Four-component quinazoline synthesis from simple anilines, aromatic aldehydes and ammonium iodide under metal-free conditions

Article abstract of DOI:10.1039/c8gc02654h

A four-component procedure for the preparation of substituted quinazolines from anilines, aromatic aldehydes and ammonium iodide is described. The C-H bond ortho to the amino group in anilines was directly functionalized under metal-free conditions. Two a

Full text of DOI:10.1039/c8gc02654h

An article presented by Prof. Guo-Jun Deng et al. of
Xiangtan university, Xiangtan, China.
As featured in:
Volume 20 Number 24 21 December 2018 Pages 5407–5552
Four-component quinazoline synthesis from simple anilines,
aromatic aldehydes and ammonium iodide under metal-free
conditions
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A four-component procedure for the preparation of substituted
quinazolines from readily available anilines, aromatic aldehydes
and ammonium iodide has been developed. The C–H bond
ortho to the amino group in anilines was directly functionalized
and used for a further cyclization process under metal-free
conditions. Two aldehydes were involved in this reaction to
provide two C1 sources and ammonium iodide was used as one
of the nitrogen sources. This reaction provides a strategy for
the facile construction of substituted quinazolines from simple
anilines and other readily available reactants.
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Four-component quinazoline synthesis from
simple anilines, aromatic aldehydes and
ammonium iodide under metal-free conditions†
Jinjin Chen,a Dan Chang,a Fuhong Xiao *a and Guo-Jun Deng
Cite this: Green Chem., 2018, 20,
5459
Received 21st August 2018,
Accepted 15th October 2018
a,b
*
DOI: 10.1039/c8gc02654h
rsc.li/greenchem
A four-component procedure for the preparation of substituted
quinazolines from anilines, aromatic aldehydes and ammonium
iodide is described. The C–H bond ortho to the amino group in
anilines was directly functionalized under metal-free conditions.
Two aldehydes were involved in this reaction and ammonium
iodide was used as one of the nitrogen sources. This reaction
provides a strategy for the facile construction of substituted quin-
azolines from simple anilines and other readily available reactants.
As an important class of fused six-membered heterocycles,
quinazolines are widespread in natural products and pharma-
ceuticals.1 In particular, multi-substituted quinazolines
display a wide range of biological activities such as anti-
cancer,2 anti-HIV,3 anti-inflammatory,4 antibacterial5 and anti-
tubercular.6 Some of them are known to act as selective inhibi-
tors of the tyrosine kinase activity of the epidermal growth
factor receptor (EGFR).7 Because of the many pharmaceutical
applications as well as the biological values of quinazoline
derivatives, the efficient construction of these compounds has
attracted considerable interest. Among the various reported
procedures, substituted quinazoline synthesis from ortho-func-
tionalized anilines and derivatives is undoubtedly the most
popular method. Various ortho-functionalized anilines such as
2-carbonyl anilines,8 2-aminobenzylamines9 and 2-amino-
benzonitriles10 were successfully used as the starting materials
to provide the corresponding benzo-heterocyclic products via a
condensation procedure with aldehydes, benzyl amines,
benzylic acids or benzonitriles (Scheme 1a and b). Besides
ortho-functionalized anilines, we and others found that more
stable o-nitroacetophenones also could be used as raw
Scheme 1 Synthesis of substituted quinazolines from aniline
derivatives.
materials for the synthesis of substituted quinazolines via a
hydrogen-transfer strategy.11 Alternatively, N-arylamides were
used as the starting materials for quinazoline synthesis via
an intramolecular cyclization process, in which preactivation
at the ortho-position of the aniline ring is unnecessary
(Scheme 1c).12 In recent years, other activated nitrogen-
containing reagents such 2-ethynylanilines,13 aryl diazonium
salts,14 2-alkylaminobenzonitriles,15 N-sulfinylimines,16 imines17
and amidines18 were proved to be alternative substrates for the
synthesis of various substituted quinazoline derivatives.
There is no doubt that the aforementioned methods can be
effectively used to prepare a wide variety of quinazoline deriva-
tives. However, most of them need to use highly functionalized
aniline derivatives or other activated intermediates, which
often require multi-steps for their preparation, thus increasing
the difficulty of synthesis and limiting the substrate scope.
Although in some cases the use of metal-catalysts can improve
the reaction efficiency,19 metal contamination remains an
issue, especially when the products are destined for human
consumption or when trace metal contamination can affect
the product performance, such as in organic electronics.
