Cu2O (5 mol%)
I
N
N
N
N
Ph
Ph
Ph Ph
N
N +
DMF, 120 o
4 h
C
Ph
X
X
X
1a
BF4
2g, 2i, 2k
3b-d
3a-X
O
OTf
I
OTf
I
I
N
2i
2g
2k
O
N
3a 3b
:
3a-OTf 3d
: = 0:85
= 90:0
3a-OTf 3c
:
= 72:0
Scheme 1 Selectivity of aryl transfer of unsymmetrical iodonium salts in N-
quaternization. The groups in bold transfer first.
Table 1 Optimization of the diarylation reaction conditionsa
BF4
BF4
BF4
Ph
[M]/base
N
N
Before exploring the scope of the diarylation, the selectivity of
aryl transfer with unsymmetrical iodonium salts in the N-
quaternization was tested by using 5 mol% Cu2O as the catalyst
(Scheme 1). Treatment of 1a with [o-MePh-I-Ph]BF4 2g or [Ph-l-
uracil]OTf 2i could afford 3a or 3a-OTf in 90% and 72% yields,
respectively, and the regio-isomeric 3b and 3c were not detected.
This result implied that less sterically hindered phenyl group
transferred first contrarying to Greaney’s case.[12] Then we
extended the examples to vinyliodonium salt [(E)-styryl-I-Ph]OTf 2k.
As expected, the styryl component transferred with complete
selectivity to exclusively deliver 3d in 85% yield.
Ph
Ph
I
N
N
+
N
+
N
DMF, 120 o
C
Ph
Ph
Ph
Ph
Ph
4a
20 h
2a
1a
3a
Entry
Metal/base (equiv)
Time (h)
Yield (%)b
3a:4a
1c
2c
3c
4c
5
Cu(OAc)2 (0.1); NaOAc (1)
Cu2O (0.1); NaOAc (1)
Cu2O (0.1); K2CO3 (1)
Cu2O (0.1); K3PO4 (1)
Cu2O (0.1), NaOAc (1)
Cu2O (0.1), K2CO3(1)
Cu2O (1)
4; 20
4; 20
4; 20
4; 20
20
42:29
40:37
0:46
0:74
trace:15
0:0
6
20
7
20
0:78
BF4
Ph
Cu2O (1 equiv)
DMF, 120 oC
20 h
BF4
Ph
8
Cu(OAc)2 (1)
20
45:10
20: 23
trace:30
96:0
I
+
N
N
Ph
R
N
N
9
R
CuSO4 (1)
20
1 equiv
Ph
10
11
12d
13e
CuCl (1)
20
1
2a
4
Cu2O (0.05)
20
BF4
Cu2O (1)
20
0:86
4b
, R = 2-Me, 80%
BF4
R
N
N
4c
4d
4e
, R = 3-OMe, 72%
, R = 4-Me, 81%
, R= 4-OMe, 88%
, R = 4-CN, 56%
N
N
Ph
Cu2O (1)
20
0:80
Ph
Ph
a
Ph
4b
Reaction conditions: 1a (0.2 mmol), 2a (0.24 mmol), copper salt (x equiv) and
base (y equiv) were stirred in DMF (1 mL). Isolated yields. The copper catalyst
was added in step 1 (4 hours) and the base was added in step 2 (20 hours). 2a
(0.2 mmol, 1 equiv). e Ph2IOTf was used instead of Ph2IBF4.
4f
b
c
4g
, 63%
-f
d
4h
, R = 3-OMe, 61%
, R = H, 75%
4i
4j
BF4
Ph
BF4
Ph
, R = 4-Cl, 83%
Initially a two-step operation was tried by choosing N-phenyl
imidazole 1a and diphenyliodonium tetrafluoroborate 2a as the
standard substrates. The reaction was catalyzed by a copper salt for
4 hours in step 1 before a base was added for another 20 hours in
step 2 (Table 1, entries 1-4). K3PO4 was most efficient and gave dual
arylating product 4a in 74% yield (entry 4). However, the reaction
was inefficient when the catalyst and the base were added at the
same time (entries 5 and 6). These results implied the base was
ineffective in step 1. Pleasingly using one equivalent of basic Cu2O
instead of the base could give 4a as the sole product in a good yield
of 78% (entry 7). While the diarylation was frustrated when cutting
down the dose of Cu2O or reducing the reaction time (see ESI†).
