Selenium-Catalyzed Carbonylative Synthesis of 3,4-Dihydroquinazolin-2(1 H)-one Derivatives with TFBen as the CO Source

Article abstract of DOI:10.1021/acscombsci.9b00090

An efficient and general carbonylative procedure for the synthesis of 3,4-dihydroquinazolin-2(1H)-one from 1-(halomethyl)-2-nitrobenzenes and aryl/alkyl amines have been explored. In this approach, to avoid of using toxic CO gas, a solid and stable CO precursor, TFBen (benzene-1,3,5-triyl triformate), was utilized. With elemental selenium as the catalyst, a variety of aryl/alkyl amines has been tolerated well to afford the corresponding 3,4-dihydroquinazolin-2(1H)-one products in moderate to excellent yields under mild reaction condition.

Full text of DOI:10.1021/acscombsci.9b00090

Letter
pubs.acs.org/acscombsci
Cite This: ACS Comb. Sci. XXXX, XXX, XXX−XXX
Selenium-Catalyzed Carbonylative Synthesis of 3,4-
Dihydroquinazolin-2(1H)‑one Derivatives with TFBen as the CO
Source
Rong Zhou,† Xinxin Qi,*,† and Xiao-Feng Wu*,†,‡
†Department of Chemistry, Zhejiang Sci-Tech University, Hangzhou, Zhejiang 310018, People’s Republic of China
‡Leibniz-Institut fu
̈
r Katalyse e.V. an der, Institution Universitat Rostock, Albert-Einstein-Straße 29a, Rostock 18059, Germany
̈
S
* Supporting Information
ABSTRACT: An efficient and general carbonylative procedure for
the synthesis of 3,4-dihydroquinazolin-2(1H)-one from 1-(hal-
omethyl)-2-nitrobenzenes and aryl/alkyl amines have been ex-
plored. In this approach, to avoid of using toxic CO gas, a solid and
stable CO precursor, TFBen (benzene-1,3,5-triyl triformate), was
utilized. With elemental selenium as the catalyst, a variety of aryl/
alkyl amines has been tolerated well to afford the corresponding 3,4-dihydroquinazolin-2(1H)-one products in moderate to
excellent yields under mild reaction condition.
KEYWORDS: carbonylative procedure, benzene-1,3,5-triyl triformate, elemental selenium, heterocycle synthesis
a
Table 1. Screening of Reaction Conditions
uinazolinones are a type of valuable structural scaffold
1
Q in natural, pharmaceutical, and agrochemical products.
As a class of useful heterocycles, quinazolinones represent a
wide range of biological activities, including anticancer,
anticonvulsant, anti-inflammatory, antihypertensive, and diu-
retic properties.2 As a consequence, numerous synthetic
methods have been reported for the preparation of
quinazolinones.3,4 Typically, the strategies used in the synthesis
of quinazolinones mainly rely on the condensation of
anthranilic acid and its analogues with imidates or aldehydes.3
Over recent years, transition-metal-catalyzed procedures have
also emerged as effective alternatives.4 Although some of the
methods provide useful approaches for the construction of
quinazolinones, some drawbacks, such as high temperature,
multiple steps, long reaction times, and poor yields, are still
exist. Thus, the development of an efficient and general
strategy for the synthesis of quinazolinones is needed.
b
entry
base
solvent
DMF
time (h)
yield (%)
1
Et3N
24
24
24
24
24
28
28
28
28
28
28
54
2
3
4
5
6
7
8
9
Et3N
Et3N
Et3N
Et3N
Et3N
DBU
DiPEA
NaOH
K2CO3
KOtBu
DMSO
1.4-dioxane
THF
toluene
DMF
DMF
DMF
DMF
DMF
trace
19
40
4
71
trace
trace
87
55
10
11
DMF
6
In recent decades, transition-metal-catalyzed carbonylation
reactions have attracted intensive interest from the synthetic
community for their wide application in the construction of
carbonyl-containing compounds and have drawn attention for
their applications in both academic and industrial fields.5 In
general, CO is used as one of the most important carbon
source in carbonylation reactions. However, gaseous CO is
toxic, flammable, and odorless and usually requires autoclave
equipment. Unfortunately, these properties restrict its
application in laboratory use. Thus, a variety of CO surrogates
were explored in recent years, such as metal carbonyl
complexes,6 paraformaldehyde,7 formic acid,8 formates,9
formamides,10 alcohol,11 CO2,12 and others.13 On the other
hand, transition metals, including palladium, ruthenium,
rhodium, and iridium, have been commonly used in these
carbonylative transformations. Nevertheless, in addition to the
a
Reaction conditions: 1-(chloromethyl)-2-nitrobenzene (1.0 mmol),
aniline (1.5 mmol), Se (10 mol %), base (2.0 mmol), TFBen (1.5
mmol), and solvent (2 mL), 120 °C. GC yield with dodecane as the
b
internal standard.
well-established noble metal systems, non-noble metal or
metal-free conditions could possibly be more preferred in
carbonylation reactions. Herein, we wish to report a selenium-
catalyzed carbonylation reaction for the synthesis of 3,4-
dihydroquinazolin-2(1H)-one derivatives with TFBen as the
CO source.
Received: June 14, 2019
Revised: July 9, 2019
Published: July 18, 2019
© XXXX American Chemical Society
A
DOI: 10.1021/acscombsci.9b00090
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ACS Combinatorial Science
Letter
a
Initially, 1-(chloromethyl)-2-nitrobenzene and aniline were
utilized as the model substrates, with selenium as the catalyst,
Et3N as the base, and TFBen as CO precursor in DMF at 120