Anilines can be easily prepared by nitroarene reduction and
are widely used as key synthons in drug synthesis as well as
other nitrogen-containing functional molecular synthesis.20
Therefore, it is highly desirable to use cheap and readily
available anilines as the raw materials for the preparation of
aKey Laboratory for Green Organic Synthesis and Application of Hunan Province,
Key Laboratory of Environmentally Friendly Chemistry and Application of Ministry of
Education, College of Chemistry, Xiangtan University, Xiangtan 411105, China.
E-mail: gjdeng@xtu.edu.cn, fhxiao@xtu.edu.cn
bBeijing National Laboratory for Molecular Sciences, Chinese Academy of Sciences
(CAS), Beijing 100190, P.R. China
†Electronic supplementary information (ESI) available. See DOI: 10.1039/
c8gc02654h
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nitrogen-containing heterocycles via direct functionalization of improved to 23% when NH4OAc was used as the nitrogen
the C–H bond ortho to the amino group. Although some func- source in the presence of I2 (entry 4). It shows that iodine can
tional groups could be directly introduced into the ortho posi- promote this transformation. Solvent plays an important role
tion of the free amino group,21 protection and de-protection in this kind of transformation and the use chlorobenzene as
procedures are usually required in most cases. It is challenging the solvent could further improve the reaction yield to 67%
to use anilines as the starting materials for substituted quin- (entry 8). Other organic solvents such as o-dichlorobenzene
azoline synthesis in one pot without tedious preactivation, and NMP were less efficient (entries 9 and 10). When an equal
purification or protection–deprotection process, which can amount of ammonium iodide was used, the reaction yield
provide the target products in a more direct and convenient decreased to 53% (entry 11). To our delight, a high reaction
way. As part of our continuing efforts on heterocycle formation yield could be achieved when an equal amount of DMSO was
using readily available starting materials under metal-free con- added to the reaction mixture (entry 12). Encouraged by this
ditions,22 herein we describe a general four-component reac- result, various oxidants such as K2S2O8, H2O2, TBHP and
tion for multi-substituted quinazoline synthesis from anilines, DTBP were investigated (entries 13–16) and DMSO showed the
aromatic aldehydes and an ammonium salt under very simple best activity. When two equiv. of DMSO were used, the yield
reaction conditions. In this strategy, two equiv. of aromatic was not improved obviously (entry 17). Decreasing the reaction
aldehydes were involved in the cyclization process and temperature decreased the reaction yield (entry 18). The reac-
ammonium iodide was used as one of the nitrogen sources tion was less efficient when the reaction was carried out under
(Scheme 1d). The four components could be selectively an air atmosphere (entry 19).
assembled into the target products in one-pot without the use
of any expensive reagents or metal-catalysts.
With the optimized reaction conditions in hand, the scope
and generality of the four-component reaction was explored by
To find the optimized reaction conditions, we initiated our using various aromatic amines (Table 2). Good to high yields
investigation using aniline (1a) and benzaldehyde (2a) as the were obtained when electron-donating substituents were
model substrates (Table 1). Firstly, several ammonium salts present at the para position in anilines (3ba–3fa). When 4-tert-
were screened in toluene to find the suitable nitrogen source butylaniline was used as the coupling partner, the desired
(entries 1–7). Among them, ammonium iodide showed the product 3ea was obtained in 95% yield. Halogen functional
best efficiency to provide the desired product 3aa in 50% yield,
whereas the use of ammonium bromide as the nitrogen source
only provided the product in trace amounts. The yield could be
Table 2 Scope of aromatic amines (1)a
Table 1 Optimization of the reaction conditionsa
Entry
“N”
Oxidant
Solvent
Yieldb (%)
1
2
3
4
5
6
7
8
NH4I
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
PhCl
50
NH4Br
NH4CI
NH4OAc
NH3·H2O
NH4HCO3
(NH4)2CO3
NH4I
Trace
Trace
7 (23)c
5
6
Trace
67
9
NH4I
NH4I
NH4I
NH4I
NH4I
NH4I
NH4I
NH4I
o-DCB
NMP
PhCl
PhCl
PhCl
PhCl
PhCl
PhCl
PhCl
45
20
53
97
26
72
44
46
10
11d
12
13
14
15
16
17e
18f
19g
DMSO
K2S2O8
H2O2
TBHP
DTBP
DMSO
DMSO
DMSO
NH4I
NH4I
NH4I
95
86
70
PhCl
PhCl
a Conditions: 1a (0.2 mmol), 2a (0.6 mmol), “N” (0.24 mmol), oxidant
(0.2 mmol), solvent (0.5 mL), 150 °C, 12 h, under oxygen unless other- a Conditions: 1 (0.2 mmol), 2a (0.6 mmol), NH4I (0.24 mmol), DMSO
wise noted. b GC yield. c I2 (0.2 mmol) was added. d NH4I (0.2 mmol). (0.2 mmol), PhCl (0.5 mL), 150 °C, 12 h, under oxygen unless other-
e DMSO (0.4 mmol). f 140 °C. g Under air.
wise noted, and the isolated yield is based on 1.