Also the acidic copper salts (entries 8-10) and other metal salts
(such as [Pd] and [Ag], see ESI†) were confirmed undesirable. A
reversed result was observed when cutting down the usage of Cu2O
to 5 mol%, in which 3a was solely generated in 96% yield (entry 11).
Pleasingly reducing the dose of 2a to 1 equivalent could isolate 4a
N
N
N
N
4k
, R = 4-Me, 79%
4l
, R= 4-OMe, 70%
R
Ph
Ph
4h
4m,
R = 4-NMe2, 74%
4n
, 57%
-m
BF4
BF4
BF4
Ph
N
N
N
N
N
N
Me
Ph
Ph
S
Ph
4q
Ph
4o
Ph
4p
, 90%
, 94%
, 66%
Scheme 2 Scope of imidazoles. Reaction conditions: 1 (0.2 mmol), 2a (0.2 mmol)
and Cu2O (1 equiv) were stirred in DMF (1 mL) for 20 h, isolated yields.
With the results in hand, the scope of imidazoles was examined
first (Scheme 2). Both electron-rich and electron-deficient
functional groups, such as methyl, methoxy, dimethylamino, cyano
and halogen, on the phenyl ring of (benz)imidazoles were well
2 | J. Name., 2012, 00, 1-3
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tolerated and gave the corresponding triarylated (benz)imidazolium
salts in good to high yields (4b-f and 4h-m) with high AE values up
to 66% (see ESI†). The bulky 1-naphthyl imidazole and
benzimidazole were both performed smoothly (4g and 4n). Notably,
N-thienyl benzimidazole also could react with 2a effectively and
afford 4o in a good yield of 66%. The N-alkyl imidazole, such as N-
ethyl benzimidazole and N-methyl imidazole, performed more
efficient and gave 4p and 4q in excellent yields of 90% and 94%,
respectively.
Then the scope of iodonium salts was examined with (hetero)aryl
substituted imidazoles under the optimized reaction conditions and
the results are summarized in Scheme 3. Various symmetrical
iodonium salts containing both electron-rich and electron-deficient
groups were compatible well and gave corresponding products 5a-h
in good yields. As expected, unsymmetrical iodonium salts could
also diarylate 1a smoothly, where less sterically hindered aryls
transferred first with complete selectivity in the first arylation and
then the 2-iodotoluene generated in situ was captured in the
second arylation (5i-k). Among them 5k was isolated in the lowest
yield because that mono N-arylated compound 3e was isolated as a
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R
R
DOI: 10.1039/C9CC05237B
X
BF4
BF4
R
R
I
N
N
Cu2O (1.1 equiv)
DMF, 120 oC
20 h
X
Ar
Ar
+
Ar
Ar
N
N
H
2 equiv
X = C, N
Ar
6
2
7-9
N
N
BF4
N
R
BF4
N
N
BF4
N
N
R
R
a
b
7a
, R = H, 71%
, R = 4-Cl, 82%
7d
, 40%(42% )
7b
7c
, 52%
R'
R'
a
8a
, R = R' = H, 76% (78% )
BF4
R
BF4
R
N
N
8b
8c
, R = 4-Me, R' = H, 61%
N
N
, R = 4-Cl, R' = H, 83%
8d
, R = H, R' = 3-OMe, 70%
R
8e
8f
, R = 4-Cl, R' = 3-OMe, 69%
c
, R = R' = 4-OMe, 65% (49% )
9
8a-f
, 50%
by-product (see ESI†). The imidazolium 5l containing a styryl group Scheme 4 Scope of triarylation. Reaction conditions: 6 (0.2 mmol), 2 (0.4 mmol)
and Cu2O (1.1 equiv) were stirred in DMF (1.5 mL) for 20 h, Isolated yields. a Yield
of diarylation using an N-aryl triazole/imidazole as substrate. 100 ℃. Yield of
8f-OTs.
could be generated in a good yield of 71%. In each case no
b
c
regioisomers were observed, it revealed excellent selectivity of this
N-/C-diarylation reaction. Generally, the comprehensive factors of
reasonable substrate ratio (1:1), high yields and anion utilization
make the diarylation exhibit high atom economy.