°C for 24 h. To our delight, a 54% yield of the desired product
was obtained (Table 1, entry 1). We next studied the effect of
different solvents, including DMSO, 1,4-dioxane, THF, and
toluene (Table 1, entries 2−5), DMF was found to be the
optimal solvent. Because of the incomplete conversion of the
substrates, subsequently, the reaction time was prolonged, and
the yield of the target product increased to 71% (Table 1, entry
6). Moreover, various bases were investigated, such as DBU,
DiPEA, NaOH, K2CO3, and KOtBu (Table 1, entries 7−11), it
is noteworthy an 87% yield of the target product was produced
with DiPEA as the base (Table 1, entry 8).
Table 2. Synthesis of 3,4-Dihydroquinazolin-2(1H)-ones
With the best reaction condition in hand, we next studied
the substrate scope with a variety of amines (Table 2). Aryl
amines with electron-donating group, such as methyl, ethyl,
isopropyl, tert-butyl, and trifluoromethoxy group, all afforded
the corresponding products in moderate to excellent yields
(Table 2, entries 1−9). Notably, those substrates with ortho-
and para-methyl groups resulted in higher yields than meta-
substitution, probably due to the electronic effects. Aryl amines
bearing halogen groups, including fluoro-, bromo-, and chloro-
formed groups also afford the desired products in moderate to
excellent yields (Table 2, entries 10−12). Moreover, the
influence of alkyl amines has also been studied. Substrates
bearing linear groups, such as propyl, butyl moieties, and
heptyl groups worked well to produce the target products in
moderate to good yields (Table 2, entries 13−15). Alkyl amine
with tert-butyl group could also gave the desired product in
good yield (Table 2, entry 16). Substrates containing cyclic
groups including cyclopentyl, cyclohexyl, and 1-adamdantyl
groups were investigated; the corresponding products were
generated in moderate to good yields (Table 2, entries 17−
19). Furthermore, 2-methoxyethan-1-amine could also afford
the desired product in very good yield (Table 2, entry 20). We
also tested 1-(bromomethyl)-2-nitrobenzenes with different
aryl/alkyl amines; the reactions were tolerated well to afford
the desired products in moderate to good yields (Table 2,
entries 21−25).
On the basis of the above results, a proposed reaction
mechanism is shown in Scheme 1. CO was initially generated
from TFBen promoted by a base, and then reacted with
selenium to afford carbonyl selenide (SeCO). At the same
time, 1-(halomethyl)-2-nitrobenzenes 1 reacted with aryl/alkyl
amines 2 to provide nitroanilines intermediate I, followed by a
deoxygenation with SeCO to give nitrene intermediates II.
Subsequently, isocyanate intermediate III was formed via the
reaction of nitrene intermediates II with Se/CO, followed by
an intramolecular nucleophilic addition to afford the final
product 3. The formation of CO2 was also confirmed by
bubbling the gas after the reaction into clear Ca(OH)2
solution.
In conclusion, an efficient and convenient carbonylation
reaction for the synthesis of 3,4-dihydroquinazolin-2(1H)-ones
have been established. Through a selenium-catalyzed carbon-
ylation reaction of 1-(halomethyl)-2-nitrobenzenes with aryl/
alkyl amines using TFBen as the CO source. A variety of 3,4-
dihydroquinazolin-2(1H)-one derivatives were generated in
moderate to high yields under mild reaction conditions with
good substrates toleration.
B
DOI: 10.1021/acscombsci.9b00090
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Letter
Table 2. continued
ASSOCIATED CONTENT
* Supporting Information
■
S
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acscombs-
ci.9b00090.
General comments, general procedure, analytic data, and
NMR spectra (PDF)
AUTHOR INFORMATION
Corresponding Authors
*E-mail: xinxinqi@zstu.edu.cn.
*E-mail: xiao-feng.wu@catalysis.de.
■
ORCID
Xiao-Feng Wu: 0000-0001-6622-3328
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
The authors thank the financial supports from NSFC
(21772177, 21602201).
■
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Scheme 1. Plausible Reaction Mechanism
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EXPERIMENTAL PROCEDURES
■
Selenium (10 mol %), TFBen (0.75 mmol; 2.25 mmol of CO),
and 1-(halomethyl)-2-nitrobenzenes (0.5 mmol) were added
to a 15 mL tube equipped with a magnetic stirrer, which was
then placed under vacuum and refilled with nitrogen three
times. Aryl/alkyl amines (0.75 mmol), DMF (2 mL) and
DiPEA (1.0 mmol) were added to the reaction tube; then, the
tube was sealed, and the mixture was stirred at 120 °C for 28 h.
After the reaction was completed, the mixture was filtered,
extracted with ethyl acetate and concentrated under vacuum.
The crude product was purified by column chromatography
(ethyl acetate/petroleum ether = 1/2) to afford the desired
product.
Caution: Because of the generation of CO gas from TFBen,
special attention should be paid and proper protection should be
given during the manipulation and workup process.
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DOI: 10.1021/acscombsci.9b00090
ACS Comb. Sci. XXXX, XXX, XXX−XXX