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groups such as chloro and bromo were well tolerated to give ponding substituted quinazoline products in good to high
the corresponding products 3ha and 3ia in good yields, yields. High yields were obtained with benzaldehydes with the
respectively. To our delight, a free hydroxy group also could be fluoro, chloro and bromo substituents at the para or meta posi-
used to give the desired product 3ja in moderate yield. No tions (3ae–3af and 3ai–3ak). A steric effect was observed when
obvious steric effect was observed and good yields were the substituents were located at the ortho position, in which
obtained even when the methyl group was located at the ortho the desired products were obtained in lower yields (3al–3ao).
position (3ka and 3ma). High yields were obtained when ani- Various benzaldehydes with two substituents were investigated
lines with two methyl substituents were used as the substrate in this system and most of them regioselectively afforded the
(3oa–3qa). Analogously, the desired products 3ra and 3sa were corresponding products in good to high yields (3ap–3au).
obtained in 70% and 78% yields when naphthalen-1-amine Substituted quinazoline 3ar was obtained in 89% yield when
and naphthalen-2-amine were used as the substrates. When 2,4-dichlorobenzaldehyde was employed. Remarkably, 3av was
naphthalen-2-amine was used, the C–H functionalization obtained in 71% yield when the steric substrate 2-naphthalde-
selectively occurred at the α position. Heteroaromatic amines hyde was used. Unfortunately, when two different aldehydes
such as quinolin-5-amine could smoothly couple with benz- are used, four products are detected. The result shows that the
aldehyde and ammonium iodide to give the corresponding reaction displays no chemical selectivity.
product 3ta in 40% yield. Notably, the free amino group was
To our surprise, stable and readily available nitroarenes
well tolerated in the present system, delivering the corre- also could be directly used for this kind of reaction when
sponding products 3ua and 3va in 61% and 43% yields, 2 equiv. of iron were used as the reductant (Scheme 2).
respectively.
Nitroarenes with methyl, tert-butyl and 2,4-dimethyl substi-
To further investigate the scope and limitation of this four- tuents were able to smoothly react with benzaldehyde to give
component system, various aromatic aldehydes were examined the corresponding products 3ba, 3ea and 3pa in 66%, 75%
under the optimized reaction conditions (Table 3). In general, and 73% yields, respectively. Interestingly, 2,4-diphenylquin-
the reactions with benzaldehydes bearing electron-donating azolin-6-amine (3ua) with a free amino group was achieved in
groups such as methyl and tert-butyl and withdrawing groups 43% yield when 4-nitroaniline was used. Furthermore, mono-
such as chloro and bromo worked smoothly to give the corres- substituted 2-phenylquinazoline (6) was obtained in moderate
yield when 2-aminobenzaldehyde (5) was used as the substrate
under the current system.
Based on the aforementioned results and some related
research, a plausible mechanistic pathway is depicted in
Table 3 Scope of aromatic aldehydes (2)a
Scheme 3. The condensation of aniline with benzaldehyde
generates an imine intermediate A, which can be detected
during the reaction. Meanwhile, the condensation reaction of
benzaldehyde and ammonium iodide affords an imine inter-
mediate B.8a,e,l,23 The cyclization reaction of A and B yields an
intermediate D according to a two-step domino reaction.24
Oxidative dehydrogenation of the intermediate D affords the
final product 2,4-diphenylquinazoline 3aa.
In summary, we have developed a four-component strategy
for substituted quinazoline synthesis from readily available
anilines, aromatic aldehydes and ammonium iodide under
simple reaction conditions. The ortho C–H bond in anilines
a Conditions: 1a (0.2 mmol), 2 (0.6 mmol), NH4I (0.24 mmol), DMSO
(0.2 mmol), PhCl (0.5 mL), 150 °C, 12 h, under oxygen unless other-
wise noted, and the isolated yield is based on 1a.
Scheme 2 Synthesis of quinazolines from nitroarenes (4) or 2-amino-
benzaldehyde (5).
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Scheme 3 Possible reaction pathway.
was directly functionalized and used for a further cyclization
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Conflicts of interest
There are no conflicts to declare.
Acknowledgements
This work was supported by the National Natural Science
Foundation of China (21871226, 21572194), the Collaborative
Innovation Center of New Chemical Technologies for
Environmental Benignity and Efficient Resource Utilization,
the Hunan Provincial Innovative Foundation for Postgraduate
(CX2018B046), and the China Postdoctoral Science Foundation
(2018M632976).
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