As we know, the N-H arylation of azoles with diaryliodonium
salts has been well established,[22] we would like to see if it could
happen in our condition. Thus a novel domino triarylation (N-
arylation/N-quaternization/C-arylation) could be realized from
simple azoles and diaryliodonium salts in one pot. As shown in
Scheme 4, various azoles could be triarylated smoothly by two
equivalents of diaryliodonium salts and gave corresponding polyaryl
azolium salts in moderate to high yields. For examples, compounds
7a-d could be obtained from simple azoles in satisfactory yields via
this triarylation.[23] Pleasingly pentaaryl imidazolium salts 8a-f were
efficiently obtained in high yields from commercially available 4,5-
diaryl imidazoles and corresponding iodonium salts. It is worth
noting that compounds 8b-e were achieved for the first time and
they cannot be afforded by Ghonim’s and Liu’s methods.[19] The
reaction of 6a and Ph2IOTs delivered salt 8f-OTs in 49% yield with
OTsˉ as the counteranion. Using 1,4,5-triphenyl imidazole 1s and 2a
to undergo a diarylation gave 8a in an approximate yield to that of
triarylation, indicating that this triarylation was very efficient.
Besides, phenanthrene-fused triarylimidazolium 9 belonging to
polyaryl imidazolium as well as polycyclic imidazolium salt was
reached in 50% yield for the first time. The triarylation also show
good selectivity in the reaction of 6a, 2a-OTf and [Ph-I-mesityl]OTf
(2l), giving 3a-OTf and 4a-OTf in 20% and 67% yields, respectively,
without mesityl transferred products observed (see ESI†).
X
X
I
N
N
Cu2O (1 equiv)
DMF, 120 oC
20 h
R
Ar2
Ar1
Ar2
+
N
N
R
Ar1
R = (Hetero)Aryl
1
2
5
Symmetrical diaryliodonium salts:
BF4
N
N
R
Ar
BF4
N
N
R
R
R'
5a
5b
5c
5d
5e
, Ar = phenyl, R = 3-Br, 51%
, Ar = phenyl, R = 4-Me, 61%
, Ar = phenyl, R = 4-Cl, 74%
, Ar = 2-thienyl, R = 4-OMe, 67%
, Ar = 2-thienyl, R = 4-Cl, 57%
R
, R= Br, R' = H, 59%
5f
Unsymmetrical diaryliodonium salts:
5g
5h
, R = OMe, R' = H, 55%
, R = Br, R' = OMe, 63%
X
N
N
Based on the above findings (catalytic amount of Cu2O for N-
quaternization and equivalent amount of Cu2O for C-arylation)
R
OTf
N
N
N
N
and previous reports,[20-22,24,25]
a possible mechanism is
R'
R
O
proposed (see ESI†). Initially, diaryliodonium salt adds
oxidatively to the CuI species generate Ar–I and a Ar–CuIII
species, which react with imidazoles to give N-aryl imidazoles
2.[22] 2 reacts with Ar–CuIII species could afford imidazolium
3.[20,24] Then an NHC–CuI complex I is formed between 3 and
Cu2O. The oxidative addition of I with Ar–I gives an NHC–CuIII
complex II, which undergoes reductive elimination to give the
final product.[21,25]
5i
5j
, R= H, X = BF4, 63%
, R = OMe, X = OTf, 46%
OTf
O
N
N
5k
, R =CN, R' = H, 32%
5k'
, R =H, R' = CN, 58%
Ph
5l
, 71%
Scheme 3 Scope of diaryliodonium salts. Reaction conditions: 1 (0.2 mmol), 2
(0.2 mmol) and Cu2O (1 equiv) were stirred in DMF (1 mL) for 20 h, isolated yields.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
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Adv. Synth. Catal., 2017, 359, 2202; (d) Y. Xie, JV.ieZwhAornticgle, OYn.liLnie,
X. Xiao, L. Zou, Y. Liu, K. Zhang and DJ.OIH: 1e0,.1C0h39e/mC9isCtrCy0S5e2l3e7cBt
2018, 3, 1655; (e) R. Pothikumar, C. Sujatha and K.
Namitharan, ACS Catal., 2017, 7, 7783.
(a) M. Wang, J. Wei, Q. Fan and X. Jiang, Chem. Commun.,
2017, 53, 2918; (b) L. Liu, J. Qiang, S. Bai, Y. Li and J. Li, Appl
Organometal Chem., 2017, 31, e3810; (c) M.-T. Zeng, W. Xu,
X. Liu, C.-Z. Chang, H. Zhu and Z.-B. Dong, Eur. J. Org. Chem.,
2017, 6060.
In conclusion, Cu2O-mediated domino N-quaternization/C-
arylation of N-aryl/alkyl imidazoles in a single operation has
been developed for the first time, where all the two aryls and
anion except the iodine atom of an acyclic diaryliodonium salt
are used. This diarylation features high efficiency, good
functional tolerance, ease operation, excellent selectivity and
high atom economy. The unprecedented N-arylation/N-
quaternization/C-arylation reaction between imidazoles and
diaryliodonium salts is achieved as a short and efficient
method to construct polyarylated imidazolium salts. This work
supplies new utilization mode of diaryliodonium salts to
inspire the synthetic chemistry of ionic compounds.
Investigation on these polyarylated imidazolium salts as novel
organic photoelectric materials are in progress in our
laboratory.
9
10 S. G. Modha, M. V. Popescu and M. F. Greaney, J. Org. Chem.,
2017, 82, 11933.
11 S. G. Modha and M. F. Greaney, J. Am. Chem. Soc., 2015, 137,
1416.
12 C. J. Teskey, S. M. A. Sohel, D. L. Bunting, S. G. Modha and M.
F. Greaney, Angew. Chem., Int. Ed., 2017, 56, 5263.
13 N. Miralles, R. M. Romero, E. Fernández and K. Muñiz, Chem.
Commun., 2015, 51, 14068.
14 L. Liu, J. Qiang, S.-H. Bai, H.-L. Sung, C.-B. Miao and J. Li, Adv.
Synth. Catal., 2017, 359, 1283.
15 Atom economy (AE) = (molecular mass of the desired
reaction product)/(molecular mass of all reactants) × 100%.
The AE values of diarylation reaction in previous reports are
listed in the ref. 3b and they are almost lower than 50%.
16 (a) A. J. Boydston, P. D. Vu, O. L. Dykhno, V. Chang, A. R.
Wyatt, II, A. S. Stockett, E. T. Ritschdorff, J. B. Shear and C. W.
Bielawski, J. Am. Chem. Soc., 2008, 130, 3143; (b) J. Wang, X.
Gu, P. Zhang, X. Huang, X. Zheng, M. Chen, H. Feng, R. T. K.
Kwok, J. W. Y. Lam and B. Z. Tang, J. Am. Chem. Soc., 2017,
139, 16974; (c) J. Wang, X. Gu, H. Ma, Q. Peng, X. Huang, X.
Zheng, S. H.P. Sung, G. Shan, J. W.Y. Lam, Z. Shuai and B. Z.
Tang, Nat. Commun., 2018, 9, 2963.
This work was supported by grants from Guangxi Natural
Science Fundation (2018GXNSFAA294037), the Ph. D. Scientific
Research Foundation of Guilin University of Technology and
Key Laboratory of Electrochemical and Magneto-Chemical
Function Materia.
Conflicts of interest
There are no conflicts to declare.
Notes and references
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For recent reviews, see: (a) V. V. Zhdankin and P. J. Stang,
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